Sei sulla pagina 1di 606

ELECTRIC

SMELTING

AND

REFINING.

GRIFFIN'S

TEXT-BOOKS.

SCIENTIFIC

IllustrationB
Edition, Thoronghly Revised and Enlarged. With Komerous
and Three Folding Plates. Price 21b.
of the
A Practical Manual
AND
REFINING.
ELECTRIC
SMELTING
Extraction and Treatment
of Metals by Electrical Methods.
Being the "ElektroSboond

Translated from the Third


Metallurgle" of Dr. W. BORCHERS.
G. M'Millan, F.I.C, F.C.S.
with Additions, by Walter
and
ComprehenglTe

"

authoritative

Full

Edition,

information.""

valuable

of

German

TA"

EUctrieian.

TREATISE

With Additional
Price lOs. 6d.

and in part Re-written.


Electrolysis, Costs, Ac.

Sboond
Edition, Revised, Enlarged,
Sections
MODERN
op
on
Theories

ELECTRO-METALLURGY.

ON

G.

Walter

By

F.I.C. F.C.S.,Secretaryto the Institution of Electrical Engineers ; late


tions.
IllustraWith
Numerous
Lecturer in Metallurgy at Mason
College,Birmingham.
Large Crown 8vo. Cloth.

McMillan,

"This
hitherto

excellent

treatise,

the

of

one

and

best

manuals

complete

most

publishedon Electro-Metallurgy."" Jff^tWeaZ Review.


Handsome

Large 8vo.

METALLURGICAL

Cloth.

With

ASSAYING.

AND

ANALYSIS

Price 128. 6d. net.

Illustrations.

Years'

Three

A. Macleod, B.A., B.Sc.,A.O.S.M.


School of Mines
Formerly Assist -Director, Thames
(N.Z.),and Lecturer in
(N.Z.),
School of
Chemistry, University of Tasmania
; Director of Queensland Goveniment

Course

for Students

of Schools

Mines, Charters Towers:


in

Chas.

F.C.S., Formerly

Walker,

; Lecturer

in

tends

volume

that the

to prove

analysis and assaying in Australia tests in competent hands.""


With

15

Folding Plates

GOLD

CIYANIDING

Assist -Demonstrator

Chemistry and

Metallurgy,

School of Mines.

publicationof this

The

and

Chemistry, Sydney University

Charters Towers
"

By W.

of Mines.

and

AND

100

teaching of metallurgical
^Vaturtf.

Illustrations in the

Text.

21s

net

Practical Treatise on
Working, Design and Construction

SILVER

ORES.

Cyanide Process ; its Application,Methods of


Julian, Mining and Metallurgical Engineer;
Plant,and Costs. By H. Forbes
and Edgar
Smart, A.M.I.C.E.,Civil and Metallurgical Engineer.
A complete story of cyanidingfrom its earliest beginningsto its latest developments.
in hand.
Practice and theory have
been made
to go hand
The authors speak with
the
of

"

authority."" Cfcemtoai Seics.


"
This very complete work
brings together in
should

be invaluable

English

Third

THE

to the

single volume

of data

mass

Edition, Thoroughly Revised and greatly Enlarged.

CYANIDE

which

Engineer.""Pa^e'"Magazine.

PROCESS

OF

EXTRACTION.

GOLD

Price

7s. 6d.

Text-Book

for

the Use of Metallurgistsand Students at Schools of Mines, "c.


With
Plates
and Illustrations. By James
Park, F.G.S., M.Inst.M.M., Professor of Mining and
Director of the Otago University School of Mines ; late Director Thames
School of
of New
Mines, and Geological Surveyor and Mining Geologist to the Government
Zealand.
,

"

to be ranked
Journal.

Deserves

"Mining

Extra Crown

LECTURES

With

8vo.

ON

amongst the

as

op

Folding Plate

existing

and

treatises

62 Illustrations.

on

Third

of

this

Tubneb,
By Thomas
Metallurgy In the University of Birmingham.

Edition, Revised.

Volume

I.

subject."

3s. 6d. net.

IRON-FOUNDING.

A.R.S.M., F.I.C, Professor

THE

best

7s. 6d. net.

M.Sc.

OF' GAS
A
MANUFACTURE.
Hand-Book
on
and Testing of Illuminating Gas, and the Assay of the
Purification,
Bye-Products of Gas Manufacture.
By W. J. Atkinson
Butterfield, M.A., F.I.C,
F.C.S.,formerly Hdad Chemist, Gas Works, Beckton, London, B.
CHEMISTRY

the Production,

Volume
*"

The
Journal

BEST

WORK

II. y

completing the Work, Ready

of its kind

which

we

have

ever

had

Immediately,
the

pleasure of reviewing.""

of Gas Lighting.

LONDON:

CHARLES

GRIFFIN

"

CO., LTD.,

ExItER

STREET,

STRAND.

SMELTING

ELECTRIC

EEFINING:

AND

EXTRACTION

THE

BY

Translatkd

AND

MEANS

OF

Dr.

W^.

from

OF

**

SECOND

G.

AUTHOR

miltb

THE

MCMILLAN,
TREATISE

ON

flumeroue

CURRENT.

Edition,

German

ENGLISH

|Mate0 and

ELECT

METALS

OF

ELECTRIC

Third

the

WALTER

TREATMENT

S.

Additions,

with

by

F.I.C., F.C.S.,
RO-XKTALLURGY."

EDITION.

Jlluatrationa in tbe ViciX.

uiv

"

"

Or

LONDON:
OHARLES

GRIFFIN
EXETER

AND

STREET,
^

COMPANY,
STRAND.

1904.

[All Rights Reserved.'^

LIMITED

\-\'j

\^

"^
-

PREFACE

In

TO

this revised

"translated

1897

the

has

the

advance

of

task

supplying

of

because

metallurgy,

of

imposed

Being

competition.
the

Author

have

feels

with

plant

extensive

metallurgical
information
at

of

Aachen,

is

works.

on

obtained

been

where, by the
he

in

has

in

of

for

his

branch

this

secretiveness

commercial

industrial

their
in

scale,

the

disposal

and

electro-

useful

laboratory

Prussian

Minister

horse-power

90

in

cases

many

Author's

the

work,

experience

investigating

liberalityof

at

of

Metallurgists who

large

year

account

of

Moreover,

required

not

the

the

to

results

the

processes

has

Education,

indebted

by

keenness

longer engaged

no

electro-metallurgical

general

of

the

necessitated

Every

made

because

by

greatly

him

favoured

has

since

increasingly difficult,

becomes

partly

manufacturers

on

German

Third

volume.

the

great advances

and

the

comprehensive

the

of

manual,

and

attention

Electro-MetallurgicalPractice
partly

well-known

Electro-Technology

in

large portion

of

proofs

full

EDITION.

Borehers'

made

progress

received

re-writing

SECOND

of Dr.

Edition

from

Edition,

THE

for

research.
electro-metallurgical
Since

the

authoritative

publication

the

dealing

works

Electro-Chemistry

of

been

have

previous edition,
with

newer

published;

the

has, consequently, omitted

the

and

introductory

numerous

theories
the

sketch

of

Author

of

this

subject previously given.


"'
"

-^

()

Digitized by

VjOOQIC

PREFACE

Yl

While

this volume

untimely death
the

TO

SECOND

THE

passingthrough

was

deprivedit
Engineers,
MMillan

Publishers

The

by

that the

of the
his

G. McMillan,

his final revision.

exceptionalknowledge

as

here and
a

there

valuable

treuislation will be

scrupulouscare

and

of

skill.
conspicuousliterary
the

confident,therefore,that

him

by Englishreaders
and

advantage of

combined

feel

inserted

notes

of the

press, the

the Institution of Electrical

metallurgywith

and
electricity

the

Translator,Mr. Walter

of the

accomplishedSecretaryof
Mr.

EDITION.

will be

addition

found

accuracy

to

appreciated
the

to

be

original

an

work,

example

that characterised

all

work.
professional

The

Publishers

Mr.

Bennett

for

press.

London,

H.

also desire

Brough

Jxdy^ 1904.

for

to

express

their thanks

kindlyreadingthe

to

final sheets

PEEFACE

In

manual

subject

which

position

now

of

way

The

well

so

chemical

his

from

scale

and
at

He,

world.

in the
short

had

elaborate

Chemistry

u/td

Nemst's

their

before

the

and

results

processes

given

of the

is

the

works

Chemistry
Traoslated

from

by

G.

the

of

the

found
viously,
pre-

business
the

to

extended

the

is taken.
electro-chemical

newer

Ostwald
to

that

Standpoint

S. Palmer.

and

fuller

for

and

the

giving

version

of

During

and

from

on

worthy
trust-

which

greatly

referred

Author

considerations

this

tests

enormous

information

which

to

the

made
the

in

service

appearance

time

much

Electro-Chemistry,

Theoretical

Thermodynamics,

that

in

of

form

to

had

prevented

student

explanations

the

and

is

be

to

practical value.

of

been

that

states

them

him

re-wrote

from

has

metallurgical

technology

been

only

sketch

and

hoped

enable

to

personal

to

Edition

conducting experimental

end

the

edition

had

electro

in

therefore,

theories, and

with

liberty to publish

obligations, he

by

years' practical work

by laying before

electro

at

owing

he

elapsed

which

progress;

work

edition

to

as

Edition,

Second

little

present volume

twelve

sufficientlylarge

years

himself

the

his

to

gained

opinion
four

which

first

had

he

prominent

but

"

on

"

Qerman

Second

the

metallurgical industries,

the

the

to

-Metallurgy

preface to

experience

which

attained

Borcbers

is needed.

fellow-labourers

the

Dr.

of

of

version

English

an

that

Electro

by

refers

and

preparinor

rapidly

in his

1896,

translated),

of

so

introduction

(that of

to

as

held

EDITION.

readers

known

has

Author,

FIRST

English

before

bringing

THE

TO

on

of

more

General

Nemst

of Avogadro'a

Rule

PREFACE.

Vlll

Theoretical

on

scientific

technical

or

Hand-

Ostwald's

research

und

Measungen*

chemischen

Versuchen,

the

and

engaged

are

recommended

are

EtUfsbuch zur

cheniischen

In

who

Those

Chemistry.

Getters

present volume, all those

in

consult

to

Auafvhrung physVcoAnleitungzu Elektrometals

in the

tion
extrac-

electric current
has
the
working of which
found
applicationare treated of; but electrolytic
any
have
and electro-typing
not been
analysis,
electro-plating,
and

touched

From

upon.

the

of

mass

material

accumulated

literature,only those papers


patent-oflSce
which
or
are
capable of practicalapplication
processes
reference.
A
short
selected for
have, usually,been
of treating
of the purely metallurgical
methods
survey
that the
the metals has been
added
to each chapter,
so
with
such methods
reader may
be in a position
to compare
the two
to see
how
electro-metallurgical
processes, and
in

journaland

be used

may

in

conjunction.
months

that

German

Edition, progress

During the
publicationof

few

made

directions.

in

the

many

ventured

add

to

bringing the

notes

and

the

passed since

Translator

The

here

have

there

has

been

has, therefore,
the

in

hope

of

He
has
nearly up to date.
of the practical
also added
accounts
working of certain
which
have
been
developed since the German
processes
work
was
placed before the public. Extra references to
English patents and the British equivalentsof the
metrical

or

in

so

that

more

All

these

the

reader

may

have

also been

added

quotationsfrom
*

O"twald's

by J. Walker.

Manual

the

into the
in

within

Tables

French

have

of Physico Chemical
"

in

the

also
text

brackets, [ ],
the

original

for the conversion

correspondingBritish

appendix.

an

have

text

square
between
distinguish

supplementarymatter.

of certain Continental

the

additions, whether

enclosed

footnotes,are
the

in

quoted

measurements

given.

been

and

work

Whenever

been

possible,

translated

Meaaurementa.

units

direct

Translated

PREFACE.

from

text, instead of from

the French
those from

and

from

IX

have

Englishsources
original.

the

the German
been

arranging the additional matter,


kept in view the industrial aspect of
In

has

introduced

one

to
referring

actual

referred to

in the

each

of the

under

been

stated

or

short

two

of
applications
It

text.

various

the

version,

batim
reprintedver-

Translator

the

has

question,and

supplementary notes

processes

not

otherwise

believed,,
therefore,that

is

metals,separately,
enough has

give a good generalidea of the present


industrial position
of that branch of the subject.
of Electro-Metallurgy
The
are
practicalapplications
especiallyon the
advancing with phenomenal rapidity,
Continent
if

to

and

America, and

in

England is to

hold her

there

is little doubt

that,

in

she also must


Metallurgy,
and more
attention to the electro-metallurgical
give more
are
smeltingand refining
cheapeningand
processes, which
simplifyingthe work of producing high-class
products
own

abroad.
In conclusion,the translator's thanks
". Hunt

and

the

and
Electrician^

Institution of Civil

to

the blocks
50b

Industries

employed
respectively.

in

and

Mason

department,
College,

BisMiNGUAM,

Jtuie 8f 1897,

due

to

Mr. A.

Engineers,to

Iron, for

Figures82a, 101a,
WALTER

meta.lluroi0al

are

and

the

use

50a

G. MCMILLAN.

the
of
and

CONTENTS.

PABT

I."

ALKALIS

AND

METALS.

ALKALINS-

EARTH

PABT

II."

THE

EABTH
I." Aluminium.

Chapter
Occurrence

in Nature,

Properties,
PrecipitationProcesses

....

The
The

by

The

Gerard

95

The

Willson

96

of
Electrolysis

98

Theory,
of Alumina

103
of

Reducing Aluminium,
of Aqueous Solu
Electrolysis

104

125

Furnace,
Fused

Compounds,
Process,

minium

125

Alu
126

The

H^roult

The

Hall

The

Minet-Bernard

The

Neuhausen-Froges Pro

cess,

tion

127

Process,

131

Process,

141
145

....

Borchers'
104

tions.

125

nace,
Fur-

Lescuyer

Methods
Electrolytic

The

TheGrabau

93

101

Reduction
Carbon.

Electric Furnace,

93

of Extraction,

Reduction
Processes,
Cowles Process,

Thermic

METALS.

Extrac

Aluminium

145

Apparatus.

Early Experiments,

108

Bradley'sJProcess,

148

Deville's

109

Kiliani

151

Process,

trolysis
Practical Obstacles to the Elecof the
The

Chlorides,

112

Teachingof Deville's and

Bunsen's

112

ImpracticableProcesses,

113

Reduction

Decomposition

Processes,1 19

of Aluminium

Compounds by the

.123
.

153

Aluminium

Sulphides,
Preliminary Treatment
Bauxite

and

154
of

Cryolite,

Conditions to be Observed
Extraction

Aluminium

Uses,
Price,

of

....

155
of

157

in the

Aluminium,
Works,
.

....

153

Process,

Electrolysis
Aluminium,

Electric

119
Johnson's Process,
The Siemens Electric furnace, 120
The
Kleiner- Fiertz Electric

Furnace,

J. B. Hall

Industrial
119

Arc,

The

of
Electrolysis

Experiments,

Successful

Furnace,
Grabau's
Process,

160
161
162
165

CONTENTS.

Chapter

theCerite Metals,
Properties of Cerium,
ElectrolyticDepositionof the
Cerite Metals,
Stockem's
Experimentsin the
of Cerium,
'Reduction
.

PART

III."

Nature,
.

HEAVY

187,

187

187

Patera's Process,
The
Elkincton
Patents,

188

188

Copper
Theory of Electrolytic
....

Wohlwill's
Behaviour

of Chlorine

Crystalline
Cathodes,
Forster
Von

Growths

Effect of
Tem])erature of
Bath on Copper,
in Copper
of Alconol
Use

Solutions,

208

-Treatment

209

Co

dustry,
Copper-refiningIn-

General arrangement of Plant, 211


211
Parallel System,
Arrangement of Electrodes in
211
Baths

....

244
in Electrolytic

Copper Refining,
.

Treatment

of

Ores,

245

Sulphidesand
246

....

The Marchese
247
Process,
The Stolbers Installation, 254
Use of Depolarisers,
257
.

The

221

Copper

Conditions

214

of
the
Details
Siemens224
Borchers* Installation,
Reduction
in Cost,
225
Schneider
and
Szontagh
227
System,

243

Refining

....

Body's Process,

218

of Baltimore

Works

213
218

242

Slimes,

at Raritan

Works,
Industrial

210

241

244

Treatment

of the Electrolytic

Castingof Anode-plates,
Anode-castingMachines,
Cathode-plates,
DepositingVats,
Borchers' Improvements,

Chicago

of Anode
at

238

241
the

Electric

210

....

Works,

Process,

Treatment

23a

241

....

at

236

Amboy

Copper Refinery,
207

Perth

at Raritan

Practice

234
235

240

....

Works,

233

lytes,
Electro-

Impure

at

22a

239

....

of

Treatment

Process

Experi-

Experiments,

Development

Smith

....

Hubl's

203
205

SeideVs

and

Process

on

....

ment",

The

199

in the

Electrolyte,

182

Process
Thofehm
New
Thofehm*8
Process,
Raritan Copper Works
Plant,
of Electrodes,
Connections
1Series System,
The
Stalmann
System,
The
Hayden, Smith, and
Randolf Processes,
The Multipleand the Series

193

Experiments,

182

METALS.

Systems,
192

Remiing,
Kiliani's Experiments,

181

I." Copper.

Methods,
Electrolytic
Electrolytic
Refining,
Earlyattempts in the ElectroDeposition of Copper,

18a

185
186

*
.

171

I Reduction
Process,
167 IReduction
of Cerium
Alloys,
Extraction of Cerium,
,
Uses of the Cerite Metals,
170

184

"; Woiss's

Hofer,
Experiments,

'

167

THE

Metallurgy,

Properties,

IMuthmann,

166

Chapter
in

Praseodidymium,

IL-^Cerium, Lanthanum,
Neodidymium.

Occurrenoeof

Occurrence
Sketch of

XllI

259

Halske
RefiningProcess.
Siemens
Modified
Siemens-

Matte-

260
-

Halske

Process,
Hoepfner Process,
The Schwarzenberg Experiments,
....

The

....

The

Process,
Applicationsof Copper,
Coehn

263
266

270
271
272

CONTENTS.

IL"

Chapter

Nickel

PAGE

Occurrence,
Propertiesof Nickel,
....

Extraction,
Andre's
Process,
....

Classen's Experiments,
Farmer's Process,
The Basse-Selve Process,
.

The

Strap Processes,

The

RickeU

The
The

and

Cobalt,

274

The
The

275
275
277
277
279

Heibling Process,

The

Le

in

Extraction

Process,

Chemical
The
The

Solution,

Review

280

Treatment

ZiervogelProcess,
Augustin, Patera, and

Kiss

Processes,

Dietzel's Process,
4Solution of the
Constituents
.

other

Silver,

than

284

Solution in other
with

Treatment

301

Plant,

Motz's

Jory's

paratus,
Ap323

....

Perth

Moebius

303

303

Ambov
and

paratus,
House-

Balbach's

324
Installation,
Nebel's
Ap326

....

Symon Process,
Apparatus,
.

Processes,
Leachingand Precipitation

338

Chlorination,
Cassel Process,

331
331
.

331

333
...

.334

Body's

.336
.336

,.

and Clerici's Process,

Process,

336

.336
.

.338

338
339

,,

339

"

CyanideProcess,
i

Theory,

Practical

Development,

Siemens- Halske

Comparison
and

340
340

of

Chemical

"
"

338

Stolp's

332
332

327
327

IV.-Gold.

330

Haycraft Pro-

Process,

"

322

....

of Moebius

form

303

333

Rae's
Pelatan

Later

303

cess,

Hannay's
Bailey^s

.291

329

Metals,
Lead,

Barker's

329

and

290

of Fine Silver,
Production
311
WohlwilPs
.311
Process,
Moebius
Process,
.317
The PennsylvaniaLead Co.'s

309

Principlesof Amalgamation,
Electro- Amalgamation,
Molloy's Process,
Breakell

III." Silver.

....

Treatment,

Mechanical

287

The

in Nature,

Properties,

285
286

284

Chapter
Occurrence

Process for Separation


of Iron and Nickel,
293
Utilisation of Anode
Reactions, 294
296
Summary of Processes,

The
.

Concentrated

of

Mattes,

282

of

288

Alloys
of Processes,

280

of Silver

Processes

Separation by

for

Experiments,
Separation of Nickel -Copper

300

metal,

284

Furster's

300

....

by solution

in anotlier

ExperimcnU,

284

SeparatingCobalt,

.282
.

Nature,

Properties,

Frasch Process,
Vortmann
Process

Ulke's

280

Chapter
Occurrence

Kugel Process,

Borchers'

The

Verrier

The

Nickel

Pure

of

Process,
Hoepfner Process,
Muiizing Process,

Deposition

PAGE

273

341

Plant,

351

Electrolytic
Precipitation

Processes,.

354

Refining
Wohlwill's

Uses,

358

Process,

359
382

CONTENTS.

XVI

X."

Chapter

and

Antimony

Vanadium.

PAGE

Antimony,
Properties,
.

Extraction,

The
The

Reduction

Process,
Process,
Precipitation
Processes,
Electrolytic
.

Borchers'

Experiments,

Practical

Workins,

Conditions
Suitaole to
Electrolytic Refining, 484
Sanderson s Process,
486

Chromium,

Nature,

in

Properties,

Process,
Furnace,

Chaplet's
Refining,

,,

Process,
Heibling's
The
Goldschmidt

or

Fused

606

....

495

Methods,
Electrolytic

495

Uses,

606

506

,,

Manganese,

507

5()7
507

....

and Properties,
Reduction,
The Precipitation
Process,
Electrolysis,
Dissolved

498

Fused

with

Nature,

510
511

XXL"

Iron.

511

Hdroult's Process,

.615

511

Harmet's

.515

,,

the

Ma

Raw

Keller's
"

513

terials.

Magnetic Separation,
PrcSuctionof Pig Iron,
Stassano

509

503

....

of

509

509

Process,

Applications,

502

608

Soluble

Anodes,
H^roult's

508

ganese
Man-

Insoluble

601

502

and Properties,

Fused

or

Compounds, with
Anodes,
Compounds,
Manganese

499

507

....

496

Chapter

513

Iron,
Siemens'
De

Pig-iron Pro

The

Laval's

619

....

Furnace,

.619

SmeltingFurnace,

H^roult

517

of Malleable

Production

The

613
514

....

505
506

....

Molj'bdenum

cess,

504

Uranium,
Properties,
PrecipitationProcess,

602

Properties,
Preparation

Ores,
Process,

Reduction

602

in

504

....

of

495

Krupp's Process,

Occurrence

504
504

....

Treatment
Reduction

492

503
.

Occurrence

Uses,

Production,

of Oxide,

Properties,

601

4S9

Tungsten, Uranium,

Tungsten,

495
496

Experiments,

Occurrence

489
490

492

Borchers'
,,
The Placet-Bonnet
Process,
Moller and Street's
,,
Feree's Experiments,
Olaser's
,,

488

Uses,

with

Insoluble Anodes,
Bunsen's

Ore,
Process,

Electrolysis,

488

of

491

mium
Chro-

Compounds,

488
.

Reduction

,,

Dissolved

487

487

and Properties,

Treatment

Reduction

495

Electrolysis,

The

Vanadium
Occurrence

Uses,

494

Process,
Process,
Precipitation

Aschermann's

Process, 487

....

490

493

....

486

Treatment,
Applications,

490
490

....

Reduction

Moissan's

Siemens-Halske

Molybdenum,
Manganese.

....

Occurrence
The

Chromium,

XL"

Chapter

PAGE

Kopp's Process,

474
474
475
475
475
476
476
479

Process,

519
521

LIST

Plate

I.

OF

ILLUSTRATIONS.

refinery, Siemens'

Copper

IL

to

system,

Siemens-Borchers-Brothers'

"

ni.

H6roult

furnace

in

IV.

Keller

"

522

operation,

"

i*

540

fnrnaoe,

"

221
224

system,

,,

",

face p.

......

PAGB

1.

Hansen's

electrolyte cell,
carbon

2.

electrode,

"

3.

Gomp-Besanez

4.

Fischer's

9.

3
5

apparatus,
1884,

apparatus,

6, 6. Graetzel's
7, 8.

3
.

6
8

apparatus,

9
,,

"

Borchers*

crucible

flanged

10.
, ,

11.

for

electrolyticreduction,

furnace

experimental

with

furnace

for

use

furnace

for

the

for the

electrolysisof
of 100

currents

,,

12.

Troost's

14.

Holer's

15.

16.

17.

Watt's

18.

JablochkofiTs

for the

apparatus

for the

apparatus

Grabau's

electrode

apparatus

electrolysis of fused

cell for

Fischer's

apparatus,

Borchers'
Grabau*s

plant,

Kasemeyer's
for the
for

apparatus
modified

32

reduction

reducing

cathode

41

apparatus,
of alkali

alkali

the

metals,

43

metals,

45

cell,

sodium-extraction

47
48

apparatus,

Danckwardt's

60

Diagram
Hood

39,

40.

41.

Fischer's

to

fused

sodium

surround

of

in

form

in

elec
53

electrolysis,

electrolysisapparatus,

sodium-chloride

of cathode,

chlorine

sodium-chloride

63
54

electrolyticapparatus,

"

Special

and

sodium

chloride,

cathode

sodium-chloride
modified

42.

"

illustrating behaviour

trolysis of

43.

sodium,
"

"

38.

25

light metals,

40

apparatus

Borchers'

31. 32.
33-37.

and

Homung

30.

24

plant,

sodium

25.

29.

15

22

36

sodium

modified

Grabau's

chloride,

"

Omholt's

Omholt's

28.

of

"

24.

26. 27.

14
.

compounds,

lithium

13

33

Rogers'

21,22,23.

with

use

e3ctraction

"

19,20.

salts,

of lithium,

extraction

for the

fused

amperes,

electrolysis of magnesium

"

13.

12

55
66

ILLUSTRATIONS.

OP

LIST

pAaB

44.

Arrangement of cathode,

47. Yautin's

49.

apparatus,
Borchers' apparatus for the productionof sodium aUoys,
improved apparatus for the productionof sodium alloys,

modification

Darling'sapparatus
nitrate,

57. Borchers'

65

of same,
the

for

for alkaline -earth

and

calcium-extraction

Stockem's

,,

,,

plant for manufacture


furnace

Cowles'

65.

"

"

85
99

alloys,

100

(cross-section),

100
of alumina

direct reduction

by carbon,

Graetzel's aluminium

70. Cowles*
71. Pichou's

115
117

cooled cell apparatus,

120

furnace,
ore-smelting
smeltingfurnace,

72. Siemens'

electric furnace,

73.

modified

121
121

123

electric furnace,

,,

124

74. 75. The Kleiner-Fiertz furnace,


electric furnace,
76. Oerard-Lescuyer's
77. The

Willson

78. 79. The


in

H^roult

81.

The

82.

Modified

Hall

patent, No. 400,766,


patent, 400,766,

furnace,American

"

"

"

"

"

"

patent, No. 400,664,


400,665,
400,666,

furnace,
(Minet) aluminium
Apparatus used at Neuhausen,
.

Aluminium

92.

Borchers' aluminium

extraction

Borchers' aluminium

94. 95. Bradley'saluminium


96. Kiliani's furnace,
Schindlers

apparatus,

furnace,

smeltingfurnace,

132

133
134

135
137

143
145

146
147
150
151

.....

aluminium

130

138

reduction.

91.

93. Modified

and
128

PittsburgCo. 's Hall furnace,

89. 90. Bernard

97-101.

section
longitudinal

for small installations,

furnace

apparatus. Hall

87.

in

......

Hall furnace, U.S.A.

86.

The

126
furnace

aluminium

aluminium

83. 84, 85. The

125

furnace,

H6roult

plan,

80.

102.

103
HI

reducing aluminium,
vessel,
electrolysing

67. Deville's apparatus for

69. Grabau's

83

section),
(longitudinal

to show

Arrangement

furnace,

furnace,

strontium-extraction
of aluminium

82

furnace,

calcium-extraction

modified

64. The

re-

80

"

63. Cowles'

metal

.......

"

62.

from sodium

of sodium

extraction

experimentalapparatus

58. 59. Borchers


60, 61.

64
.

duction,

88.

62
63

alloys,

plant,

sodium-extraction
electrolytic

53-55. Becker's

68.

61

,,

52. Castner's

66.

60

.....

50. 51. Apparatus for the productionof lead-sodium

56.

58

experimentalwork,

electric furnace for

45, 46. Borchers*

48.

67
.....

furnace,

Section of Borchers' furnace.

152
172

XXI

ILLUSTRATIONS.

OP

LIST

PAGE

no.

103.

Weiss's

Section of Muthmaiin, Hofer, and

104, 105, 106. Furnace


108, 109. Stockem's

172
176
179

for cerite metals,

furnace

107. Borchers'

of cerium

for extraction

furnace,
metals,

productionof cerium

for

furnace

180

alloys,

201

solution of copper anodes,


irregular
Diagram illustrating
111-117. Typicalanodes and cathodes,
for castinganodes,
used by Morrow
118, 119. Mould
machine,
120, 121. Hixon " Dyblie'sanode-casting
110.

122.

217
""

""

""

""

(Siemens),

vat, showing anode


copper-refining

Section of

of copper

131. Siemens-Borchers'

iofact

136a.

141.

Stalmann's

"

143-146.

Moulds

150, 151. Method


152. Section

of

of

of

Plan

with
anode-strip

vats, showing method

248

Casarza,
conductor

at

dJasarza, 249
249

(Casarza,

161.

Arrangement

251
251

depositing-room,
depositing-room,

of anode

252

253

process,

259
.

cell for treatingcopper


electrolytic

" Halske

262
263

),

"

265

265
.

cell,
electrolyte
single-compartment
Farmer's nickel depositing
plant,
the
for
preparationof lead chlorate
Apparatus

271

167. Coehn's

170-173.

278

and

261

process,

(Siemens-Halske),

form of tank (

ore,

cell (1889),
electrolyte

in the Siemens-Halske

of vats

162. 163, 164. Siemens

168. 169.

250

electrolyte

of the Marchese

" Halske

Siemens

the
circulating

of the Casarza

scheme

160.

of

installation,

158, 159. Body's apparatus,

Newer

main

238
,,

250

Interior of the Casarza

form

at

at

....

Cross-section

166.

of matte

250

155.

New

vat,

Hayden's

.......

Plan of the Casarza

165.

237
237

attachingthe lead liningsto the vats (Casarza),


of circulatingthe electrolyte
vats, showing method

154.

157. General

236

of

(Casarza),

156.

231
.

in Stalmann*s

"

224

228

(cross-section),

for castinganodes

(Casarza),
153.

vat

of electrical connections

Scheme

223

apparatus,

installation,

"

147, 148. Connection


149.

of Thofehm's

of electrical connections

Scheme

142.

copper

222

electrode connections,

Stalmann's

221

to/oce

Thofehm

Anaconda

221

Plate XL,

137, 138, 139.


140.

(Siemens),

(cross-section),

electrical connections

The

vats

section),
(longitudinal

"

"

The

in copper

vats

copper

132.

133. 134, 136.

220

of electrical connections

130. Scheme

218
219

(Siemens),showing cathode,
vat (Siemens),

vat

of copper

Longitudinalsection

127. 128, 129. Plate I.,

136.

215

"

"

"

125. Cross-section
126.

213

216

Walker's

1*"*

124.

212

nickel at the cathode,

at

the anode
295

.....

ILLUSTRATIONS.

OP

LIST

XXll

PAGE

no.

174. Dietzers
175. The

Moebius

.....

apparatus, showing

Moebius

178.

apparatus

section

"

"

"

"

,,

,,

,,

Moebius

180. 181. The

Moebius

182.

The

183.

Moebius

184.

Balbach's

186.

and

compartment

showing cathode,
through A R C E (Fig.178),
.

process

modified

NebePs

324

of apparatus,

324

(new form),

connection

anode

321

of elecltrical
connections,

^latestform

"

326

apparatus,
.327

Unk,
electrolysis
,"

i"

"

319
320

The

MoUoy amalgamating pan,


vats,
187" 188. Hannay's electro-amalgamating
Motz's
sluice,
189, 190.
electrolytic
191. Stolp's
gold-extraction
apparatus,
186.

.318

plan.
scheme

179.

in half

.......

section

177.

anode

318

section,
176. The

304

vat,
alloy-separating

.337

192.

modified

"

340

apparatus,

193. 194, 195. Construction

.....

of wooden

341

separatingvats,

346

iron

196, 197.

""

"

198, 199. Section

plan of vat,

and

showing

",

Butters

and

Mein's

tributors,
dis347

.......

dischargedoors for tanks,

200-203.

Bottom

204-210.

Details of side

211-213.

Illustration of

348
....

dischargedoors for tanks,


tanks for use in
electrolytic

349
.

Siemens-Halske
'

355

cyanide process,
214.

Cowles*

zinc retort,
electrically-heated

385
....

Dorsemagen'szinc and silicon carbide furnace,


Experimentalchlorination barrel used by Dorsemagen,
217. Chlorination cylinderto be used in practice,
with subsidiary
electrodes in zinc deposition,
218. Connections
of zinc solutions,
219-222.
Apparatus for electrolysis
zinc chloride solution,
tank
for
223. Hoepfner'selectrolytic
215.

216.

386

390
.

.391

402
428

430

431

224,225.

Keith's

.......
plant,
vat,
lead-refining
Antimony extraction plant(section).
(plan),
tank (section),
electrolytic
(plan),

226-228.

229, 230.
231.
232.

233.
234.

"

"

"

236.

467
.467
480
....

.481
.

"

"

Borchers'

"

Moissan's

"

235.

.483
.

.483

"

491

furnace,

electric

.....

.493
"

237. Chaplet's
238.

,.

"

"

"

239. Harmet's

modified

493
......

"

electric

furnace,

electrical smelting plant,

240. Keller's arrangement,


241. 242, 243. De Laval's electric furnace,

493
....

516
....

518

......

.520
.

LIST

OF

ILLUSTRATIONS.

XXUl

BLECTRIC

techny.
at

It melts

at

SMELTING

AND

temperature
temperatures exceeding1,100" C.

the metal

are

they may

become

but

REFINING,

of 500"

Large

little altered

to 600"

and

C,

and

boils

thick

the

piecesof
air,although

by exposure
in the presence
oxidised,especially
superficially
of moisture; they may
be melted
in an
crucible
even
open
without
risk of burning. In the form
of a fine powder or thin
and at a higher
plate,however, magnesium oxidises very readily,
brilliant
bums
with
which
it
is particularly
a
light,
temperature
rich in the chemically
In the presence
active rays.
of only a
restricted quantity of air,magnesium nitride is always formed
well as oxide.
The property possessedby magnesium
of
as
combining with nitrogen,at a moderate red heat, might be of
value in the synthesisof nitrogencompounds, if
great practical
of producing the metal
should
be
a
sufficiently
cheap method
to

discovered.
The

powdered metal also,when once moistened,cannot be dried


without
At the ordinarytemperature
undergoing complete oxidation.
which
it r^idily
contains
water
even
a
decomposes
small proportionof dissolved salts,but it has less effect on
Finely-dividedmagnesium bums
freelyin superpure water.
heated
and
the
in
in
steam,
sulphur,
halogens. Magnesium
dissolves readilyin most
acids and salts;in the latter case
it
either displaces
the metal which
the salts contained
previously,
basic compounds with
it forms
the salts themselves.
Its
or
is so great that the metal is
solution-pressure
electro-positive
able to liberate,not only other metals, but even
metalloids,
their compounds, so that,for example, carbon
from
monoxide,
carbon
reduced by it,
dioxide, silica,and boron trioxide are
with separation
and boron respectively.*
of carbon, silicon,
On
of the strong reducing-action
of magnesium, paraccount
ticularly
be devoted
must
on
compounds, specialcare
oxygen
of the substances
to be used in the extraction
to the preparation
of the metal.
Just as the oxygen
compounds of magnesium are
avoided
is to be

in the selection

compounds,
completelyremoved
salts)to be used.
oxygen

of the

extracted,it

materials

is necessary
such a,s water,
from

that

from

which

all accidental

should
sulphate,""c.,

the

metal

traces

be

of

most

the

compounds (forexample, haloid


The
alkali-metal
double magnesium and
used
chlorides
for
are
magnesium reduction in preferenceto
the haloid, and
indeed to all other, salts of magnesium, not
but
only on account of their chemical and electrical properties,
of the comparativelylow cost of producing tJiem.
also by reason
be remembered
It must
that although the bulk of the water
of
of these salts is expelledwith comparativeease,
crystallisation
small quantities
retained even
at a brightred heat.
are
"
also CI. Winkler
The Reduction
of Oxygen Compounds by
on
Berichte
cJiemiwhe
deiUechen
der
OeseUschaft,voL xxiv.,
Magnesium,"
1966.
and
873
pp.

See

MAGNESIUM.

Magnesia, like
held

all other

to be unreducible

oxides

that were, up to the year 1891,


carbon, is capableof reduction through

by

the agency
carbon.
of electrically-heated
This is readilydemonstrated
with
the aid of the small electric furnace
described
in
the first edition
action

of Borchers'

quantity of the
of magnesium on

Early

metal

*
but no
ElektrometaXlurgie
;
thus be obtained,owing
can

appreciable
to the

compounds alreadyreferred to.


oxygen
It appears,
in Beduotion.
therefore,

Experiments

"

unquestionablethat Davy's experiments,!in which he reduced


white-hot
of potassium vapour, did not yield
magnesia by means
by the description
magnesium. This view is confirmed
pure
of
the
the
o
f
metal
obtained.
given by Davy
Bussy,t
properties
Buff," and Liebig|{obtained pure metal because they adopted
Wohler's
aluminium
process, decomposing the chloride by means
of potassium.

Bunsen's
Fig. 1.
cell.
electrolytic

Fig.

"

Electrolytic

Bunsen's

recognisethe

the first to

chloride

2.

carbon

Beduotion

chlorides

Bunsen's

electrode.

Process.

of
possibility

and
by electrolysis,

"

to

Bunsen

"

decomposing
indicate

fused

the

manner

was

magnesium
in

halogen compounds in the


fused and
anhydrous condition might also be decomposed into
this
and
metal
on
halogen. In 1852 he published a noteH
which
Fused
the
translation
:
followingis a
subject,of
nesium
magchloride is so easilydecomposed by the current, that
of heavy metallic regulusmay
several grammes
be obtained from
other

which

metallic

or

"

"

it in

short

time

with the aid of


chloride

few

carbon-zinc

elements.

is best

prepared by Liebig'swellknown
For the decomposing cell it is convenient
to use
method.
about
and
ins.
ins.
crucible
2
a
wide,
(Fig.1)
high
3^
porcelain
divided into two compartments by a diaphragm,reachingfrom
"

The

magnesium

Published Leipzig,1891 ; see p. 62.


t Phil, Trans.,London, 1808, p. 336.
de Chim. midicale,1849, vol. vi.,p. 141.
t Joum.

" Pogg. Ann,f vol. xviii.,p. 140.

Ann., vol. xix.,p. 137.


Ann.^ 1852, vol Ixxxii.,p. 197.
Lvsbig*9

IIPogg.

8MELTINO

ELECTRIC

the top half way


chlorine escapes

to

the

AND

bottom

RBFINIKO.

; in

of these

one

hberated

the

upwards, and is thus preventedfrom obtaining


magnesium depositedin the other. The diaphragm
of a thin porcelaintile,broken
consist
to the required
may
shape with the aid of the notches of a key. The crucible is
of ordinary fire tile,filed into shape,
covered with a lid made
and bored with two
holes (Fig.2) through which
the poles are
These
of
the
which
from
cut
out
material
are
passed.
poles
the battery carbons
are
prepared,a process that presents no
such carbons
as
easilybe bored, turned on the
difficulty,
may
and
thread.
The
even
lathe, filed,
provided with a screw
carbon
fastened
the
the cover
of
to
by means
poles are
which
also
of
and
which
to
are
d^
serve
carbon,
wedges d,
grip
the platinum stripsthat are
the current
used
to convey
to
to the

access

and

the

from

pole
the

in
the

of

form

would

there

be

the

experiment

the

it,are

to

electric circuit is then


Bunsen

top

absence

of the

crucible,with
with

from

for

minutes.

115

intervals
of reduced
to

10

of this

the

cover

until

fused

the

in

tive
negain- them

collects

arrangement,

heavier
relatively

liquid
conducting
and
the poles
red hot, they are
In

they are
magnesium chloride,and

the

which

the

completed."

way of example an
carbon-zinc
elements

experiment in

quotes by

current

notches

which

burned.
partially

first heated

filled to the brim

next

the

least

at

saw-like
metal

In

float to the

and

attached

reduced

the

regulus.

would

metal

The

apparatus.

retain

From

the

allowed

was

that

measurements

to

operate
made

were

at

of five minutes, he calculated the theoretical quantity


which
would
spond
corremagnesium at 4*096 grammes,
a

of 4*7 amperes.
arrangement of the

current

of the size and

what

to ascertain

in this
Matthiessen's

electromotive

Since

no

details

batterycells,it

force

was

used

is

are
given
impossible

for the

position
decom-

experiment.
-Chloride

Double

Process.

"

Matthiessen's

double-chloride

of magnesium and
proposal* to substitute the
the
for
single
potassium(camallite)
magnesium chloride,which
obtained
is with
difficulty
anhydrous, is especially
worthy of
notice,as it has been adopted at a later date for the production
of magnesium on
a
manufacturing scale. The camallite,as it
in nature, cannot, however, be so used direct,by reason
occurs
other impuritiesthat it contains, which
of the sulphatesand
interfere with the dehydration,fusion,and
of the
electrolysis
salt.
Berthaut's

in the
carbon

use

and

chloride.

Berthaut's

patentedprocess!consisted
of a soluble anode made
by compressinga mixture of
and
magnesia,
employing it in a bath of magnesium
This was
imitation
of Deville's proposalX to use
an
Process.

"

Jaurn.
Chem, Soc.,vol. viii.,
p. 107.
t Eng. Patent 4,087,of 1879.
"

J See Alumviium.

MAGNESIUM.

anode

an

composed of

aluminium.

and

aluminium

Electrodes

carbon

for the reduction

of

of this

however, are liable


description,
of the oxide, and thus
to fall to piecesowin^ to the extraction
the bath.
This
to contaminate
known
to
disadvantage was
Le

Chatelier,* who

it by enclosingthe
sought to overcome
anodes
cells. Although Deville's and Le Chatelier's
in porous
inventions
were
primarilyintended to be appliedto aluminium
redaction,they are equallyavailable in the extraction of magnesium,
Berthaut
has
as
recognised,for he has included the
reduction
of both these metals
in his patent, and has adopted
Deville's proposal as his own
invention.
Everyone, however,
who
has experimented with electrodes of this descriptionhas

Fig. 3.
become

convinced

of

"

Gonip-Besanez apparatus.

their

Although the idea is


possibleto carry it into
that are
mountable.
insurpractically

uselessness.

undoubtedly sound, it has not been


owing to technical difficulties

effect

simpleapparatus for lecture


by v. Gorup-Besanez:t a clay
experiments
pipe is supportedin a holder (Fig.3),and the bowl is filled witn
the double-chloride of magnesium and potassium, which is then
burner.
melted with the aid of a Bunsen
A knitting-needle
is
introduced
into contact
now
through the stem until it comes
Small-scale

Apparatus.

has

been

"

A very

described

See Alumimum,
t Lehrhtich der

anorganischenChenu,

4th Ed., p. 517

(Gorup-Besanez).

ELBCTRIC

with
the

fused

the

negativepole of

coke

connected

the

pipe

solidified
reduced

needle

the

above

other

serves

magnesium

are

in this

pole

with

the cathode ; a fragment of


dipped into the bowl of

and

be found

the

outside

connected

anode.

as

to

of salt ; but

mass

being

batteryforms

with

from

of
globules

The

salt.

REFINING.

AND

SMELTING

After

cooling,small
through the
the magnesium

distributed
of

greater part

experiment is burned.
of the

type suggestedby
for the electrolytic
Fischer,*in 1882, in discussingother methods
have
into
of
not
even
use
come
decomposition camallite,
suitable for
experimentally. An apparatus, also by far more
Fischer's

Apparatus.

"

Apparatus

F.

by F. Fischer at a slightly
crucible (from the Royal
the porcelain
case
Porcelain
enclosed
within
two
in
was
cylinders,
Factory Berlin)
and
made
sheet
with
asbestos
iron lined
a
of
6,
(Fig.4),bound

lecture

recommended

purposes, was
later date.f In this

Fig. 4. "Fischer's

by

three

strong

The

objectof

the

crucible

red heat.

the

beneath, and supported on three feet,".


to equalisethe temperature, so that
rings was

wires

might

The

asbestos,and

be

cover,

had

an

steadilyand
g?,was

that

from

the

hot
*

gases

uniformlyraised

also coated

on

the

opening through which

easilypass, in order
protectedfrom the
The

apparatus, 1884.

it should

action

of the

three

rest

upon

flame

by

burners

the
a

under

to

side with

crucible
thick

clear

might

iron

wire^

pipe-claytube, .r.
circulated evenly around
a

Jmirn., 1882, vol. ccxlvi.,p. 28.


pofytechnisches
Diiigler'a
Wagner-Fischer,Jahi-esberichf der chem. Techn., 1884, p. 1317.

MAGNESIUM.

the

inasmuch

crucible

pass downwards
the arrows.
As

they

as

between

the

double

compelledJto
by

direction indicated

h in the

and

afterwards

were

salt

melted, a circular
crucible,and pressed into
plate,t?, was placedupon
close contact
with the rim by a heavy cast-iron ring,/. Passing
the
asbestos
cover
a claytube, o (made by removing
was
through
soon

as

the bottom
holes

from

provided

chlorine.
This

These

form

Through

which
with

served

of tube

the
as

clay
positiveelectrode,and

side connection, r, for the

kept

were

the side of which


tube there were

in
batterycell),

porous

bored.

were

both the carbon


tube

was

the

asbestos

was

in

chosen

placeby
in order

obstructions,and to enable
stopper,to test for the evolution

of
application

stripof

of

plates.

the

operator, after

of chlorine

by

the

length of iron wire,",


mm.
negativepole,and had its lower end
bent into a ring so as to encircle the carbon.
A very gentle
of reducing or neutral gas, previously
dried by passing
current
introduced through the tube ^,
through calcium chloride,was
and made
When
its escape along with the chlorine through r.
the
and
coal gas was
used,
hydrogen
hydrocarbons present in it
a

thick,served

combined

with

as

litmus

small

to facilitate the removal

of accidental

raisingthe

few

passed

removal

of asbestos

means

paper.

the

the chlorine.

dynamo built by
affordinga current
Uppenbom
of about 50 amperes
at from 9 to 10 volts;and the dynamo was
driven by a 1-H.P. gas engine made
by Korting,of Hanover,
crucible was
When
one
employed,the current-strength
averaged
crucibles
but
35 amperes
in
i
t ranged
two
series,
by
coupling
;
from
to
from 22 to 25 amperes, which was
44
to 50
equivalent
and the hourlyout-turn
of magin the two
together,
amperes
The

electric

and

current

derived

was

Gackenholz, and

from

capableof

10 grammes
[154grains].The metal was
but
depositedin the form of a slime upon the negativeelectrode,
melted
at a clear red heat into globulesof the size of a nut
nesium

amounted

to

which

slowly rose to the surface. Instead of the iron ring,", a


be used as cathode,and from
carbon platemay
this the globules
of magnesium detach themselves
than
more
readily
they do from
the former.
of magnesium may
the reduction
By this method
made
the
of
b
e
lecture
a
subject
experiment.
readily
the apparatus is certainly
For lecture and laboratory
purposes
useful ; but in no case
is it adapted for regularuse
on
a
large
would
from
the
it
be
to
account
as
scale, one
given in
suppose
der cliemischen Technologie
Wagner-Fischer'sUandbuch
(edition
described.
where
the
form
could
is
It
it
1893),
only
only be
made
of comparativelysmall size,and even
then would
be very
fragile.
A short time before the publication
Graetzel's
Apparatus.
of the above
This
taken out.
process, Graetzel's patent* was
"

"

German

Patent

26,962, 18S3.

ha,s been

patent, which

of several
the

AND

SMELTING

ELECTRIC

REFINING.

described

ideas.

The

was
a
very frequently,
followingaccount is taken

bination
com-

from

:
specification
The
lytic
present improvements in the apparatus for the electroproductionof the alkaline-earth metals on a manufacturing
scale from
fluorine compounds,
their respectivechlorine and
"

"

Fig.

5." (iroetzel's apparatus (transverse section).

Fig. 6.
the

with
the

section).
apparatus (longitudinal

subsidiaryassistance

hand, in the
and, on
electrode,
negative

consist,on
as

Graetzel's

"

the

one

tie

two

produced at

the

of

electrodes in

of

cuiTent

of the

use

the other
such

electrode
positive

can

of

reducing gas,
meltingvessel itself
hand,
that

way
be caiTied

in the tion
separathe chlorine
off

separately

10

SMELTING

ELECTRIC

in

It is closed

shape.

carbon

electrode

it is

is
with

above

with

and

q,

coupling of
the

in
m

representthe connections

For

the

reduction

the

bottom

with

the

of

is somewhat

apparatus

of

vessels

chlorine

the

at

in

the

with

the

aluminium

the

modified.

This

effected

battery is

of

top

like the
installation. The

the

in

into

indicated

as

manner,

The

tube, p\
main, p, which,

the

give

to

anode.

the

its sides

on

or

side

crucibles

melting

which

through

cover,

carbon

chlorine

all the

serves

several

usual

and

the

in

compartment

mains

passed,whilst at the bottom


serve
perforations,
g, which

provided
melted
to the
charge free access
G
in
generated
escapes through
the

REFININQ.

AND

where
illustrations,

dynamo.
of

ari-angement

metal

tends

the

sink

to

to

of the

into contact
melting vessel,and so to come
consist
which
should,
therefore,
electrode,
negative

of aluminium) independent
separate metallic conductor
(preferably
of, and inserted within, the crucible. Accordingly^
the crucible,
s (Fig.
stoneware, or other
7),is made of porcelain,
equallyrefractory
material,and is protectedfrom direct contact
a

with

the

The
metallic
by an outer sheathingof metal.
the
within
is
connected to
conductor,r, placed
negativepole
8,
of the dynamo.
If preferred,
the cathode-cell may be introduced
into a graphitecrucible instead
of into a porcelainvessel,in
which
be

flame

the outer

case

used

in

course,

be

In

order

and,

conjunction
lessen

to

the

time,

same

becomes
electrolyte
consist
of

of

carbon

electrode,but

combines

with

enables
unite
The

the

the

with

followingclaims

1. An

apparatus

of the

earth

which

serves

are

reduction

magnesium,

with

in this

The

it.

in these

present in

made

of

the

carbon

rods,and
the

of

which

rods, M,

G, parallelwith

compartment,

that is

supply

for that of

carbon

quite independent

the chlorine

apparatus,

the

for the

carbon

the oxygen
of the oxide
metal
previouslycombined

the

as

plates or

and

magnesia and

into

of

bath

the

it may
must, of

or

applied.

resistance

the

of alumina

of

or

introduced

to be

heat

enrich

exhausted,

mixture

aluminium,

are

may
metallic

internal
to

be omitted ;
vessel,which

sheath

with

the
capableof resisting

the

at

metallic

thus
to

oxygen

the

compartment.
:
patent specification
"

for the

manufacturing scale

productionon a
their anhydrous chlorine and fluorine
of
compounds, consisting a closed metallic melting vessel.A,

outlet for

metals
also

from

the

as

reducinggas,

negative electrode,with

in combination

and

with

fire-resisting
G, which surrounds
vessel,
K, and is provided with openingsin the

to insulate the

removal

electi-odes from
of

the

one

inlet

and

the
the

non-conducting
electrode,
positive

sides

another,and

or

at the

bottom,

to facilitatethe

facture
halogen produced. 2. In the manuof aluminium
scale
the
in
above-described
on
a
large
the use
of metallic conductors,especially
of aluminium
manner,
introduced
into the melting vessel as negative electrodes,as

separate

11

MAGNESIUM.

described with

reference

within

resistance

the enrichment

the

first

apparatus

of the

diminish

3. To

Fig.7.

to

the

electric

well

described,as

for

as

smeltingbath

it becomes
as
impoverished^
and
platesor rods, M (Figs.6 and 7), of alumina
of
and
in
carbon, or
carbon,
equivalentquantities
magnesia
should
be placed within
which
the vessel,G, independently
respectively,

the

of

use

of the electrode.

The

of

noveltyin
platesor rods

the

the

whole

of

patent
and

magnesia

the

was

carbon,

duction
introof

or

carbon, to be used in the productionof magnesium


and this has not proved successful ;
aluminium
respectively,

alumina
and

acttuU

only
and

and
in the aluminium
discontinued
magnesium
at the time that Graetzel was
managing
factoryat Bremen even
The eflFect
of these plates,
like that of Deville's oxidethe works.
carbon anodes, wa,s only to introduce
impuritiesinto the bath,
its

use

was

and thus

to

and
irregularity

cause

In order to bring about


the equation

MgO
the

temperature

higherthan

of the

is desirable

desired

C +

CLj

MgClj

would

have

bath

in the

inconvenience

the

reaction,as

either for the

working.

fonnulated

in

CO

be maintained

to

much

productionof

magnesium,
preservationof the apparatus, or for preventing the
of
destruction of the platesthemselves
through the removal
for the

the oxide.
The
introduction
was

made
had

also,had

of reducinggases into the cathode chamber


But this proin the specification.
a prominent claim
posal
been made
in the year 1882 by F. Fischer.*
Hiller,t
arranged for the use of a reducingatmosphere in the

cathode chamber
and

lithium.

of his

apparatus for the reduction


Moreover, this precautionarymeasure

in

the

of
electrolysis

of strontium
is

entirely
Practicallythe

camallite.

unnecessary
whole of the magnesium remains
adhering to the immersed
walls of the crucible,provided that a
to the
electrode and
of suitable strengthbe used and that the fused salt be
current
not connected
up with the battery until it has been melted

long, and
sufficiently

at

high temperature,
sufficiently

drive off the last traces of water, which


the most
obstinate pertinacity.The
use

therefore,necessary
immersed

this

on

in the fire almost

top

of
but

account;

to the

retained

are

rim

by

to

it with

reducinggas
if the

is not,
crucible be

it will be found

that

in the absence

of reducing gases the walls of the vessel become


^vithin.
stronglycorroded above the level of the fused mass

This is due

owing

to

the

to the combined

the acid
the
"

metal

of the

crucible

becoming chloridised,
without
and
fire-gases
above
being always present

effects of the

hot

gases within, the latter


when
surface of camallite
it is melted

See footnote, p. 6.

in the

t F. Hiller,Lehrhiick

der

presence

Chemie, 1863.

of

12

ELECTRIC

"ven

small

above

the

proportionof

level

AND

8MBLTIM0

of

crucible

The

air.

melted

through, whilst,in addition,the


to

the

over

creep

and

there, aided

rim

by

by adopting
This

crucible
ins. from

2|
with

its

part

is

top, with

portion
being thus
cool
sufliciently to reduce

of

the

remains

the

in

crucible

to

of acid
in

come

Borchers'

"

for

flangeii

which

as

Davy

long ago

here

of

an

serve

Uiose

walls

which

substances
cathode

as

mass

uppermost margin
within

not

the crucible

this level would

be

be at

once

solidified.

melting vessel as cathode,claimed by


invention,was
anticipatedin actual practiceby

Graetzel

Napier's

with

in contact
crystallised
with
the comparativelycool walls,
yet any thin layer of fused salt that

might reach above


Finally,the use
so

upper
air

the

tendencyof the melted

if the

^^ the fused

electrolytic should

reduction.

his

it

the formation

fused

with

The

even

9.

support
The

the side of the


creep
up
cause,
is completelyprevented be-

to

crucible

crucible

only

the crucible

within, and

2 to

gases and the corrosion


Thus the furnace gases

in contact

surfaces.

Fig.

to

both

contact

portionsof

salts

Borchers.

of about

fire.

minimum

structive
de-

prevented

exposed freely to

of the vessel.

are

surface,
most

however, be
may,
crucible
used
by

immersed

tends

outer

it exerts

provided,at a distance
which
serves
a
flange,

lower

roded
rapidly cor-

camallite
the

to

on

gases,

of

construction

(Fig.9)
the

vessel

the

furnace

Tliis action

influence.
the

of
the

walls,therefore^

become

substance

fused

the

REFINING.

of the

as

the year

Electrolytic

1808.

Vessel.

An

"

account

apparatus patented by Napier*

indeed, originallyintended
find combined
in it,even
we

for

the

at

in

extraction

this date, the

may
1844.
of
most

be

given

It

was,

copper,

but

important

elements

reappearingin Graetzel's and other patents afterwards.


Napier used a largecrucible or other convenient vessel made
of some
conductingmaterial,of which the inner side,with the
exception of the bottom, was lined with a coating of clay. The
mixed
ore, roasted as free as
possiblefrom sulphur,was
copper
with
mass

such

the necessary fluxes and fused in the crucible ; the melted


then submitted to the action of the galvaniccurrent
in
was
that the crucible itself formed
the cathode, whilst
a
way

the anode

end.
iron rod united
to a plate at the lower
was
an
It is thus clear that even
in 1844 an apparatus for the reduction
of metals had been patented,!which consisted of a meltingvessel
"

EnglishPatents

Frankhn

10,362, 1844, and

Imt,, 1889, vol.

+ Cj\ GraetzePs

Patent

cxxv.,

684, 1845.

p. 376.

claims, pp. 10, 11.

Cf. Houston, Jonm.

15

MAGNESIUM.

conducting material and serving as the negative


and fire-resisting
with a non-conducting
electrode,in combination
the
and
electrode
the
at
bottom,
surrounding
vessel,open
positive
the electrodes and facilitating
of insulating
the
for the purpose
made

of

some

of the anion.

removal

In accordance
with
the
Process.
and
the
Troost's*
of
above,
following
explained
pattern
principles

Magnesium

Borohers'

Fig. 10.

"

"

Borchers' experimeDtal furnace for the


of fused salts.

electrolysis

apparatus, the cell surrounding the carbon electrode being reduced


in size,whilst at the same
time taking into account
the

experience which led to the adoption of the shape of crucible


depictedin Fig.9, the author has designedan apparatus (Fig.10)
of experiments in the electrolysis
suitable for a largenumber
of

fused

salts.

Within

cathode, is suspended

the
the

iron

carbon
*

crucible,K, which forms the


rod. A, as anode, surrounded

See p. 22.

14

ELECTRIC

AND

SMELTING

REFINING.

ducting
porcelaintube, C. The anode is connected to the conof the screw
wire from the dynamo by means
clamp, V,
and is supported by the ring-shapedporcelaincover, L, whilst
tube rests by means
the porcelain
of a collar on another annular
the
the
whole
crucible is in turn
d
of
weight
porcelainplate, ;
of
Perrot
borne by the chamotte-plate
a
D,
furnace,upon
cover,
which
it is held by the flange,F ; and this,by an extension
on
the
electrical
with
makes
connection
one
side,
negativepole of

by

the

Fig.11."

Borchers' furnace

for

use

with

currents

of 100 amperes.

dynamo through the bindingscrew, N. The furnace consists


chamotte
O, protectedexternally
a wide
cylinder,
by a sheetbe
which
either
feet
attached
iron jacket,
M,
supported
by
may
is closed beneath
to it,or by a temporary stand ; and the whole
plate,B, provided with a central opening. The
by a chamotte
the heated
to convey
internal fireclay
W, serves
cylinder,
gases
of
first
all upwards and
from a sufficiently
burner,
powerful gas
and thence downwards
around the crucible,
through the annular

the
of

15

MAGNESIUM.

The
W
and O to the flue,Z.
Kpace between
of the flange,F, with the negativemain,
of

means

In

upwardly
N,

bent

end

by

is connected

screwed

using

joint.
apparatus, the empty

the
is

the camallite

heated

first be

should

for

crucible

in
being melted, preferably,

its appurtenances

and

considei-able
second

time, while
crucible.

of
the crucible just described is suitable for currents
with the
it is possibleto employ 100 amperes
50 amperes,
apparatus used in Borchers' laboratories in the Technical College
of a
This apparatus is heated
by means
at Aachen, Fig. 11.

Whilst

about

Fig.

12." Borchers*

furnace

for the

of magnesium
electrolysis

compounds.
Rossler
and

to

advisable to

is here

An

arrangement

to 300
use

an

amperes

adapted
is shown

apparatus much

figured,not only

to

coal

filing

in

Fig. 1 2.
largerthan

for structural

that

but

on
reasons,
of the size of the electrodes that would
be required
them.
of the distance between
It is preferableto use
a

account

and

of 250

current

It is not
which

furnace.

gas

both

of vessels of ordinary
size connected
up in series;
the crucibles must
be supported in separate
between them through
furnaces,in order to avoid short-circuiting

greater number
that

but

in

the

depositionof

case

soot

or

other

conductingmaterial.

Several

16

REFINING.

AND

SMELTING

ELECTRIC

be served with fuel from


a
single
may
be
fuel
solid
whether
or
used,
firing
grate,
gas
be
crucible
that
the
may
separate chamber, so

meltingvessels,however,
generator.

The

is best built

in

protectedfrom the direct


being requiredduring the

material
the

small

It is necessary
spare

progress

facilitate the

To

may
in the illustration.

to

for

arrange

heat
extra
(little
and
electrolysis),
be
prevented
may

of

leaky crucible

chamber
collecting

shown

as
crucible,

actual

fuel.

the

flowing into

from

of

fluid contents

that the

of the flame

action

be

provided

heating chamber,

of such

remoinal

beneath
which

in
be

clay portionsof the

kept
apparatus may
porcelainor
be replacedwithout
loss of time.
that damaged parts may
heated by the waste gases from the
chamber is conveniently

hot, so
This

furnace.
in the

of the

Preparation

Preliminary
extraction

of

magnesium

Charge.
the

on

^The first

"

stage

manufacturing scale

is

The salt as it occurs


anhydrous camallite.
is too impure for immediate
treatment
in nature
by electrolysis
;
for the production of the magthe carnallite necessary
hence
nesium
is prepared from
magnesium chloride and potassium
the

productionof

chloride, the

of the

exhaustion

which

of

latter

magnesium

is

in

in

part

the

fused

bath
of

Under

after

recovered
under

the

lytic
electro-

the

a
new
Hemelinger
patent
Magnesium Works,* natural camallite can be
rendered
serviceable for electrolysis
by fusing it,without any
in
of
chloride
previous purification, admixture with so much
magnesium or chloride of sodium, or of dehydrated artificial
camallite,as may be necessary to bring it up to the percentage
25-66,
41-66, KCl
32-66, and NaCl
composition,MgCL
the
fused
NaCl.
A
formula
KCl
to
MgCl,
corresponding
and
bath
of this composition is well suited for electn"ly8is,
be added gives a metal which flows readily
if a little fluorspar
together.
method
the mixture
of salts is prepared,the
By whichever
is
followingprocedure usuallyadopted: Crystallised
magnesium
is fused in an open hemispherical
chloride,or artificial carnallite,
in
iron pan, either of these salts melting with comparative ease
of crystallisation.
The necessary quantityof potassium
its water
in the Hemelinger patent,
chloride,or of the mixture
specified
which
is at first pasty,but
to the fluid mass,
is then added
which
solid
rapidlybecomes
again as it loses its water of crystallisation.
During the intermediate pasty stage it is necessary to

treatment.

Aluminium

and

'

"

stir the

mass

drying of

the

brisklywith

an

iron

tool,both

to

charge and to prevent the adhesion of thick


It
portionsof the walls of the pan.

of salt to the hotter


known

facilitate the

that without

the addition

chloride

hydrated magnesium
"

German

of the

would,
Patent

salts above

when

115,015.

crusts

is well

mentioned,

evaporated in

the

18

ELECTRIC

oxide, which
Oettel,as

nesium
masses.

the
carnaUite
the

in

checks

addition
the

at

form

SMELTING

AND

their

unitingtogetherinto larger
mends
recomsimple remedy for this difficulty,
of a small
proportion of carbon to the

the

like, decomposes
heat, as follows:

This

of fusion.

time

carbon, which
dust, sawdust, sugar,

wood-charcoal

of

REFINING.

the

sulphate at

magnesium

may

be

flour,or
dull

red

"

MgS04
Beduction

The

Frooess.

originally
present,and
the

"

of the

salts,the

of

mixture

MgO

CO

SOj.

After

the removal

oxide

formed

fused

during the

will,at

mass

of the

sulphate
fusion

clear red

of

heat,

become

this point has been


tranquiland clear. When
the
lifted
of
is
out
its
seat and its contents
reached,
melting pan
are
vessel,taking care
emptied into a pre-heatedelectrolytic
that any sediment, consisting
of impurities,
is left in the melting
The anodes, with their porcelainenvelopes,which
must
pan.
soon

also have

been

of

heated

then

beforehand, are

introduced,and

the

is started.
electrolysis

process
If all the

have been properlytaken, the magnesium


precautions
the lower part of the walls of the
to depositon
vessel
in
globules,which increase rapidly in size,
electrolytic
while the chlorine,risingthrough the porcelaincylindersurrounding
the anodes, escapes above.
that
It is most
important
the temperature of the bath be not permittedto rise much
above
that of the meltingpointof magnesium, because at this temperature
the metal
is specifically
and
heavier than the electrolyte,
of the vessel.
will therefore
remain
at the bottom
A higher
will be

found

temperature
and

of bath

is favourable

of the

the

re-solution

of

nesium,
magrequiredwill be sensiblyhigher; it
pressure
loss of magnesium, because the metal at a bright

the

leads also to a
red heat is specifically
lighterthan
to float up

to

the fused

salt,and

so

tends

bottom, in which case a considerable proportion


magnesium will be burned, either at the surface or at

from

the

the anode.
with

of
current-density

least

1,000 amperes
per
of
[93 amperes per sq. foot] cathode surface,the
square metre
at the surface of the anode
will be about
ten
current-density

Working

unusuallythick carbon rod be employed.


In
pressure of only about 7 to 8 volts is required,
be
reduced
whidi
by 1 or 2 volts (where an economical
may
the size of the anode.
is
installation
sought)by increasing
for a sufficiently
After
continuingthe electrolysis
long time,
the
of
the
contents
of
crucible,through the clear
an
inspection
the requiredquantity of the metal
fused salt,will show when
The
has been
accumulated.
current is then broken,the screw
and
the
connections
are
opened,
cover, dj togetherwith all that
from
the melting vessel.
it supports,is removed
The flame is
much, even
spiteof this,a

times

"

at

as

if an

19

MAGNESIUM.

increased,and

somewhat

now

is detached

walls

correspond with

the

sheet

iron,which

that

still adheres

the

to

The

then

And

the

globulesof

shot

may be melted
the less pure metal

clingingto the
shaped to
scraper

iron

an

of the

and

walls

solidified

off.

of metal

mass

of

poured

be cold

must

scraped

but

are

the
aid

surface

inner

of the vessel

contents

the

with

crucible.

into

dry,and
perfectly
the

of

vessel

And

purer
crucible
in

any
be rapidly

cooling,is broken
up,
The
magnesium are picked out.
largerpure
togetherwithout flux in a plumbago crucible,
be fused

must

and

refined.

ordinary fire,but the less


must
always be submitted

an

larger
togetherin a
and

pure
to

The

"

the

heat

red

dull
metal

pressed into
raised

to

^which

the

the
to

one

that

brightred

The

the surface

crucible

in the form

of

is

magnesium

then, liquatingfrom

metal

with
far

as

crucible,
At

its aid
as

temperature is now
heat, until a point is

specific
gravityof the

flux.

removed

of the
The

mass.

of

introduced, and

is

bottom

the

lying at

rod

iron

an

the

possible
gradually

reached

is less than

its

grained
fine-

refining
operation.

this purpose
carnallite is melted
in an iron
into the fused mass.
the crude magnesium is thrown
For

and

of

after

mass,

Electro
-deposited
Magnesium.
of
pieces
magnesium may be melted

material

whole

made

metal

must

of

Melting

The

flat box

at

that of

floats
impurities,

globulesof considerable

size,and

is

perforatedsieve-like ladles. The surface-tension of


magnesium is so great that the metal cannot flow through
of the ladle,although the flux may
thus
the fine perforations
drained
be
The
purifiedmetal is finally
completely away.
in
melted
crucible
iron
to
an
together
separate the last traces
of slag,and to enable it to be cast into the bars or rods required
in

melted

for the market.


Eleotro-thermal
Liedderboge* have
mixture
circuit

magnesium
from

the

of

manner

one

thus

"

magnesium

the form

carbons

oxide

reactingwith

Magnesium.

smelt

proposed
magnesia in

carbonic

and

of
to

and

of carbon
after

Beduotion

in

by placinga

of rods in
an

produced

arc

an

electric

lamp
to

were

another, either by

and

Knofler

the

the

be

vented
preintroduction

by conducting the whole experiment


The
in vacuo.
probably be workable, but it is
process would
whether
would
be successful financially.
it
The
questionable
force
considerable electromotive
requiredfor the operation,the
of
the
in pure magnesia as compared
magnesium-unit
high price
that magnesium is volatile atthe circumstance
-with carnallite,
temperatures much below that required for the decomposition
of condensing the resulting
of the oxide, and the difficulty
of

reducing gas

or

from
its admixture
with carbon
monoxide
and
metallic vapour
sufficient grounds for predictingthe practical
other gases, are
"ulure of the process.
*

German

Patent

49,329, Feb. 6,

1889.

20

ELECTRIC

SMELTING

The

AND

RBFIKINO.

recommended

by Hilbei^*
improving both the process itself and the yield of metal
the surface of the
possess no advantages. He proposes to cover
with a layerof asbestos cloth,with the objectboth
fused mass
blows
shocks of any kind,
of protectingthe electrodes from
or
and of lesseningthe frothingof the bath.
The asbestos is also
intended
of the electrolytic
to prevent the atmosphericoxidation
this
still
further
the space
to
and
object
magnesium,
promote
Process.

Hilberg'8

"

meanfi

for

above
with

fused

the

is to

mass

indifferent gas.

an

rendered

be

what

From

been

concerning the process, it will be obvious


that it is not necessary
the
to introduce
order

in

Hilberg patent

to

above

written

the

man
practical
of
complications the

to

difficulties of

the

overcome

to be filled

or

vacuous,

has

the

process.
of

Applioations
been

Magnesium.

extended
considerably

of the valuable
the

the

of late,since the
alloywith aluminium.

Aluminium

and

Griesheim-Elektron

Besides

the

Suter,at

Works,

Magnesium

Chemical

Works

later process worked


electroKjhemical
works
at

magnesium, by
and

magnesium has
discoveryby Mach
of

use

propertiesof its

Hemelinger

Bremen,

The

"

ducing
proKathenau

by

out

near

is also

and kept
Bitterfeld,

secret.
rigorously

most

the

Otherwise

use

of

of aluminium
introduction

of

might

remain^

have

be utilised in the
for the

the source
; its employment, however, as
light in pyrotechny and photography is by
The

sodium,

price of

has

of
no

the

to

latter purpose

powerful

siderable.
incon-

means

that

of
compared
magnesium,
present time)and the alkali metals,especially

(atthe

aluminium

facture
manu-

unfulfilled,
owing

advantageous methods

more

the

and
restricted,

remains

magnesium

hopes,at first entertained,that it

led to

with

as

its introduction

into the chemical

industries

in spite of its high reducing


only in very limited quantities,
It is,however, especially
well suited to the dehydration
power.
of

alcohols,ethers,and

its reaction
substances.
mann,

in

dissolved

with
If

water

it be

melting
in

the

which
properties,

because

oils,because

the

formed

nickel

by
these

of
quite insoluble in most
still employed, as
proposed by

metal,

is

to

the

remove

it is less

Magnesium

Utst

account

on

it possesses in common
of magnesium that

any excess
with
the nickel.
alloy

hydroxide

with

Fleitoxide

traces

of

of

reducing

its

aluminium,

be added
does
may
is also recommended

than
not

for

the

silver,and
refiningof other metals,such as copper, German
added
effect
the
small
to
removal
of
steel,being
quantitiesof
dissolved oxides,sulphides,
and phosphides. In laboratories it
is employed as a powerfuland reliable reducingagent.
*

English Patent

of Feb. 6, 1898.

16,659,of July 30, 1898, and

German

Patent

110,403"

21

LITHIUM.

CHAPTER

11.

LITHIUM.

mineral

occur

waters

in

fluoride

and
lepidolite

in

Of
Katnre.
in nature, the chloride

lathimn

of

Occnrrenoe
which
lithium

"

the

compoundB of

is found

in

silicate is met
a
triphylite.Numerous

phosphate in
few plants(e.g.y
also
a
tobacco),

minerals, togetherwith

lithium,but
4 per cent,

the richest minerals

even

of this
of

Properties

Surfaces

metal

vaporisedby

than

more

Troost

"

soft metal

of the metal

group.
white
silver-like lustre.

contain

never

other

contain

"

0-5936)is

gravity
specific

witL

metal,and usuallyonly from 1*5 to 2 per cent.


Lithium
Metal.
(Li ; atomic weight 7 ;

the

"

many

togetherwith

at

protectedfrom

It melts
clear red

belongingto the alkali*

at

180"

heat

C,

the air have


has been

and

(about 1,000'C).

At

temperatures below 200' C. it may be melted in the air without


taking fire,but at higher temperatures it bursts into flame,
and
becoming converted into
emitting a blindingwhite ligh^
oxide

the evolution

of much

halogens under

similar

with
the

and

lightand

It unites with

sulphur

circumstances,evolving both
It decomposes water
at the ordinary
ture,
temperathe other alkali
to the surface where, unlike
without
tranquil,
melting,givingrise to flame,

heat.
floats

and

heat.

metals,it remains
or
lightingthe hydrogen

produced by the reaction. It is obvious


must
be very energeticupon a metal
which
able
is
to decompose water, and the salts
such as lithium,
of which are, almost without exception,
soluble.
so
easily
^The many
of Lithinm.
methods
Sxtraetion
proposed for
that

the

of acids

action

"

of these

the treatment
is in all
or

rendered

cases

chloride.

As

in addition

to

the

minerals
soluble

natural
more

solution with
at

lithium.

present introduces

so

far alike that the lithium

result of this treatment, it follows that


easilyseparablemetals,the alkali- and

alkaline-earth metals,which
the

are

by convertingit into the sulphate

are

The

always present,must
separationof these

and
great difficulties,

to Uie cost of the process.


if it be intended

Such

adds

pass into
latter salts

considerably

necessary
operationis,however, unto produce metallic lithium,because
be completely
dition
this metal may
separatedin a perfectly
pure conthe
of
the
with
absence
and
magnesium
greatestease (in
alkali-metal and alfused
of
mixture
kaline-eart
a
electrolysing
salts)by

metal

chlorides.

an

Bunsen

and

Matthiessen

in 1854,

22

BLKCTRIC

8MBLTINO

AKD

REFINING.

that the successful eleo*


working with lithium chloride,showed
fused
alkaline
chloride
o
f
was
trolysis
quite possible;and the
former*
follows
this
wrote
on
as
point: "The lithium chloride
of
is melted in a small thick-walled
porcelaincrucible by means
Berzelius
4
and
then
with
the
from
to
is
treated
current
a
lamp,
6 zinc-carbon elements.
The current
is passedthrough the fused
chloride from a pointedfragment of gas carbon to a pieceof iron
the lapse of a
wire the thickness
of a knittingneedle.
After
few seconds
to be
only a molten silvery-white
regulus is seen
mersed
imand
the
to
forming upon
clinging
"

portion
have

to the size of
grown
metal is obtained,with

electrode

be

minutes,
an

of

ounce

short

ProoesB.

work

is

apparatus

for

of fused
electrolysis

lithium chloride.

by

of which

one

pole, K;

matter

three

of

reduce

to
in

quite a

The

"

led

results
in the

publication
naturally to

direction.

same

these

of

confirmation

In
sults,
re-

fied
Troost,t in 1856, described a modithe
of
in
view
apparatus which,
tors,
by later invenpatent claims advanced

Fig. 13.

covered

operation

intervals

easy
lithium
chloride

publishinghis

the

this

as

an

Bunsen's

further

Troo8t*s

pea.
of a

aid

the

time."

Troost's

of

; and

repeated at
it is

small

melted
raising the
solution,togetherwith

by
spoon,
regulusout of the
may

it will

three

to

small

the wire

within

wire ; and
minutes

and

The

a-half

of the

two

cast-iron

A
specialattention.
crucible,T (Fig.13),4| inches

worthy

of

high and

2 inches

used

the

at the

wide

as
melting
lid,D, providedwith
close-fitting

was

whilst

diameter, there

0*2 inch

wide, and served to


through the other, which

mouth,

was

This

was

vessel.
two

admit
was

perforations,
the

l\

negative
inches

in

sheet-metal

passed
cylinder,having an
internal diameter
of 1*14 inches, and
to
reaching downwards
half the depth of the crucible.
Within
the metal
cylinder was
tube forming a sheath
for the positivepole.A, and
a porcelain
of
for the separated chlorine.
The
lithium
means
a
escape
the apparatus
at the negative pole,and
graduallyaccumulated
could be left to itself for an hour at a time, provided only that
the decomposed chloride
was
replaced from time to time, as
the
introduction
of
fresh salt through the porcelain
required,by
was

tube.
*

Liebig'sAnn., 1855, vol. xciv., p. 107.


t Comptea Rendua, 1856, vol. xliii.,
p. 921; and Aim,
1856, vol. li.,p.112.

de Chim,

et de

Phys.,

^'l :

LITHIUM.

According

author's

the

to

experiencewith

just described,lithium

kind

in them
electrolysed

for

and

other

short

that all the

so

with

time.

level of the fused

the
So

far

itself harmless
the

on

salt

and

of the

side

inner

readilyattacks

both

be
may
the
if
however,

the iron

the

of the

chlorides

Even,
from

surface
the

and

cover

makes

and

tube,

sheet-iron
which

below

apparatus
part of the negativepole.
is concerned, this action is in
are

form

soon

separationof lithium
the
; but, unfortunately,

the

as

crucible

the

portionsof the

iron

apparatus

metallic

insulated
negativeelectrode be initially
the
metal
floats to
crucible,
separated
electrical connection

23

becomes

metal

deposited

tube, and as lithium


alumina, the porcelaintube

sheet-iron

silica and

very
with

in contact
is so attacked
that it is soon
which the metal is now
rendered porous, and the inner surface of the iron then becomes
The result T)f
the principalseat of reduction for the lithium.

this is that the electrodes

porcelaintube. Such
continuouslyfor any
that

the

in

either acted
the

did

so

metal

apparatus

arrangement,
as

the

as

described

Troost

the very
that

negativepolefrom

cathode

shortof the

not, therefore,be used


may
length of time. There can be no doubt
an

electrolysis
(forTroost
from

and
separated,
insufficiently
through the porous substance

are

brought about

is
circuiting

does

wire),or,

mention

not

if it

insulated

were

it,the

crucible

beginningof
it

was

the

insulated

that
first,

at

it

short time
a
afterwards, for the reduced
very
the
surface of the liquidin
accumulates
rapidly
upon
within

sufficient

the

quantityto bridgeover

space

between

it and

the

electrode.

originalwire

Accordingly,in 1856, we find Troost* using "for the production


of metals from their anhydrous chlorine compounds, a closed
metallic vessel,which
also as negativeelectrode,
in comserves
bination
with a non-conductingand fire-resisting
vessel, which
the positive
is open at the bottom, and surrounds
electrode,with
the
electrodes
and
of conducting
of
two
the object
separating
the chlorine produced."
away
Hiller'8

the

Apparatus.

productionof

extraction
In

is

Hillerf has described

strontium
from

of lithium

Fig 14, t

"

that

is

an

apparatus for

well adapted
especially

to

its chloride.

porcelaincrucible

which

contains

the

fused

chloride. The cathode consists of an iron wire, of which


the end, k, is enclosed in the bowl of a clay tobacco pipe,p. The

lithium

lighterthan the
separates at k, and, being specifically
the
surface
the
collects
of
chloride,
liquid in the
upon
which
it
from
the
re-oxidation
pipe-bowl,
protects
completely
lithium

fused
that

otherwise

would

advisable, before
air

from

the

result from
the

contact

with

the

to
electrolysis,

air.

It

is

the

remove
commencing
pipe. To effect this, a glasstube, g, is attached

*
on
pp. 10, 11.
Compare Graetzel's claims in his patent specifioation,
t F. Hiller,Lehrbuch dtr Chemie, Leipzig,186.3.

24

BLBCTRIC

AND

SMBLTIMG

KEFININO.

cork ; beyond this is


of a perforate"l
pipe-stemby means
narrow
tube, "?. The
a
glasstube, d, leadingto a caoutchouc
second glasstube is fitted to the first with the aid of a cork at c,
tube is passed the iron
and
this cork and the outer
between
to the

electrode
small
the

The

wire.

glasstube
of

centre

at

the

wire

dy and

when

several

covering the

times

end, kj has

the

pipe-bowl,the

firmlyin
The

is wound

whole

been

around

adjustedin
is

arrangement

joint,c, with

the

held

plasterof Paris.

positionby
of perthe pipe is displacedby passinga current
fectly
bowl
the
caoutchouc
the
tube,
e
dry hydrogen through
;
pipe is then dipped into the fused chloride,the caoutchouc

air in

of the

Fig. 14.

"

Uiller

apparatus for the extraciiun

of liihium.

hydrogen generator,the bowl is


and
depth indicated in the figure,
with
rubber
tube
c
losed
It
the
is finally
a pinch-oock,
would,
q.
however, be still simpler to substitute hydrocarbon vapour for
hydrogen; to this end it would only be necessary to introduce
into the upper part of the pipe-bowl. On immersing
some
paraffin
the bowl in the melted
would
salt,the paraffin
vaporiseand
drive out the air before it through the caoutchouc
tube, ^, which
could then be closed by the clamp as before.
In order to prevent
the contact
of the separatedlithium with the walls of the pipe,
tube

sunk

is disconnected

which

would

the inner
The
with

from

into the chloride

lead to the contamination

side of the bowl

graphiteis first made


a

dilute

painted

over

the

to the

solution

of

is coated
into

thick

of the metal
a

thin

with

layerof

silicon,

graphite.

paste by stirringit well

chloride ; the paste is then


and after it has become
pipe-bowl,

lithium

the suiface of the

with

26

SMELTING

ELECTRIC

the

by

alkali

silicates

metals, in

AND

REFINING.

of the

consequence

reduction

the

of

them.

by

notable

ignoranceof past work in practical


is shown
electro-chemistry
by Guntz,* who, in December,
1893, presented to the French
Academy the descriptionof a
the followingaccount
is taken :
^A mixture
process, from which
of 200 to 300 grammes
of potassiumand lithium chloride in equal
an
proportions(fusingpoint 450' C.) is melted over
ordinary
burner.
When
Bunsen
fusion is complete the electrodes are
Guntz's

ProcesB.

"

"

introduced.
latter

The

anode

the cathode

of

is enclosed

within

applyinga

stands

which
fused

salt.

glasstube

at

obtain

To

20

thick.

mm.

10 amperes
for about
fluid column
of
a

than

more

the metal
of the

above

cm.

the electrodes

are

After
hour

an

lithium,

that of the

the
separated,

the fluid lithium

and
liquid,

The

wide.

ram.

meter,
dia-

in

mm.

glasstube

level of

is raised out

rod

3 to 4

tube

glass

in the

carbon

iron wire about

an

of 20 volts and

current

will be found

there

of

consists

which

floats upon the surface of the melt is removed


with the aid of an
iron spoon and poured into a dry ingotmould.
All this,however, had been
accomplished thirty years previously,
economical
only the earlier experimentershad been more
of electric energy, of which
they had used but one-fourth pai-t
of that

employed by Guntz.
already been shown,

has

As

of liUiium

extraction

those

be

to

observed

are

of

in

the

the

the

conditions

requiredfor the
simplest,as compared with
of

case

the

better-known

alkali

metals.
of

Treatment

lithium

Ijithium

minerals,

the chlorides

solution

Minerals.

In

"

is first obtained

of the alkali- and

the

treatment

which

contains

alkaline-earth

This

metals.

of

only
soln-

evaporated to dryness in iron vessels,and it should


alkaline in order that it may
not take up much
kept slightly
A small quantity
iron from the pans in which it is being boiled.
of iron salt in the resultingchloride is not objectionable,
ever,
howof the subsequent
for it is decomposed at the very outset
and
the
does
iron
reduced
not
electrolysis,
alloywith lithium.
tion is then
be

little sal-ammoniac

and

the

is fused

mass

may,

if

above

the

is

now

for

added

neutralise

to

in
electrolysis

an

any free alkali,


iron vessel,which

The
that shall serve
cathode.
desired,be the one
as
in
for use
ari*angement of the electrolytic
plant recommended
sodium
be
manufacture
the
If
or
magnesium
may
employed.
former
(p.12) be selected,the rim of the crucible which projects
which

flangeshould
is

water

produce

thin

crucible at the

lithium,which

circulated,in

with

order

to

keep

salt
layer of crystallised
upper

might
*

be surrounded

level of
otherwise

the

up

the

the

tube

it cool

upon
chloride
bath.

creep

ConipteaRendus, 1893,

metal

through

and

so

to

sides of the

Globules of
side,are retained

vol. cxvii.,p. 732.

27

LITHIUM.

continued

layer of solidified salt.


so
long that the lithium

between

the walls

this

by

anode

has

lithium

than

of lithium

case

connection

difficulties will

same

of the
After
of

the

of

in

as

there

extraction

necessarilybe

will

of the vessel in

the contents

of

that

in

that

occur

apparatus.
accumulated, the method

be exactly the same


procedure may
magnesium already described; but
greater loss of metal in pouring out
the

metallic

porcelainsheath

the

be

not

descriptionof Troost's

the

quantityof

sufficient

the

otherwise

must
electrolysis

forms

of the vessel and

explained in

were
a

carbon,

The

In

magnesium.

order

to

charge may be cooled in the melting


importantthat the latter should be made
salt loosens itself in solidifyconical in shape. The crystallised
ing,
be easilyseparatedfrom the walls of the crucible
and may
applied to the outer surface. The
by blows from a hammer
adhere
shots of metal
firmly to the inner wall of the vessel.*
of knives or scrapers, and separated
removed
by means
They are
from adheringsalt by melting them
togetherin a paraffinbath
ISO** to 200" C; the
which
is kept at a temperature of from
prevent

this

vessel, but

then

metal

whole

loss,the

then

it is

the

floats to

the

of

surface

bath,

whilst

the

salts

is removed
in
this bath the lithium
From
and
washed
in
afterwards
ladles
is
it
then,
benzene,
perforated
;
it is either cast in the shape of small
after re-meltingby itself,
under
gasoline(sp. gr.
rods, or it is pressed into this form

sink

to the bottom.

0*56).

It is

stored
finally

Kahlenberg'8

FrocesB.

in

sealed.
glasstubes hermetically
method

"

of

great scientific interest

by Kahlenberg,*
owing to the
use,
practical
unsuitable propertiesof the solvent employed for the electrolyte.
Lascynski and Gorskif had already,in their determinations

for the reduction


but

of

it

has been

of lithium

that

found
conductivity,

be

to

scarcelyprove

can

discovered

of

chloride

lithium

was

soluble with

dissociation in pyridine; and Kahlenberg succeeded


electrolytic
solution of these
concentrated
in depositingthis metal from
a

compounds, using
current-densityof

[0-013 to

carbon
from

plate as

20

anode,

and

employing

30

to

cm.

per
square
amperes
inch] at a pressure of 14
per square
ampere
lithium
under these conditions
being obtained in a

0*19

volts, the
metallic form.
dense, adhesive, silver-white,
be electrolysed
In a permanent installation the chloride would
the aid of the apparatus described in the chapterrelating
with
of that metal ; but in
to sodium, as suitable for the reduction
this
never

The

case

be

it must

be

high
depositionof
so

a-s

remembered
is

that the

employed

lithium

is effected

amperes
per square
of cathode surface,at a pressure

should
current-density

or

about

of sodium.
of about
current

extraction

by

[0*64ampere

metre

1,000

for the

per

square

5 volts.

Joum.
of Phy8, Chem., vol. iii.,
p. 602.
fZeitschr./iirMektrochem,, 1897, vol. iv., p.

290.

inch]

28

8MBLTIHO

KLBCTRIC

of
purification
that

the

metals

compounds,

to

metallic

considers

author

the alkali
the

the

be

the

for

REFINING.

described,as

electrolytic method

The

AND

well

product, offers

this way
purpose
the

simpler than

the

as

of

separatinglithium frcHQ
lithium
of obtaining pure
troublesome
separationof

lithium
The
obtained
solution.
salts in aqueous
metals.
alkali- and alkaline-earth
free from

Uses

of

Lithium.

"

Lithium

has

not

arts

on

is absolutely

found

applicationin
simplicityof the

of its high price. The


account
extraction
it out for
electrolytic
process marks
salts. The
of pure lithium
proposalto
the

subsequent
difficulty,

little

so

use
use

in the
lithium

production
for

generationof hydrogenin aeronautics (1 lb. of lithium affords


at the normal
25*5 cubic feet of hydrogen at 0** C. and
over
still be relegated
to the future.
must
atmosphericpressure)
the

2^

SODIUM.

SECOND
SODIUM

GROUP.
POTASSIUM.

AND

CHAPTER

III.

SODIUM.
in

Kature.
metals, sodium

Oocurrenoe

alkaline-earth

"

the

alkali -metals

Like

all

occurs

in nature

chloride,in rock-salt,NaCl

and

only in the form

fluoride,in cryolite,
;
Glauber's
salt,Na^SO^ 10H.p ;
AljFg.6NaF; as sulphate,in
as
borate, in borax,
as
nitrate, in Chili saltpetre,NaKOg;
and
other
borates
carbonate, in soda,
NafBX)^ IOH2O,
; as
NajCOj.HjO, and in trona, (NaHCOg)* NagCO- 2H2O ; as
of salts

; as

as

For
soda
the
manufacture
ot
pounds
comfelspar,"c.
the larger scale the chloride is mainly used; and
on
be obtained
either by a metallurgical
reduction
the metal
may
the carbonate
from
or
hydroxide,or by electrolysis
process from

silicate,in

chlonde.

the fused

Properties

of

the

specificgravity
pounds, and which
23 ;

hydroxide,is

white

Metal.

"

Sodium

0*974),which
was

(Na';

first obtained

metal,

the

atomic

is contained

weight

in these

by Davy

freshly-cutsurfaces

from

com

the

of which

be
silverywhite lustre ; it is soft and may even
at ordinary temperatures. It melts
at 95*6" C, and
red
heat
clear
about
at
at
900" C.
It
to
i.e.,
begins
vaporise a
of
forma
alloys with the other alkali metals, and with some
Of these alloysthe amalgam, and
the heavy metals.
the lead
of more
and tin alloys,
less importance in electro-chemical
are
or
ammonia
is also a simple solvent
practice. Anhydrous liquid
the
metal
with a blue
for sodium,
dissolvingin this medium
haloid salts of sodium, especially
Molten
the chloride,
oolotir.
have also the property of dissolving
the metal, and it is stated
of the compositionNagCl * is thus formed.
that a sub-chloride
of sodium
The fact of the solubility
in its chloride
is beyond
but there is as yet no decisive proof of the formation
dispute,
of this sub-chloride; indeed, the phenomena attendant
the
on
of fused
sodium chloride point much
rather to the
electrolysis
in
state
of
similar
that
metal
of gold in
to
a
solution,
being

exhibit
kneaded

"

Roee, Poggtndorff*8
Annalen, vol. xzxi., p. 133.

30

ELECTRIC

AND

SMELTING

KEFIMNU.

Sodium
oxidises very rapidly
glass*or in pure water.
be melted without
in the air,yet it may
danger in a dry vessel
that
heated
much
above
it
is
not
over
an
open flame,provided
it is ignited in air that is dry and
its melting point. Once
with
free from
carbonic acid, it bums
a
yellow flame, evolves
much
heat, and yieldsthe peroxide,Na^O.^.It also combines
It decomposes water
witti the non-metals.
even
energetically,
at the ordinarytemperature,forming sodium
hydroxide,and
stored
in
be
must, therefore,
oxygen-freeliquids,such as petroleum.
which
metal
As
can
a
water, it is
decompose even
attacked
by acids,forming salts which are, almost
very violently
without
It is a powerful
exception,easilysoluble in water.
reducing agent, decomposing compounds of the metals,and even
of many
non-metals
(CO^,Si02,BjO^,kc.).
of fused
After
the experience gained in the electrolysis
have
and
lithium
chlorides,attempts
naturallybeen
magnesium
the readily-purified
made
from
to obtain sodium
electrolytically
molten

sodium

chloride

in

the

molten

condition,but, up

to the

present,

practicalresults have not been entirelysatisfactory.Up to


of
for the reduction
the year
1890
purely chemical methods
sodium
used
of
in
oxidised compounds
were
practice.Only
here.
these
be
outline
of
can
a
slight
given
processes
very
the

PROCESSES.

BEDUCTIOir

a
largescale,sodium was first t produced by distilling
of anhydrous carbonate
mixture
(calcinedsoda) and carbon ;
of the metal was
whilst until comparativelyrecentlythe bulk
consisted
Castner's
in a reduction of
obtained by
method, { which
of iron and
the hydroxide by an
intimate
mixture
carbon,

On

thus

the

:
"

3 NaOH

Fe

Cj

3 Na

Fe

CO

COj

" avoided the use of iron by causing fused


carbon
contained
in
to drop upon
a layer of heated
furnace.
retort or reverberatory
Netto

3H.

caustic soda
an

upright

EIiECTBOLYSIS.

Davy's
the

Experiments.

hydroxidesof

"

The

potassium and

electrolytic
decomposition of
sodium

led,as

discoveryof these metals.


Davy||
his
which
for
research
he
employed
apparatus
to

the

thus

is well

known,

described

in this direction

the
:"

*
Zfligmondy; see ZeiUchr,/iirMeJdrochem,, 1898, voL iv.,p. 646.
t Brunner, Schtaeigger's
Journey vol. Ixxi.,p. 201 ; and St. Claire Deville,
Ann, dt Chtm, et "U Phys.^
1852, voL xliii.,
p. 5.
t United States Patent 342.897, June 1, 1886.
[Eng.Pat. 7,395,1886.]
Patent 45,105 and 52,555. [Eng. Pat. 17,412,1887.]
" German
H PhU, Trans, of 1808, pp. 1, 333 ; 1810, p. 16.

31

SODIUM.

"By

of

means

to the
applieid

flame

in

The spoon
the

of

containingpotash,this alkali

platina
spoon
minutes

gas from
spiritlamp, which was
of oxygene

stream

gasometer

thrown
for

on

kept
perfectfluidity.
with the positive
of
preservedin communication
the power
of 100 of 6 inches,highlycharged; and
from
the negativeside was
made
by a platina

strong

was

batteryof

the connection

red

heat, and

in

state

was

some

of

wire."
The

conduct

of the

largescale was not possible


by Davy ; and Castner,in
solve
the
first
to
the
was
1890,
apparatus problem,and so to
render Davy's process industrially
practicable.
Davy had proposed another method, in which a platinum dish
connected
was
containing
mercury
up as the negativepolein a
concentrated
solution of caustic potashor caustic soda,a galvanic
of current.
The alkali metal
battery
being used as the source
thus separatedby electrolysis
formed
an
amalgam from which it
the
off the mercury.
But
to be recovered
was
by distilling
of
not satisfactory,
to
metal
method was
the
bearing
yield
owing
too unfavourable
a
proportionto the expenditureof electrical
however, contained ideas which have
proposals,
energy. Both
since been
re-discovered
repeatedly
^namely,the use of a vesnel
of conducting nuUericU which should serve
simultaneouslyas a
the
the
and
one
as
for
of
poles
of the decomposim
electrolyte
receptacle
tion cell; and, further,the use
m
etallic
cathode to
of a liquid
absorb the alkali metal during ^
electrolysis
of its aqueous
with

apparatus

an

of

process

^e

on

type

used

"

solution.

OF

EL.ECTROLYSIS

SODIUM

CHLORIDE.

^The first suggestion


of
for the manufacture
Process.
Watt's
alkali- and alkaline-earth
metals originated
with Charles Watt."^
"

The
"

ran
patent specification
second part of my
or

obtainingthe

united

action

follows

as

The

metals
of

"

invention

consists of

of the alkalis and

and
electricity

heat.

mode

alkaline

of preparing

earths

For

performing
and
electricity
in Fig. 17, which
is
heat I employ a vessel of the form shown
made
of iron or other suitable material capable of bearinga full
A
is the vessel,which
should
red heat
In this figure,
be at
of iron, previouslyto its
least half an inch thick,and, if made
being used should be coated over its exterior with clayor other
by

this

the

part

of my

invention

substance to preserve
head

it from

collection

for the

by

the united

action of

the action

of the fire ; B, movable


with their
C, electrodes,

of the

metals

to support the vessel upon the furnace.


D, flanges
The covered compartment, F, being that in which it is intended
the metals,is suppliedwith a carbon electrode,
to eliminate
a^^-

attachments,

Eng. Pat. 13,766,Sept 26,

1861.

Ogle

32

ELECTRIC

the

uucovei*ed

but

I wish

the

form
particular
it is in

level shown

The
a

of

vessel

is

action

of

would

furnace

heat,and

the dotted

metal

where

it

when

can

is

be

apparatus supplying the electric current


intensityof which should,at least,be equal to

suppliedby

Fig. 17.

apparatus for the extraction

Watt's

"

temperature
the

will

it is

metal

the instantaneous

ensure

the

subjectedto
is in

state

currents, the

or

that which

would

eliminated,and

in-

of sodium.

but, of course, this depends upon the nature of


tensity,
which
is being decomposed. The fused salt is maintained
which

The

battery arranged for

Daniell's

cells of

ten

the

decomposing vesset and

the
be

[ihe

eliminated

eliminated,the

the saline matter


the

that

oxidised.

be

to

the

so

line

also excludes

the metal

the

between

be used

to

dry saline matter,

other,and

each

cause

is made

contact

material

it shall reach

in which

compartment

full red

the

to

gold electrode ;
myself to

restrict

not

figure]
; the partitionkeeps

placed in

of fusion

I do

apparatus,or

reactingupon

which

suppliedwith

that

of fusion

in the

the

access

REFINING.

vessel is filled with

state

substances from
air from

of

AND

is

compartment

it to be understood

for electrodes.
when

SMELTING

the

salt

at that

volatilisation

of

receiver

a proper
as
(sucha one
usuallyemployed for the preparationof such metals will
with the narrow
tube projecting
answer) is connected air-tight
The metal is received and preservedin any confrom the head.
venient
fluid hydrocarbon. The
salts which
I usuallyemploy
as

are
or

is

the

chlorides,iodides,or bromides

alkaline
The

describes:

of the alkalis

earths.''

salts which

compounds

of the metals

the

of
but

alkali-

neither

has
specification

used

the inventor
before

it been

and
nor

have
may
alkaline-earth

the

metals,

haloid
as

he

publicationof that
distil in an iron vessel the

since

possibleto

the

been

34

ELECTRIC

REFINING.

AND

SMELTIKQ

of alkali-metal
chlorides are
electrolysis
the
of a
lie
in
designing
chiefly
great They
unquestionably
the
of
The
the
tube
for
removal
durable apparatus.
sufficiently
in
of metal ; and porcelain,
chlorine must
not be made
especially
the
for
thickness
of
the
required
pieces
close-grained
purpose, is
at the high temperature employed. Then,
very easilybroken
if
the
tube
arranged to convey the metallic vapour to the
again,
of porcelain
be made
condenser
or
prepared
any other material
become
from clay,it will very soon
perforatedby the action of
condition.
But
the alkaJi metals
in the liquid or vaporous
a
Even
if the electrode,
metal
tube is equallyunsuitable.
6, were
be
insulated from the surroundingtube, the metal sheath would
be
that
of little value ; because,granted even
it might
possible,
by the use of sufficient heat, to maintain so high a temperature
and therefore the formation
that the separationof fluid metal

the

to

ariungement

"

of

metallic

would

be
necessarily

throughout the

tube

insulated

intermediate

side

of the metal

that

next

the

this is that

but

be

"

This

process.

avoided, there

be

the outside of the


the

from

results

fact that

tend to
placed in the electrolyte
the
between
surfaces
poles,the
electrolysing
the anode
next
functioningas a cathode,and

cathode

acting as

intermediate

The

anode.

an

reactions

of
consequence
produced,which cannot

are

working of the
durabilityof

the

prejudicialto

Under

b and

substances

metallic

form

c^ could
sodium
o
f
on
deposition

between

contact

the

these circumstances

process as a
the metallic

whole.
sheath

naturallyof the shortest. Later modifications of the original


in the arrangement of the electrodes and
construction,consisting
in the form
of concentric
of their separating partitions
tubes,
the difficulty.
have failed to overcome
In the year 1884, C. H. W. Hoepfner*
Hoepfher'8 Frooess.
patented a process, of which the followingis an account derived
chloride is melted in a crucible,
"Sodium
from his specification:
with a layer of copper or silver.
the bottom of which is covered
be employed, with
Instead of the latter,other heavy metals may
low
which
too
boils
at
the exceptionof mercury,
a temperature.
is

"

"

The

side-walls

crucible
the

The

serves

means

or

at

of
one

carbon

an

or

cathode

metal

metallic

burns

in the

of

metal

may

of the

presence
be collected
the

anode, forming
*

of the

fused

sodium

at

chloride

once

if the

distilled.

the
with

dynamo,
below

completedby immersing

now

in the

Patent

of

either from

introduced

chloride which

German

ducting
non-con-

some

bottom

is,therefore,connected

from

While

sodium

excluded, the

the
attacks

fuses at the

30,414.

above, a

sets in ; the

latter be

surface,the chlorine

upper

of
the

galvanicbattery,

air,but
or

at

or

or

rapiddepositionof

separates at

it

copper wire
If the circuit be

iron

side.

metal

of

anode, and

an

as

be made

must

layer

correspondingpoleof the

by
a

crucible

of the

material.

lightmetal
the

metal

high

tenx-

35

SODIUM.

of

the anode

weight
Even

the

operation,so that by continuing the


solution ; but on account
undergoes electrolytic

perature

the chloride
after

at the bottom

remains

current

of its

of the crucible."

short

experimental trial it can be easily


that,
long-continuedcurrent, the separation
does
not proceed as smoothly as it at first has the appearance
of doing,for the metallic chlorides do not remain
aj9 quietlyat
the bottom
of the vessel as
the patent specification
suggests.
With
the density of current
required for the depositionof
quite a

ascertained

with

sodium, the copper, silver,or


anode
would, in a short time,
in such

and
quantities,

in

so

other
be

metal

dissolved
the

re-depositedat

coherent
slightly

at

the

cathode

condition,that,

off again by the


it would
be washed
every precaution,
fused
and
of
in
form
this
salt,
(especially
apparatus)would be
the
would
there
be no
anode.
Not
returned to
only
chloring
evolution,which the invention aims at avoiding,but in a short
be no deposition
of alkali metal either.
time there would
has patentedthe apparatus
A. J. Kogers''^
Rogers' ProoesB.
in Fig. 19, which
shown
sectional elevation of
is a longitudinal
the whole
apparatus along the line y y (Fig.20),and in Fig. 20,
which
is a plan of one
portion of the apparatus along the line
B the fire-grate.
The
X X
(Fig. 19). A' shows the masonry,
which
is
with
be
C,
a
C,
provided
melting-pot,
cover,
may
in

spiteof

"

fsusten^ down:

the

on

middle

of

this

is

cover

funnel, c\

the
automaticallyby a ball-float valve, c, when
crucible
The
is sufiiciently
is
charged.
safety-valve,
Cg,
vided
prosudden
evolution
of gas.
to guard against risk from
a
The
D, is divided into two compartments
deoomposing-vessel,
material, such as
by the wall,"/,which is made of some
porous
chamotte, and reaches nearlyto the bottom of the chamber.

which

The

closes

between

and

D, and a
regulate the flow of melted material from C to
P the positiveelectrode ; the wire
D.
N
is the negative,and
for the electrodes within the cells are
connections
insulated,and
the attack of acid,gases, "c.,
time protectedfrom
at the same
tubes,n and p, in which they are respectively
by the chamotte
The tightly-fitting
enclosed.
D', is connected
by two
cover,
fitted
and
is
with four
necks, F F', with separate condensers,
closed doors at the pointsf f and /'/',shown in Fig. 20.
The
be
to
the
must
cf,
gas-tighteven
top of
separatingpartition,
up
the roof,D'.
Through the roof of the negative compartment is
the
passed
pipe, K, with the valve, ky by which hydrogen or
The
other
vessel,D, is set
reducing gas may be introduced.
tube, ",

cock, e,

serves

in thin

masonry,

forms

and

must

connection

to

be

constructed

of

non-conducting

1 foot wide,
and
material, and should be
fire-resisting
3 feet long, and
4 feet deep. The
decomposing-vessel bears a
that
of
to
Watt, but it is not so faulty in
strong resemblance

about

"

United

States Patent

296,357, April 8, 1884,

36
the
be

ELECTRIC

details

of

SMELTING

AND

its oonstructioii.

expected that

of the alkali metals

Nevertheless, it

advantageouslyused

be

it could

REFINING.

the material

; and

is

scarcelyto

for the reduction

of which

it is made

is

incompatiblewith great durability.The distillation of sodium


in clayvessels is an
undertaking of very doubtful expediency.
The
iron pre-heatingvessel,C, filled at a bright red heat with
melted
unserviceable
salt would, by its own
weight, become

Fig. 19.

"
F'
x_ir

rp

Fig. 20.

Rogers'apparatus
after

hours.

few

for the extraction

of sodium.

To

attach
the tube, E, sufficiently
firmly
clay vessel,D, and to maintain a tightjointwhen
the
whole apparatus is charged with fused sodium
chloride at a red
heat, would be no easy task. Rogers has, meanwhile, had an
the faults of the apparatus.
opportunityof discovering
Omholt's
Omholt's
Apparatus.
plant* (Figs.21 to 24) for
the continuous
productionof the lightmetals, appears also to
to

the

"

"
,

German

Patent

34,727, June

6, 1885.

37

SODIUM.

belong to

that

when

then,
patentee

are
opportunityoffers,

writes:

**The

"

(both in elevation

and

with

half

two

are

the

whilst

those

marked

marked

partition,

retorts,h and
such

enclose

from
the

22, consists

divided
In

a.

way
the

d,

into

of

two

of these

each

c, borne

supports, d

b b contain
c

and

hearth
a

parallelto one another on


material,placed side by side in
are
separated by a short space
half retorts

in

Figs.21

the

and

patentedand
test. The
practical
section
longitudinal
first

are

to the

shown

plan),in

in

reverberatoryfurnace,
separate compartments by

compartments

put

apparatus

The

which

class of inventions

horizontally
fire-resisting

of

that the half retorts


sole

of

the

hearth.

the

negativeelectrodes,e e,
positiveelectrodes,// The

lies melted
the hearth
on
halogen compound to be electrolysed
at such a height that the electrodes
in the half retorts are
pletely
comimmersed.
The metal separatingat the cathode, and the
halogen set free at the anode, collect within their respectivehalf
retorts, and are there protectedfrom contact with the furnace*
is formed
by the dipping
gases, owing to the liquidseal which
of the half retorts into the melted charge. The half retorts are
of a fire-resisting
and non-conductingsubstance,and are
made
the interior with a lining of carbonaceous
coated on
material.
The latter material consists for the most part of carbon (graphite
or
facture
used, for example, in the manuwood-charcoal)
; the mixture
of plumbago crucibles being suitable. The admixed
clay
to the carbon.
.serves
only to give plasticity
"The
electrodes are made
of carbon or other resisting
material.
tration,
They lie lengthwisewithin the half retorts,as shown in the illuswhilst at the one
side (at g in Fig. 23) they penetrate
the

of the furnace, and


there make
the necessary
nections
conmasonry
for the circulation of the electric current.
To prevent

separationof halogen or metal on the electrodes outside the


half retorts,the exposed portionsbetween
the faces of the retorts
and the brickwork
of the furnace
insulated
are
by a coveringof
cfaamotte.
By this construction,I [thepatentee]allow for the
the

renewal
or

of broken

half retorts

without

damaging

the

electrodes

alteringtheir position.
"The

half retorts,b b,are connected


with the fire-resisting
forechambers, kkjhj short tubes,hit,which should be as wide as

possibleand

which

best

placedvertically
; these tubes,h h,
of some
mixture
are
containingcarbon. The positionof
the upper
the level of the
edges of the tubes, hh, determines
melted
in
each
hearth.
The metal
the
charge
compartment of
the half retorts,b 6,
at the electrodes,
e c, collects under
.separating
are

made

on

the upper

liquidor
k

as

surface

vapour,
kj beneath, where

of the fused

through the
it accumulates

salt,whence
tubes,h A, into
in vessels

it passes, either as
the fore-chambers,

placed to receive it.


Each
fore-chamber, k, is closed by a mouthpiece,w, similar to
with coal-gas
those used in connection
retorts, through which the

38

vessel

REFINING.

pipe,/*,may be
metal, and replacedby

fullycharged with

sodium

Omholt's

empty

an

it is

when

withdrawn

the

placedbeneath

Fig.21."

AMD

SMELTING

ELECTRIC

one.

These

sectional elevation).
plant (longitudinal

Fig. "22. Omholt's


"

sodium

i"lant(plan)

xJ

Fig.23.
vessels
and

are

are

"

removed

allowed

to

Omholt's
as

sodium

plant(cross-section).

quicklyas possiblefrom

cool

either in

neutral

gas

the
or

fore-chambers^
in such

way

39

SODIUM.

air is excluded.

that

chambers,
The

"

after the

neutral

gas is also passed into


of air.
exclusion
complete
A

A:^ to the

halogensproduced

the fore-

half retorts,c c, are led away


the metallic vapours justdescribed,

in

of

the

removing
margins of the uprighttubes,II,projectslightly
upper
the level of the fused salt in the furnace,in order to guard
above
against an overflow of the liquid into the fore-chambers,mm.
but

manner

the

of a pipe connection.
halogen is conveyed from the latter by means
The halogencompound may be charged into the hearths
and either in the solid or in the
continuously or intermittently,
of the melt by
fused
condition.
To prevent the contamination
The

ashes
like

be

from

the fuel

muflBe

the

like,the

To facilitate the

blocks,o
of the

o.

make

to
practicable

Instead

electrodes
them

at

use

of

be

may

constructed

is
gas-firing

exchangeof

worn-out

be constructed

retorts, the furnace arch may

chamotte

furnace

The

muffle-furnace.

or

recommended.

half

or

with

or

also to

broken

removable

nections
arranging the electrical conin
it
is
more
side,as
Fig.23,
below, as in Fig. 24, where the

of
the

from

electrode,e, is supposed to be the cathode ; the anodes, however,


connected
are
similarly
up with the dynamo from below.
"

To

avoid

the

of the

use

of neutral

lightmetal

gases, I

[thepatentee]effect
the

surface

the

of the

accumulatingon
charge in the half retort, 6, in such a way that it passes
through the upright tube, /* (Fig.24), into a fore-chamber, k,
inactive
which
is so far filled with
a
petroleum
liquid (e.g,y
of the
the
that
curtain
of
wall,S,
high boilingpoint)
product
of the
the
forms
access
a liquid
seal,preventing
compartment, k,
outside atmosphere. The lightmetal flowing through h collects

removal

melted

40

SMELTING

ELBCTRIC

in

REFINING.

AND

be di*awn

vessel,Wy placedbeneath, which

movable

may
when
full,raised through the entrance, u v, of the
K, and replacedby another empty vessel."
a

far the

So

No
patent specification.

experiencein

the

fore-chamber,

who

one

out

has

electrolytic
separationof the

had

any
of the

metals

in vessels,which
are
placed in
and which are made
of such
direct contact with the furnace-gases,
described
half
will
the
material
retorts
are
Omholt,
as
by
porous
verdict
the
this
moment's
hesitation
to
a
as
nave
upon
process.

alkalis,
earths,or

alkaline-earths

furnace
in the reverberatory
have, especially
furnace-gases
in
favourable
the
of
most
just described,
opportunity circulating
whilst
with the fused chloride,
contact
intimate
they are only
of sodium
by a partitionthat is
separatedfrom the vapour
extremely perviousto gases. The rate at which the metal is
lyte
separatedis reduced in proportionas the resistance of the electroThe

the bath of chloride becomes


increases ; the rate at which
with oxides and hydroxidesbeing proportionately
very

loaded

great. This
the

hot

with
furnace-gases

diifusion

through

oxidation

is

latter circumstance
the

of the metal

the

charge,either

wall,and
partition
and

in

of the

result

part

the

to

directly

after

or

is in

of

contact

due

to

the

decompositionof

the

part

chloride.
The
for
from

diminishinglysmall yieldof metal that must be predicted


the proportionof impurities in the bath, increasing
minute to minute, and finally
causingthe completestoppage

it,and

of the current, would

alone

condemn

suffice to

apparatus of

an

description.In

this

favourable
passing un-

judgment
plant,no

has

account

the

of

losses

this

upon
been

taken

resultingfrom

that
greater irregularities
occur,

such

fracture

as

the
must

of

retorts

other evils.

and

F. Fischer*
Process.
Fisoher'B
has described his experiments with
"

the

arrangement
follows

as

divided

by
"

Fischer's apparatus.

the

level of the

melted

in

iron

three

electric

generator by
"

is

compartments

chloride

first division

salt in

is introduced
in such

into

quantity

the

closed decompositionthat of the line,a.


The carbon

may stand at about


as
anode, is either continued
plate,c, which serves
of the cell,or
makes
connection
through the cover

compartment

Fig.25,

crucible

I'eachtransverse partitions,
The dry
nearlyto the bottom.

alkaline
the

that

An

"

into

shown

two

ing
Fig. 25.

"

protectedmetal

wire.

An

iron

Jahrtsbericht,
1886, p. 222.
W"gaer'YiBohei^a

upwards
with

the

plate,",

42

RLfiCTRIC

"The

cathode

opening,the
the usual
chloride

is open

AHD

added,

RBFINIKO.

both

at

original
charge is

mechanical
is

SMELTING

ends; and through the


introduced,with the aid of

devices for such

and
a purpose,
has been
that which

to make

upper

any of
afterwards

decomposed
good
that the
in such a manner
during the electrolysis
; this is done
cathode
always remain
perfectlyfull of salt,which thus
may
forms a close cover
to the apparatus at this place. The lengths
of the cathode and of the anode, respectively,
chosen that
are
so
the weight of the chloride charge in the former
suffice to
may
maintain
the level of the liquidin the anode-cell at such a height
that all communication
formed
and

by

the

sleeve,S.

sodium

the

off between

is cut

The

chlorine

the two
formed

compartments
the

at

anode

produced at the cathode, during the


are
operation,
kept apart by the sleeve, S, the
progress
former passingto the tube, C, the latter to M.
In proportionta
the decompositionof the salt,fresh chloride sinks into the bath
from
the cathode, and
this is continuouslyreplacedby fresh
vapour

of the

above.'

additions
The

whole

combination
been
For

strikes

arrangement

of devices

serviceable

thoroughly
example, the use

of

of

amid

carbon

anode

vessel and

fortunate
unbeing a most
which
each separatelyhas
its original surroundings.

one

crucible

has

as

as

combined

successful

position
decom-

in the

proved
apparatus
employed in 1854 for the reduction of chromium
(see Chromium). The employment of hollow electrodes through
the solid electrolyte
which
might be charged,dates back even
farther,for J. H. Johnson's
tion
applicationfor provisionalprotecsuch an
in England, described
arrangement in 1853 (see
the
The
have
disco vei'ed that
inventors
now
Aluminium).
in
the
substance
the
tube
doe"
take
of
not
interruptedly,
place unsinking
and have
introduced
a
rotatingspiralwithin the
electrode in order to prevent stoppage. The separationof the
and of the substances
electrodes,
produced upon them, by means
chemical
old as electroof non-conductingpartition
as
walls,is a principle
itself.
decomposition
and halogen are
If the metal
to be separatedin Hornung
and
is
to replacethe short
it
Xasemeyer's apparatus,
necessary
and
provided
separatingtube by a cell closed at the bottom
with perforations
then the life of the
But even
at the sides.
it*
could not be very long,since the metal
iron crucible cover
which

Bunsen*

surrounded
substance

the heated

with

it is in contact
of

with
the

furnace

chlorine

which

gases
has

without, whilst
diffused

through

the

the
apparatus
Among
some
are
which, although they have
a few
faults,
yet possess the advantage of comparativesimplicityin
Grabau's
Apparatus.
Although the ideas embodied
these
of
inventions
it
is
not
are
some
undoubtedly good,
pos-

graphite

previouslydescribed

crucible.

within

there

"

"

Poffg.Ann., 1854,

vol.

xci.,p.

619.

43

SODIUM.

sible that

the

continuous

processes

work,

methods

employed
their hydroxidesor

could
could

nor

for

be

for
employed satisfactorily

they compete

the reduction

of the

with

the

chemical

alkali metals

from

of the

difficulty
of the process is shown
by the
application
able to produce
account
published by A. J. Rogers,* who was
2-5 to 3 kilogrammes [5-5to 6*5 lbs.]
from the chloride
of sodium
in 24 hours, providedthat the apparatus
per electricalhorse-potoer
The
durable
allow of uninterruptedwork.
to
toas
sufficiently
carbonates.

That

the

source

lies in the technical

Fig.2S.

"

Grabau's

apparatus for the reduction

electro-chemical efficiency
of the process
but the apparatus employed was
still

of alkali metals.

therefore

very high,
imperfect. In the same
was
published,Grabau
patented his
year that Rogers' paper
intended
was
apparatus which
primarily for the electrolytic
their halogen compounds ; the
from
extraction of alkali metals
In this
f was
patent specification
published on May 2, 1890.
A
surrounded
is
the
by
melting vessel, (Fig.28),
arrangement
*
Journal
t German

was

Inst,, 1889, vol. cxxviii.,p. 486.


8, 1889.
51,898, October
[English Patent

of the FranJdin
Patent

October 8, 1889].

15,792,

44

SMELTING

ELECTRIC

REFINING.

AND

air-bath,L, heated by the hot gases, which circulated in the


this vessel are
Within
it
a
bell-shaped
space, G, around
suitable
other
of porcelain
"cathode-cell,
or
B, made
fire-resisting
the carbon
are
material, and
positive electrodes,C, which
an

Arranged around

the latter.

The

is closed

whole

by

cover,
the wall, w, bulgesout
a

D.

and
lip of the cell,B,
N
of
the
fused
the
then
and
over
level, N,
upwardly
electrolyte.In this way a space is providedbetween the wall of
the cell,
melted matter
cannot
117 ; and
as
p, and the outer jacket,
From

the lower

is continued

penetrate this
the

with
that

outer

the

cell-walls

to be made

between

the cathode

salt does

space, the fused


surface of the

permit

can

the

melted

not

wall,f", and
any

direct

matter

into

come

it is thus

contact

impossible

electrical connection
and

within

that without

cell.

The electrode cell,B, is connected


by a tight joint,with a
the
hollow iron cap, E, from which
side
a
tube, a, passing over
rim of the

with the receiver,


makes
communication
meltingvessel,
electrical
and
makes
forms
the
negative pole,
cap, E,
with the fused salt by means
of the rod, n, placedwithin
contact
the bell. The screw-plunger
attached to the frame, H, is provided
The

SS.

for the purpose


in the
of removing any stoppages that may
occur
Since the alkali metals
are
tube, ".
lighterthan
specifically
their

chlorides

in the

fused

state, the

fluid metal

accumulating
of the
the
by
upwards
pressure
melted electrolyte,
and flows oflFthrough the tube, a, as fast as it
is produced. The collection may, for example, be effected in a
be
the cylinder,M, can
petroleum filled vessel,S, in which
filled with a neutral
through the tube, c. The
gas admitted
chlorine evolved at the anodes duringelectrolysis
escapes through
into the melting vessel
d, whilst the charge of salt is introduced
thix)ughe.
*
In a supplementarypatent dated September 19,1890, Grabau
of three chlorides (of sodium,
recommends
the use of a mixture
of potassium,and of an
in equivalentmolecular
alkaline-earth)
bility
proportions,the advantages thus gained being : a greater fusiof the mixture, the prolongationof the life of the vessel,
is said
and an improved yieldof metal.
The
resultingsodium
metal.
to be nearlyfree from potassium and alkaline-earth
tion
Grabau
approached with his apparatus very near to the soluof
of the problem of sodium-extraction
by the electrolysis
the

in

cathode

cell is forced

"

salt ;

common

fortunate
"

indeed,even in
circumstances, have

[EnglishPatent

16,060, October

this form
a

an

life of

9, 1890.

apparatus
several

In this

may,

days, or

under
even

Grabau
specification

sodium
cules
chloride for every 6 molemolecules of strontium
of the mixed
chloride was
alkaline
chlorides.
Strontium
preferred
to the calcium
salt,because it is more
easilyobtained in the anhydrous
The sodium
but
either
stale
be used.
barium
chloride)
(or
;
may

proposes

to

employ equi-molecular proportions of potassium and

chlorides,and

to

add

produced

contains

no

strontium, but may

retain

,3 per

cent,

of

potassium. Trans.]
"

4"

SODIUM.

weeks

; but

the

startingof the process would necessitate many


and every
breakages,
derangement of the plant that calls for a
the
of
suspension
might entail the loss of the whole
process
apparatus. The mixing of several salts to effect a reduction of
the meltingpoint is not new, for Bunsen
have
and Matthiessen
and
referred
the
the
be
to
said
same
frequently
principle
;
may
of

the

observation

that,under

metal

is alone

metal

and

alkaline-earth

In

the

author's

separatedin the

the

of KCl

he
experiments, which
obtaining alkali metals

intixxiuced

ihe socket
and

by
potassium.

Apparatus.

"

as

than

the very

reducingthe

^The

and

two

other

had

that

of

alkali metab.

in this case^
sodium

even

this salt is

apparatus

with

rather

fusible mixture

if fresh

decomposed,the

will
electrolysis

melting vessel,G,

tube,M,

double-socket

contain

used

only

is shown

in

opening surrounded
by
tubular
with
R.
necks,
openings

porcelaintube, J,

an

fitted into

the

socket,M,

N was
closed
again fitted the iron socket tube, N.
iron
which
the
iron
an
was
by
plug,through
passed

in this

above

fast

as

obtained

sodium

Borohers'
Fig. 29. The
The

with

Borchers' apparatus for

proportionof

small

he started

NaCl

be

alkali

of alkali

undertook

that
; but he has demonstrated
be
current-density not excessive,and
+

the
chloride
metallic
if

"

of mixtures
electrolysis

chlorides.

with
object of
producing pure sodium,

Fig. 29.

circumstances,the

certain

46

ELXCTBIC

rod, K
immersed

SMELTING

as
; the latter served
in the fused salt.

REFINING.

AND

cathode,and
The

was

therefore

partly

sodium

separatingupon the
cathode
upwards through the tube, ^,
part
And collected there until it overflowed
through the side tube, n,
into a suitable vessel placed to receive it. The
level of the
melt was, of course, maintained
high to enable the
sufficiently
the liquid was
overflow
and
of the sodium
to take
place;
of
preventedfrom forcingits way through the flangesby means
lower

of the

lead.

metallic
Within
And

the

the

porcelaintube, C, was
suspended,
the carbon
anode-rod.A, which was
again was
by the copper grip,H, restingupon the annular cover, D.

held

neck, R,

this

within

The

floated

chlorine

conducted

was

(notshown

tube

for the

served

through the tube, c. A


away
of
the
same
heightand width
Fig.29)

in

designed for use with


65
a yieldof from
possible.
theoretically
was

afforded
This

iron, at

chlorides

other.

tube

Of

found

was

become

per cent,

to

of the

50

and
amperes,
of
metal
weight

the

of furnace

gases

on

double-flanged
porcelaincomponents,
readilybroken, a fault which would
increased.
the size of the plant was
as

for

Both

"

side and

one

be very

to

BequirementB
Apparatus.

the

on

the

the

serious

more

possess

of 30

current

to 70

R,
apparatus

electrolyte.The

Cast
apparatus has not proved to be very durable.
the
effects
red heat, will not for long withstand
of
a

alkali-metal
the

of the

introduction

third
as

an

this

Eleotrolytio

apparatus

disadvantage that

and

sodium

Sodiiun-

Extraction

by Grabau

that devised

into

brought
inevitablybe
is

direct

loss of
for there must
a
porcelain,
aluminium
the
metal
the
action
of
by
upon
silicates at these points, whilst the porcelainitself is rapidly
be derived from the negative
corroded.
The
lessons that may
summed
obtained
be
results hitherto
may
up shortly in the
of a suitable apparatus
following rules for the construction
contact

with

sodium

caused

for sodium

1. A

extraction

:
"

refractorymetal only may

preferablythe

better

sorts

be used

as

the material

for the cathode

"

of iron.

be collected in, and conveyed from, the cathode


with any reducible substance.
"cellwithout coming
also as
chamber
be made
to serve
walls of the cathode
.3. The
may
with the electrobe in contact
lyte
not
they must
cathodes, but in that case
2. The

alkali metal

must

into contact

their outer surfaces.


be made
of carbon.
anodes must
5. The anode compartment must allow of an easy escape for the halogen;
material that will withstand the action
be made of some
and its walls must
of the halogensand haloid salts.
with the
6. The walls of the anode compartment must not be in contact
separatedmetal.
the
not have
must
7. The electrolyte
any metallic object in it between
the
current.
of
the
in
path
polesor
material
8. The whole
apparatus must be made of a fire-resisting
on

4. The

47

SODIUM.

conditions

These
of

apparatus;

one

improvement
in the

that

at

were

time

that introduced

was

his earlier invention.

on

of the cathode

arrangements

fulfilled in

by

Grabau

in

1891, as

It differs from

bell,so

that

forms

only two

it

this alone

an

only
now

requiresexplanation.
later

Qrabau'8
The modem
has

cathode

"

cell

wider

nally
space than that origithe bell
provided between

its bent

and

Apparatus.

Grabau

wall.

outer

arranged a
connectingpipes,Z

space
with

for the

admission
of

objectof
of

crust

this

In

coolingtube

is

and

and

removal

A,
spectively
re-

coolingliquid.The

this is to maintain
a thin
solidified salt upon
the

wall of the cell;and in order


that the crust may not become
too
thick the coolingtubes within the

outer

U-shaped jacket of
packed in

the

material

conductance

for

of the

having

heat.

to

the inner

The

fused

are

low
perature
tem-

salt within

the bell is maintained

high

bell

sufficiently

prevent solidification on
mous
walls,owing to the enor-

density of the current


passingthrough the

is here

that
trolyte.
elec-

Borehers'
Sodium-Extraction
^Another
Plant.
form
of apparatus
"

described

was

in 1893.
in

This

the author*

by

apparatus is

shown

Figs.31 and 32, which


one-eighthof the full

about

It consists of

two

togetherby

chambers
a

are

size.
nected
con-

specialjoint.

One of these,the cathode

chamber,
iron, whilst the other,
the anode compartment. A, is of
chamotte. Thus
the anode, a, is
K,

is of

providedwith

the cathode,
and
used

salt,or

obtamed

at

from

the

shapedcathodes
*

shield
which

through
cannot

within

cathode.
for

the

by

the

Grabau's

cathode

no

attacked

chlorine
from

modified
cell.

can

pass

without

the

to
the

by
metal
powerfully-reducing

It is in this way possible


to use
and removal
of the

collection

Borehers, Alkalimetalle,"in
**

which

be

"if^,30."

tube-

metal,

ZeiUchriftfur angewandte Chemics

48

ELECTRIC

AND

SMELTING

REFINING.

be produced
of which
is that the deposit can
advantage
the
nowhere
for
surface
is
in
inner
the
outer
side,
only upon
the

with

contact

the

electrolyte.

difficultieswere
encountered
between
vessels.
It was
the
joint
Great

and

Figs.31
R,

held

32, by

means

togetherabove

reallyimpermeable

material

DoolicgW"lier

and

Figs.31
^f
no

of
the
the

A,
the

an

apparatus

and

Wftter
Efic"pc-A|^-CooUDg

32.

Borchers'

"

is the

being

fluid salts.

The

able

Admission.

sodium-extraction

itself
electrolyte

material

other

first in

making a good
in
accomplished,as shown
metal water-cooled ring,
of a hollow
The only
below by the clamps,Z.
available
for such portions
that is
at

to

withstand

apparatus.

solidified

by cooling,
long the action
chamotte
portion of
for

breakage of the
apparatus is avoided by placingan asbestos washer between
water-cooled ring and the flangeof the anode
compartment,

the

in order

to

minimise

adjacent parts.

chlorine.

difference

the

tube, C,

sieve, S, with

is

little

of

temperature between

provided to carry off the


asbestos
restingupon it is

50

ELECrKIC

FigB.33,34, 35, 36, and 37.

SMELTING

"

Danckwardt's

AND

REFINING.

scxiiuin -ex traction

apparatus.

51

SODIUM.

admission

the

for

the

of

anode

heavy
j2, serves
A

chamotte
as

with

overflow
the bottom

order

drawn

B,

set

the

back,

the
has

gas

ky
receptacle,

iron

an

the

heat, and

loss of

dynamo by

of the

means

also the flow of the chloride

in

operation,the anodes. A, are


inlets,a^,c^,rf^,
e^,/^ are
The
hot
blast,
lighted.
t,
gas
gases, after
oflF through B k^.
When
a
high
sufliciently
furnace

of the water

been

attained

stopped,the

is

and

B,

into

tapping.

the

cocks

flow

temperature
blast

pipe,a\
escape-pipe,

to assist the distribution of the fused

serves

of

time

to

opened and
heating A,

floor,a,

bent

of

cover

of

at the

In

and

manhole, j\

negativepole of the

flowingfrom

material

The

to B.

of the

the receptacle is inclined


slightly
in
the
ends
on
and,
side,
f,
compartment,
opposite
k^,
of
A
series
iron
pipe,
arrangedvertically
plates,

the

towards

the

The

I J^,

leads,

^a8

by

jy with
plate,

means

compartment, B, consists of
with masonry,
(i\to minimise

connected

into

salt from

cover.

surrounded

on

fused

is cooled

cathode

The

the

of the

chamber

in the

chambers,

two

carbons,A, are

the

B,

forward

moved

into

A,

them
is well filled up with
loam, common
space between
the
blast
and
is
salt is introduced
through J^,
again lit. The
gas
and
flows
then
in
fresh
salt is added
into B;
sslt melts,
part
the

fused,the charge

until,when
overflow

the

The

pipe,k^.

reaches

almost

current-circuit

up to
is now

the

edge

of

closed,and

The
of the chlorine.
opened for the removal
the
of
lower
on
cathode, m, being
deposited
specific
gravity,rises through the fused charge,and flows through k"^
D.
Salt is added
time
to the charge from
into the receptacle,
has
of
that
which
take
to
been
the place
to time, as required,
decomposed. At the end of the operation,the current is first
from
until
the tube, c?*,
switched
off,the clay plug is removed

tube, j\

the

the whole
is

is

metal

alkali

of the chloride

has

off into

run

and

E,

the blast

then

stopped.
Instead

first

of

meltingthe

portion chargedmay
is then

which

burned

is melted, alternate
through j\ When
at

the

other
When

bottom

while

The

be

in

the

it is desired
chlorine

technical

to end

is the
the

The

aid

with

of

and

charcoal

are

completely melted,
floats
same

as

on

its

when

the whole
so

portion

charged

it remains

surface,D^.

as

alone is charged,
to

up.

be useless for

charcoal

use

In

is used.
gas-firing

of the salt is used

impure

proposal to
mentioned

blast,the
charcoal,

this

When

charcoal
operation,

is not

gas
layer of

of air.

salt

charcoal

carbon,until

produced

purposes.
apparatus is

covered

salt is

the

the

current

layers of

respectsthe process

instead of salt and

^he

salt with

for

heating

without
possibility,

only
actuallytried. But no charcoal available is free
from
salt contains
the commerciallypure sodium
ash, and even
the
introduction
of others
of
itself
without
sufficient impurities

having been

^with

the ash of the fuel.

as

52

ELECTRIC

inspectionof the

RKFINING.

Salt without
An
External
Firing.
this furnace gives the impression

of Fused

Eleotrolysis

AND

SMELTING

"

drawings of

and
warmed
by
apparatus used for electrolysis,
heat, and it is somewhat
electrically-produced
surprisingthat

that it is

an

of working, which
its
owes
quite recentlythis method
industry,has not also been appliedto
originto the aluminium
salt. A number
of common
of experiments in
the electrolysis
tried in Borchers* laboratory
this direction were
during the year
The first series of experimentswas
made
1899.
by A. Fischer,
until

and

the

them

following

extract

be

may

made

from

his

account

of

"

experiments of Grabau and Borchers, a mixture


of the chlorides of potassiumand
quantities
(equivalent
fusible than sodium
sodium) was used, the mixture being more
chloride alone, and the loss of metal increasingwith the temperature.
in the

"As

of salts

study

to

the

separationat
in which
rod

until

an

mutual
the

after
tried

The
the electrodes.
was
placed between
partition
of salts was
stamped into a sheet-iron vessel,and an
cathode
then caused
tx" approach a carbon
anode
was
arc

formed

was

which
electrodes,
salt

whether
globules,

flowing on

the

them,

so

that in

short

time

between

the
conducting
until
of
a well
graduallyseparated
(see Fig.38). The surprisingfact was

the

mass

.sodium,as

largeor

small

surface

soon

as

of the

it had

size,remained

of the stream

in the midst

untouched, even
cathode.

form

then

were

of

between

to

formed

was

observed, that

now

"

electrodes,
preliminaryexperimentswere

sufficient salt melted


molten

order

In
Chlorine.
and
chlorine

and
sodium

Sodium
of
action

no

mixture
iron

of

Action

"Mutual

fused

bath

for

united
a

long time

of chlorine
from

into

the anode

bubbles
to the

The

somewhat
flattened in shape ;
largerglobuleswere
when
the
close
anode
to
brought
intentionally
they remained
there for a notably long time.
The low specific
of the
gi-avity
sodium, and the colour of the metal burning with a yellow glow
under
upon the surface of the bath, facilitated ready observation
the conditions
of the foregoingexperiment,even
in the case
of
small globulesof metal ; and it is due to this circumstance
that
of loss
one, and that probablythe most
important,of the sources
in
research.
discovered
this
current-densities
the
At
was
readily
of small bubbles of
necessary for this work a very brisk stream
chlorine rise to the surface,and there unite to largerbubbles,
many

It

can

of which

remain

readilybe

through the

unaltered

for

comparativelylong time.
of chlorine in rising
of liquid. The
flow
a
accompanied by

understood

that the bubbles

bath are
of this is that in the lower

part of the bath there is


consequence
flow set up towards
the anode, whilst at the upper
surface of
a
the fluid charge the chlorine bubbles with the liquidadheringto
*

Zeitschr, fflrElektrochem,, 1900, vol. vii.,p. 349.

53

SODIUM.

them

tend

the anode

to flow from

to the

being entirelyindependent
This
flow of liquidis
of

iu;tion.

carried

far

tendency

that

the

If

gravity.

anode,

of the

cathode, are

spiteof

the

ward
up-

possess
low
specific
observed

be

bath

it appears
as
though the
tween
rises to a point situated bethe anode
and
cathode, and

sodium

not

to

though

the

cathode

from

this

itself,and

as

it is then

point

direction

The

to the cathode.

drawn
of

of the parthe flow of liquidand


ticles
of sodium
in the bath is shown

by

dotted

In

the

lines and

bath

sodium

from

at

6 to 10

Depositing

Apparatus.

of this

the
wide

to catch

the

globulesof

sodium

oflffrom

the electrode.

for

Figs. 39
copper

this
and

surface

enough
torn

hood

first

is shown

purpose
it consisted

40;

bell surrounded

ring through
placed between

round
sur-

hood

charge,and

The

come
outto

was

with

little beneath

the

of

of the fused

used

[2*4

The

"

experiment
cathode

the

tance
dis-

cm.

Modifioations

Fisoher's

globulesof

the

surface

the cathode.

from
ins.]

dipping

the

Fig.38.

in

arrows

used,

rise to
of about

"

in

above

from

to 4

the

chlorine

in

they

their

of

"x"nsequence

of sodium
and
chloride.

portion of

lower

direction

the

in

the

from

circulation

active

so

behaviour
Fig. 3^S. -Diagram illustrating
of fused sodium
in electrolysis

sodium, detached

cathode,such

produced by electrolytic
of
that the particles

that

which
the

with
water

was

inlet and

Figs.39

in
of

and

by

40."

Hood

Fischer

to

ployed
emround
sur-

in sodium
cathode
chloride electrolysis.

cooling
caused
the

outlet

to

circulate,a

for

the

partition

water,

causing

54

ELECTRIC

the water

to

hood

attached

was

which

formed

because

it

fuse

to

flow

dip

combustion
be

must

cathode.

found

wide

an

into

This

whole
to

ring.
the

iron

The
rod

was
adopted
loweringthe hood

arrangement

necessary before
of bath that, when

area

lowered, the bell

completely fluid

of sodium

of the surface

REFINING.

be

to

to include

as

The

area.

salt,for if it is to prevent the


surface of the bath its lower rim

the

at

far immersed

so

AND

the
through practically
of a sleeve
by means

the

was

so

should

SMELTING

considerable

proportion

objectof coolingthe edge

of the

bell

produce a solidified crust of salt on the rim, which thus


becomes
insulated,so that the separationof sodium is restricted
rod and also to any unprotected portions of the
to the cathode
inner surface of the hood.
The sodium
was
tapped off by means
of a pipe,as shown
in the arrangement illustrated by Fig.41.
The
effect
was
found, however, to be too great,for the
cooling
solidified
beneath
the hood, and sodium
salt soon
then appeared
to

was

Fig. 41.

"

Fischer's

sodium-chloride

the side of the rim nearest

on

much

so

heat,that the

the

to the

crust

separationof the

"Fischer

hoped to

this

overcome

In order

the sodium

was

ing
allowin patches,
away
take place at these places

melted

was

sodium

that all unnecessary


be dispensedwith, the walls of the
made

anode, and, burning,evolved


to

hindrance.

without
bell.

electrolysis
apparatus.

to act

made

made

were
as

cathode

oval in

of such
also

form, and

by
difficulty
partsof the

pipe used

thickness

the

so-

for the removal


pipe could

that the

(compare Fig.41). The


was

of

larger
apparatus might
use

placed over

the

hood

or

cathode

of
be
bell
that

positionof the front rim ensured the inclusion of all globules


within the space covered by the bell,so far as could be
of sodium
the

predictedfrom previous experiments. The front rim was also


sunk more
the hinder
rim, the sole
deeply in the bath than was
the
with
of
the
latter
exclusion
of
air.
even
being
But,
duty
side
sodium
of
the
this apparatus,
outer
soon
began to depositon
the coolingring at the part opposed to the anode, and quickly

55

SODIUM.

increased
which

the

quantity in spiteof

in

had

free

of anode

current

chlorine

to it at this

point.
that in the arrangeproved by various observatious
ment
hitherto adopted the copper bell acted as an intermediate
electrode
the first ; for although a soMd crust of
from
subsidiary
salt was
formed
immediately the cooled ring was immersed, this
It

"

was

crust at the

its

access

of immersion

moment

conductance
electrolytic
the

from

acting as

switched
formed
fused

the

on

rim

rapid
of the

under

material

the

at the

that

apparatus

electrode

be

was

sodium

earlysolidification of
thus readilyexplained;

the
but

given of the way in which


All metallic portionsof the

was

overcome.

l"e included

to

of

amount

the

bell,and
hood, were

not

were

the current

when

the

in

increase

indication

time
same
an
these difficulties could

that

warm

reduced
to presufficiently
vent
the
electrodes
between
placed

intermediate

an

The

on.

so

not

was

substance

metallic

thin and

so

was

in

the

system

of

con-

lIBiiii^
Fig. 42.
ductors

Fischer's

"

direction
vessel

before

was

again used

as

all

removed

from

as

the

bath.

possiblewith sufficient
Experiments in this
apparatus : The melting

of

"

in the

first

experiments ; and
water-cooling
arrangement

formed

by a
pipe for tappingoff the
(see Fig.42)."

was

led

experiments

of the
But
had

fused

in

allowed

apparatus,
a

to

material

the fractured
been

the

always happened
coolinghad been

far

The

these

charge

in

as
sheet-iron,

cathode

compartment.

as

followingform

chamber

solidification
whole

provided

marble.

lined with

sodiuiu-cliloride electrolytic
apparatus.

immersion

led to the
made
of

the cathode

But

be

must

insulation

modified

markedly

considerable

or

the

to

showed

at

the

here
The

cathode

of the mass,
after the
then
had
been

cool, and
that

characteristic

only

was

result.

same

commenced

surfaces

sodium

this

solidification

way,

whether

slightin extent.

the

layer

material
black-coloured
permeated with fine particlesof
sodium
from
the upper metallic surface of the portion
extended

of

56
which

been in the cathode

had

REFINING.

AND

SMELTING

ELECTRIC

to the

portionunder
compartments, just

compartment

bridgeseparatingthe anode and cathode


the one
to the otiber.
if a viscous material had flowed from
where
anode
ended
the
it was
This
in
compartment,
layer
rounded
off in a parabolic
curve.
Evidently the heat evolution

the
as

the

rapid increase in the


surface of the cathode caused
by
separationof sodium ; the
solid.
fused mass
became
first viscous, then pa^ty, and finally
the
viscous
which
the
in
was
mass
finely^iivided
period
During
sodium
doubtless
was
entangled in the pasty mass, and thus
when
the charge
of the latter,
the conductance
maintained
even

at the cathode

retarded,owing

was

to

the

in

cathode

the

cathode

extended

was

into

solidified.

had

compartment

this way
the
compartment, and metal

anode

the

In

separatingbridge facingthe
anode ; this metal would
then obviouslybe for the most part lost.
could have been overcome
by a timely
Probably this difficulty
at
increase in the current-density,
but, unfortunately, the time of
these experiments the strongestcurrent available in the Aachen
side

the

deposited

was

on

of the

laboratories

240

was

On the other
view

in

the

research,which

the

construction

of

and

long

working
sodium

s^^^
duced

would

involved

must

to

all,be
therefore

be left unanswered

It

apparatus
removed

appeared to

should

as

fast

accumulation
made

in

the

be

the

intro-

difficulties the
which

of

When

area

the

that

sodium

the

arrow

be

time

by

appreciably.This
shown
with

the

in
an

sake

the

should

it had

before

for
figure,

end

Fig. 43,
inclined
of

ness,
clear-

greaterthan was used


trolysis
slowlyrotated during elec(Fig.43),the sodium, as it

is somewhat

of tlie

not,

used,

by other workers
current-density

of cathode

is

The

the

but
spiralstaircase,

this electrode

in the direction

and

the cathode

with

that

formed,

was

moval
re-

would

present.
made

pre-eminentlynecessary

of the form

use

fashion

be

plane in place of steps. In


the angle of the incline
practice.

have

time

for the

constructed

so

it

as

to increase

gained by

was

in

loss of

unnecessary
this form of

Meanwhile, however, experimentswere


design an apparatus suitable for use

available.

smaller

and money.
described
apparatus last
may
if higher current-densities
be
satisfactory
an

questionwhether
after

stitution
sub-

apparatus

an

on

of
have

the

runs,

of

for

an

evolution

on
process for use
industrial scale,and

for

of cathode
collection.

was

of

an

Fig. 43." Specialform

hand,

objectof

of tne

apparatus

peres.
am-

58

ELECTRIC

from

which

they
But

apparatus.
above

within

the

Formation
attention
which

of

the

this

ladled
case

out

Sodium

Alloys.

electro-chemists

sodium

"

Fig. 46.

"

case

be

may

was

to

the

capable of

The

of Castner's

suspended from

use

early directed

of

alloyingas

Borchers* electric furnace

for

for

described

above

chloride

Borcliers' electric furnace

"

in the

as

cathodes

of sodium
electrolysis

Fig.45.

REFINING.

vessel.
electrolytic

of

in the

be

can

in

AND

8MELTIN0

fluid metal
it

culties
diffithe
with

separatedout.

experimentalwork.

experimental work.

have
alloysof sodium
only those with mercury
chemical
i
n
the
application
practical
industry. Mercury,
however, at the ordinary temperature, can dissolve only a small
proportionof sodium without losingits fluidity
; whilst,on the
low
that
has
other hand, its boilingpoint is so
it
only been used
the cathode in the electrolysis
of solutions of salts.
in practice
as
is merely an
the amalgam
intermediate
In this case
productsuch

Among
found

59

SODIUM.

which

becomes

produce a
is employed

final

the fact that such

and

does

not

works, but only one


product in metallurgical
of caustic potash or soda, there

of

to introduce

tried

Alloys.

salts; but

alkali

has

had

yet

"

fluid cathode

experimentallyas

this purpose

application.
Rogers* has given an

Tin-Sodimn

and

of fused
electrolysis

process

account
pages an
this end in view.

apparatus proposed with

been

for

these

into

Ijead-Sodium

tin have

for the
or

Taking

of mercury

in the manufacture

Preparation
metals

it is formed.

as

use

that

need
to be no
appears
forms of
of the many
Liead

fast

decomposed again as

consideration

into

any

no

ratus
appa-

permanent

experiment in this
direction,as follows :
During the last three years (1886-1889)
I have experimented on the reduction
of sodium
chloride,using
molten
Lead, tin,
negative electrodes,and especiallylead.
cadmium, and antimony all readilyalloywith sodium, a large
part of which can be recovered from the alloysby distillation in
iron crucible.
an
They can be heated to a higher temperature
than
sodium
acid crucibles without
the sodium
in
attacking
pure
the crucible.
In the followingexperiments a dynamo machine
used to supply the current.
In one
iwas
experiment a current
and
33 volts was
passed through molten
averaging 77 amperes
sodium
in two
crucibles arranged in series,
chloride,contained
of the

account

first

"

"

for

put
as

hours.

two

30 lbs. of salt ; in the first was


of tin,in the second 470 grms. of lead,each serving
contained

104 grms.
cathode, connection

crucible.

end of two
cooled and
of

Each

The

hours

broken

rod

made

open,

force

used

the

bottom

for the anode.

removed,

were

the lead

or

electromotive

through

used

was

carbons

the

17 per cent.
There
in the tin alloy,
between
or

sodium,

found

carbon

being

was

found

45 and
was

the

at

the

crucibles

96 grms.
90 grms. of sodium
per cent."

50

unusuallyhigh,but

of any indications
in the paper
apparatus, it is not possibleto form any
absence

the

to contain

about

were

When

and

of

as

to

idea

the

the

of

in the

size of the
current-

account, however, suffices to prove that


for the electrolytic
productionof lead-sodium
This

density employed.
method
a
practical
tin-sodium
In another
or
alloyshad thus been found.
paper^
himself
somewhat
to the
as
Rogerst expresses
optimistically
He expects
consumption of power in the extraction of sodium.
obtain
lbs.
the
chloride
from
fused
of sodium
to
to
6^
5^
E.H.P.
According to the results already
per
per 24 hours.
ever,
such
is
a
described,
yield scarcelyto be hoped for; he, howadds
the specialrestriction,"provided the apparatus is
durable
to permit uninterruptedwork
during the
sufficiently
time."
"

Proceedings of the WMC07isi7i Nat.

Aluminium.
t Journal

of the Franklin

Hist,

Soc., 1889

(from Richards*

Inst.,1889, vol. cxxviii.,p. 486.

60

ELECTRIC

The

AND

SMELTING

REFINING.

had

of devisingsuitable apparatus, which


difficulty

again become

hindrance

led Vautin

to progress,

to

thus

forward

put

do not call for


proposed improvements. His first patents''^
his
latest
be
referred
but
must
to, because
mention,
specificationf
some

it describes

as

England

far back

so

new

inventor, proposed

which

apparatust

an

1844.

as

to

Napier,

patentedin
the

was

fused

from

metals

separate

been

had
who

original

substances,

conductingmaterial, which
with
coated
down
to the
non-conductor
was
a
(slag)internally
This descriptionaccuratelydescribes
the latest form
bottom.
of apparatus described
and
illustrated
in Fig. 47by Vautin,
But
the absence
of any
apart from
originalityin Vautin a
cathode

using as

this

arrangement,
when

used

crucible of

for

work

durable in character
it is described in the

be

cannot

apparatus

the

for

some

which

patent specification.There
material
continuous

the

portion of

cathode

as

of the

cheap ;

but

because

apparatus.
Plant

which

i-atus

for

is essential

in

hollow
above

one

for the

consisted

below.

cone

provided

was

Soditim

with

The

The

receptionand

be

for

lining
Vautin

nothing
rejected,
in any

use

continuity
profitableapplication
electric-energy.

or

The

earliest appaproductionof a sodium-

Fig.48. The
short cylinderterminating
a
wall of the conical portion

of

inner

shown

in

terraced

formed

uppermost (and deepest)groove

melting of

metals.

the

to

Alloys."

which
projections,

another.

ture
mix-

and
operation,

author

lead,or
iron melting vessel,K,

to

it is worthless

applied to the
readilyfusible,alloy,is

the

other

if it cost

even

of heatBorehers'

being

fused

alkali-earth

still have

continuous
Vautin's

argued that the


Cmagnesia)used by

it would

"

vessel

in

nally
exter-

an

be

It may
material

Fig. 47.

with

salts of the alkali

haloid

metal, earth, or

is

of

surface

days,

few

no

survive

contact

vessel,the

fired

employed

for

in

is

could

even

use,

insulator

an

as

that

known

the

lead,which

was

gi*ooves,
served

introduced

The remaining
into the apparatus through one
funnels.
more
or
flowed over
intended
which
lead
to interceptthe
were
grooves

them,
enable

so

as

it to

to

one
electrolyte,

its surface

renew

take

up

as

often

greater proportion

of the mixtures

of

salts

as

and
possible,
For

of sodium.

alreadygiven

was

to

(Cf. Zeil nek riftfiir Elektrotechnih


English Patent 13,568, 1893.
Etelfroche.mie,1894, vol. i.,p. 139.
t English Patent
20,404, 1893.
Patent
X English
10,362, 1844; and 684, 1845.
"

to

the

be
und

61

SODIUM.

in the melted

used

condition.

The

carbon

anodes, A,

with

their

hung from the chamotte


tube-shapedporcelainshields,C, were
the
As in
analogousapparatus described previously,
cover, D.
rods were
the carbon
supported on the covers, c/,by the clamps,
also served

V, which
with

the

to make

positiveleads,P;

the necessary electrical connections


the return
leads,N, being connected

the crucible itself. The tubes,R, carried off the chlorine


up
and the melted alloywhich accumulated
generatedduring electrolysis,
with

of the

in the bottom

Fig. 48.
loss

"

operation had,

overflowed

by

the

The

pipe,X.

apparatus for the production of socliuiu alloys.

Borchers'

of salt which

cone

was

of course,

decomposed during the progress


to be made
good. In order

of the
to

charge,and to keep it in a fluid condition,the crucible


F, in a heating chamber
which, in
suspended by the flange,

the

form

here

system

of

shown,

had

been

found

to

be

economical

of fuel.

fuse
was

the
A

bustion
side-firing adopted ; the heated products of comthe
the
flue,H, passed into
enteringthrough
heating
was

chamber, and, being deflected upwards by the circular chamotte


W
and
baffle, W, returned
through the annular space between
furnace walls,M, findingan
exit by the flue,Z.
In order
the

""2

to

KLKCTHIC

catx:h any

SMELTING

that

matter

channel, S,
collecting
from

this the material

The

inner

should
built

was

could

be

in

AND

KEFINING.

leak

from

defective

of the

front

off at will.

pot,

and
fire-bridge,
For

small

mental
experisutHced.
burner
a largeFletcher's
installations,
gas
This apparatus has since been improved by the removal
of the
tubes, which are very liable to breakage and other
j"orcelain
damage. With this objectthe upper part of the meltinor vessel
has been
raised and surrounded
with a coolingring (Fig.49).

layer
the

of

wall

Fig.

49.

evolved

"

vessel

salt, which

solidified

chlorine

the

of

run

Borchers'

on

the

lead

may

be

becomes

surface

of

for

improved apparatus

introduced

the

with

covered
the

protects it from

sodium

The

thus

carbon

the

action

of

electrode.

productionof

alloys.

into the

uppermost

groove

of the

manner
formerly described or
above the firing
E,
melting
placed
separate
pot,
chamber.
is
The
connected
by a pipe, leading
alloyingcone
is heated by the
from the bottom, to a side reservoir,B, which
the alloy may
be removed
Hence
for use
flue gases.
waste
or

alloyingvessel,either
(ashere)from

after

the

The anode may


be made
for test,as desired.
carbon rod, or of several smaller rods.

either of

one

thick

63

SODIUM.

Fig. 49 shows the arrangement


A
plant of
large installations.
actual

size of the

of 300

amperes,

If

volts.

be

sodium

correspondsto

which

5000
amperes
The
surface.

illustration,is adapted

ahove

per sq. metre


electromotive

lead

required,the

per

sq.

more

electromotive

of
ft.]
be

required may

alloy containingnot

to

the

current

of
current-density

[465 amp.
force

for

recommended
of masonry
this kind, fifteen times

about

cathode

only 6

to

10 per cent, of
during the whole

than

force

exceed 8 volts.
process need never
would
have been very considerably
The cost of producing sodium
of
reduced
the cost
the
this
use
as
by
apparatus, especially

IB

jj)

Fig. 60.

Fig.61.

Apparatus for
of

the

than

plant

in the

would

case

the

have

of the

productionof
been

lead-sodium

less,and

alloys.

its

durabilitygreater,
correspondingplantrequiredfor the production

of pure sodium, if it had not been for an unfortunate


which led to unexpected losses.
The sodium
alloys
found to float on the surface of the
gravitywere
specific

circumstance
of lower
stream

of lead

flowing beneath

them,

so

that

alloyscontaining

8 to 10 per cent, of sodium


alternated
with others containing
Under
these circumstances
there was
scarcely1 per cent.
a
loss
of
sodium
the
of
the
metal
the
by
heavy
re-dissolving
on
from

64

ELECTRIC

of the

surface

the

overcome

alloyis
into

shown

AND

REFINING.

super-saturated
alloy. An apparatus designed to
the
in composition of the
of
difficulty
irregularity
and
in Figs.50
51 ; but it has not
been brought

for which

have

methods
lead-sodium

other

because

use

SMELTING

the

taken

the

place of

have

alloyswould

the process

been

useful,

questionhas diRappeared.
An
apparatus admirably adapted to the production of leadhis
But
from
sodium
alloyshas been described by Hulin.*
soda
the
the
direction
of
in
caustic
by
obtaining
experiments
of the resulting
treatment
alloyswith steam, it may be assumed
for the alloysin question.
that there is no very great demand
and

the interest in the

so

SEPARATION
The

OF

Castner

Prooess.

above

As

"

of caustic soda
electrolysis

for the

is

process

HYDROXIDE.

THE

mentioned, Davy's process

has been

of apparatus introduced

the construction

by

FROM

SODIUM

practicable

rendered

by Castner, t

whose

universally
adopted.

now

T.s^

Fig.62.
The

450

which

the

mm.

the cathode
somewhat
both

and

[1 ft. 6

cathode,
H,
in

and

filled with
this in

and

of

an

600

is inserted

part
800

consists

wide
ins.]

positionand

narrowed

wide
[31ins.]

"

Castner's electrolytic
sodium -extraction

apparatus (Fig.52)

about

it,are

"

mm.

to

of the

melting-pot,A,

[2 ft. high],into

mm.

bottom.

through the
the
ensure
a good joint,
vessel,with

the

time

before

solidifies.

To

hold

lower

tube, B,

[2ft. 8 ins.]
long,which

caustic alkali

short

iron

plant.

80

and
mm.

is attached

to

lysis,
startingthe electroThe

bath

of caustic

Zek9chr.Mr
EUktrochem,, and Jahrbuchfur EUktrochem,, 1894.1897.
Patent 53,121 ; and English Patent 13,356 of 1890.
t German

66

SMELTING

BL19CTRIG

AND

REFINING.

device, provided with the object of caosing the electrolyte


that
within
it to become
to solidify,
so
pastj, or, if possible,
the tube and the closing
escape at the jointbetween
The cathode, B, is of metal, or, if necessary, of retort

none

may
ring,a^.

shape,to ^Militate the


globulesforming upon it ; but it
escape upwards
be of any other shape that fulfils this object. Fig.54, for
can
example, illustrates a specialform of cathode, consistingof a
of rectangular,
number
square, or round bars,^, cast on to the
metal support, 6^,which
is attached
The object
to the rod, b.
of
the superficial
of this device is to increase considerably
area
the depositedmetal in a small
the cathode,and so to concentrate
and completely surrounds
The
is
anode, C,
ring-shaped,
space.
be made
in one
the cathode ; it may
piece or in several,and is
of the electrolyte
of retort carbon or of metal, accordingto the nature
with which
it.is to be used; it is suspended by one
or
These
more
rods,c, which serve also as conductors.
supporting
is made

carbon, and

conical

somewhat

in

of the metallic

rods

that

anodes

greater

they

must

heightmust
metal

not

not

surface

outer

reach

anode

the
to the

or

other

the cathode

separatedfirom

between

exceed

cone,

the

to

are

that

than

anode

The

fastened

so

are

by

itself and
of the

bottom

part of
a

the

the

distance
cathode.

vessel.A,

and

its

that of the cathode.

D, insulated from

the

apparatus, is

suspended

to collect the globules of


cathode,and is intended
the
the
the
surface
metal
to
of
electrolyte.Around
floating
edge of the cone is an upright,or nearly upright,rim, d, whilst
in the middle there is a risingtube of fairly
largediameter, and
This tube, e, is closed above either by a thick
with thick walls.
hinged cover or otherwise,and is provided with an exit pipe,/,
inclined slightly
downwards, and passingoutwards
through the
wall of the containingvessel,A, being insulated firom it by the
other suitable substance.
The
or
ring,/^,of asbestos,porcelain,

the

above

of the

diameter
that

of the

that

all

cathode

metal

cone,

cathode, B, and

D,

less than

globules which

metallic

be somewhat

must

that

become

greater than

of the

anode, C,

detached

from

whilst the gases


pass into the conical receiver,
The conical
around
the
outside.
escape

at the anode

D,

must

the

not

be

height of

immersed

the

in the

rim, dy so

so

the

generated
collector,

bath

to a greater depth than


electrolyte
may not cover
therefore
always exposed freely

that

upper surface is
to the air,and, in consequence,
any excessive rise of temperature
If the electrolyte
in the vessel should become
is avoided.
too
be
cooled
either by directing
of
a current
hot, the cone, D, may
the

cone.

The

the

to fall upon the


cool air upon it,or by allowingdrops of water
If
where
preferred,some
surface,
they instantlyevaporate.

system of coolingmay
Fig. 55 shows, by way

other

conical

portion of

which

be used.
of

example, a

is made

with

conical

double

receiver,the
walls, through

67

SODIUM.

which

is

of

or
a gaseous
liquidcooling-medium
coolingaction being the reduction of the
temperature to such a point that the metal produced does not
distil off,and, on
flowingthrough the tube,/, is not oxidised

the

"

a
pftssed

current

effect of the

outside.
The

is connected

receivingcone

by means
portionof

of

resistance

the main

so

current

the

negativeconductor,^,
only a very smaJl
through it. In this way the

to

calculated
passes

that

supplementarycathode,and the metal liberated


cathode becomes
at the principal
negativeagain as it rises in the
whilst it flows along in contact with the inner surface
collector,
becomes

cone

of

the

and

cone,

The

apparatus.

in

the

which

tube

between

space

the

it out
of
conveys
main
cathode, B, and

is traversed

supplementary cathode,D,
that the sodium
cannot
again become
; and

it

as

soon

forms, as

given by

of

way
for it.

If the
The

so

diissolved
in

the

by

contact

with

the

quickly
lyte
electro-

the cone,

D,

it were, a part of the negativeelectrode,


and cannot
shown
is only
by the bath. The form of the cone

be attacked

anode

fitted with

the latter makes

as

the metal

the

example ;
are

gases

vessel.A,

to be

shapesmay
the
collected,

providedwith

obviouslybe
whole

tuted
substi-

apparatus is

pipe.
or
on
supported on a foundiationof masonry
it the electrolyte
is maintained
in a molten
of heat generated from the current
passing
; but, as only the middle portionis thus kept

cover

other

vent

is

casting. Within
by means
through the bath
Since
to the apparatus as a whole.
a long life is secured
fluid,
the metal
the
i^
from
cooled
moderate
to a
tube, X
flowing
it is possible
temperature by one of the methods above described,
of any requiredshape placed beneath
to receive it in a mould
the dischai^ pipe,provided that the metal is not of too oxidisable a nature.
If, however, the metal is readilyoxidised,a
mould
which
be
used
be closed nearly gas-tight,
and
can
may
which
is providedabove with an opening through which the end
of the tube,/^,is passed.
a

condition

Bsthenau
have
best

Suther'a

and

observed

that

to electrodes

the

with

"

diaphragms

sodk.

are

The

not

Rathenau

and

Suther

lightmetals,especially
sodium,adhere
conical tops, when
or
dipped but

convex

In this
distance into the bath.
detached
even
by gases evolved at the
a

abort

Proceas.

the

is not
that
same
so
electrode,
of
for
the
fused
caustic
required
electrolysis
case

metal

sodium

be ladled from
then
the
separated may
it is allowed
into funnel-shapedvessels,where
cathodes
to
in
from
it.
The
soda
soda
entangled
separate by liquation
any
off through a valve at the bottom
of this vessel,
is then run
and,
the sodium
itself is tapped into moulds
finally,
through the
flame

outlet.
*

German

Patent

96,672 ; and EnglishPatent 21,027 of 1896.

68

ELECTRIC

REFINING.

AND

SMELTING

this process it is possible


with cathode current*
to work
to 10 amperes
cm.
[0*93amp. per sq. ft.].
per sq.
other results obtained
are
kept secret.

With

densities up
The

SEPARATION

FROM

NITRATE

SODIUM

(CHILI

SALTPETRE).
Darling's
of

Process.

the

experiment
with
saltpetre,

the

soda

320%

direction

the

at

attendant

on

of

of
recovery
the nitrate
the

of

temperature

300^

over

obtained

C,

from

the

lysis
electro-

hydroxide led Darling to


Chili
from
obtaining sodium
nitric

acid

melts

at

separationof

oxidising
agent

powerful an

so

results

sodium
readily-fusible
in

melts

The

"

may

caustic
The

culties
diffifrom

like sodium

metal

sodium

as

Whilst

31 S*" C.

at
nitrate,especially

have

doubts

rise to

given

the

of the process when


the patent specification
practicability
first published,but Darling appears,
nevertheless,
been successful in putting his invention
into practical
to have
an
him,*
shape. According to the account
mental
experipublishedby
posing
decomof
of
twelve
furnaces
plant,consistiug
capable
300 to 400 kilogrammes [6 to 8 cwts.]
nitrate
of sodium
to

as

was

in all per diem, has


chemical
of
works

been

in

since

use

in the well-known

1901

Harrison
Bros., in Philadelphia,U.S.A.
electrolytic
apparatus first adopted by himt was
led to the determination
not
but
of the
durable,
sufficiently
favourable conditions
for the separationof the sodium
most
the
that
sodium
shall
with the
into contact
not come
namely,
molten
nitrate.
could only be done by placing
This, evidently,
and
the
time
at
a
same
refractory
diaphtogm between
porous
After a long series of fruitless experithe anodes and cathodes.
ments,
the followingprocess was
adopted for the preparationof
the diaphragm :" Magnesia,which
had been fused in the electric
furnace, was crushed and pressedinto the hollow space between
The

of

form

"

walls

the

plates.
400

of

This

double-walled

vessel

760

mm.

pressedinto

place,the

thickness

Otherwise

diameter.

simplest. A

the

construction

of

cast-iron

of the
mm.

the

melting vessel,set
as
chamber,
anode; a layer,150 mm.
of refractory
insulatingmaterial was laid on
served

vessel,and
*

Joam.

tU.S.A.
March

20,

the

Franklin
Patent
1894.

above-described

magnesia had

the

of the walls

that the internal dimensions


so
[4 inches],
660
mm.
[26 inches]in height and 200
the

of

[15|inches]in diameter,and, after

mm.

been

was

perforatedsteel
[30 inches]in height,and

vessel, made

furnace

in

mm.

cylinderwere
[7|inches]in
was

of

simple firing

[6 inches]thick,
the

bottom

diaphragm rested

Inst.,1902, vol. cliii.,


p. ft6.
517,001, March
20, 1894;

100

was

EngUsh

on

of the

the middle

Patent

6,808,

SODIUM.

of this

layer,leaving a free space


the
melting vessel and

between

filled with

was

of

charge
wrought -iron

sodium
sodium

of about
the

nitrate,whilst

hydroxide.

tube

served

as

mm.
[3 inches]
diaphragm. This space

the

75

diaphragm received
length of 4-inch
According to the

short

cathode.

author's

of the years
patent specifications
1899-1900, an iron
also
the melting vessel and
suspended between
cylinderwas
diaphragm to serve as the true anode; but this cylinderappears,
the modem
from
to have been found
descriptions,
unnecessary.
in the accompanying Fig. 56.
It is,however, shown

Pig.56.

"

Darling'sapparatus
^

sodium

for the

extraction
nitrate.

of sodium

from

is heated moderately,and, during electrolysis,


electrolyte
yields sodium at the cathode and nitrogendioxide and oxygen
The

The
sodium
is ladled
the anode.
anode gases are collected and converted
at

"

of the

vessel,and

the

into nitric acid.

sheathing of the porous diaphragm obviouslyacts as


intermediate
electrode in the circuit ; in thus taking part in

The

an

out

iron

reactions
it would
electrolytic
clearlysuffer in respect of
this
durability. Darling obviates
difficulty
by diverting,
through
iron sheath
0*05 of the current
the
of the diaphragm, about
the

70

ELECTRIC

AND

SMELTING

REFINING.

passing through the whole cell,in such a waj that the iron
is charged positively
throughout the whole of the run.
The electric fusion of the magnesia for the diaphragm was
so
that
has
costly
Darling
finally
adopted, as a cheaper substitute,
of finely-ground
a mixture
clay,burnt magnesite,and Portland
The
cement.
cement
produced by castingthis mixture, after
the

addition

the

iron

and

useful

Each

of the

of

15

takes

volts.

of 400

current

amperes
heating is

External

and

USES

older

the

Among
of

uses

OF

average
in
necessary
of changing
time

chemicallypure

organicsubstances in the aniline


of compounds of the rarer
elements.
one

ceased

Its
time

use

in the

considerable

to

keep

The
the

be mentioned

may

the production

of
hydroxide,the reduction
colour industry,and the reduction
-reducible
more
or
difficultly

manufacture

of

quantitieswere

since the introduction

hours.

SODIUM.

of sodium
sodium

an

only

preparinga furnace for work and during the


the diaphragms, which
last from
425 to 450
now
heat produced electrically
in the furnace
suffices
the
charge in
rightcondition during the run.

at

lasting

diaphragin.

furnace

pressure

within

sufficient water, into the hollow


space
cell gave, after it had set, a very

of

walls

of the

H^ronlt

aluminium,

for which

required,has quite
Latterly,
process.

for sodium
for the
large demand
of
and
the
double
peroxide
cyanide of
Of
these
is
potassium and sodium.
compounds the former
and
substitute
for
barium
used
as
a
already widely
hydrogen
the
with
latter, prepared in accordance
peroxides; whilst
the
fusion
of
Erlenmeyer's reaction,by
potassium ferro-cyanide
with
sodium, K^Fe^Cyg + Na,
Fcg + (4KCy + 2NaCy), is
employed in the extraction of gold.

however,

manufacture

there

has

been

of sodium

71

POTASSIUM.

CHAPTER

IV.

POTASSIUM.
Oocnrrenoe
form

of

in

Nature.

In

"

salts,in

halogen

salts;as

it is found

nature

sylvine,KOI,

in

only
and

the

camallite,

in the alums, KjSO^.Al2(SO.)3.


as
KCLMgOVGHjO;
sulphates,
i
n
the
and
in mica
as
silicate,
felspars,
24H2O ;
KsAls^SiO^)^,
and
other
and
minerals
numerous
products of weathered
It

minerals.
processes

residues, such
the

play

to

appears
plantsand

of

animals

wood-ashes,

as

wool-washing
potash industry.

the

of

Properties

the

Metal.

when

lustrous

like

both

"

that

it is softer than

metal,

It
its boilingpoint are
fusing point
750'' C, the
700'' and
fuses at 62'' C, and
vaporisesbetween
colour.
having a green
vapour
Its chemical
propertiescloselyresemble those of sodium, but
the
violent in its action,and this is especially
it is usuallymore

and

its

weight

in

it is white

in that

sodium,

freshlycut, but

materials

raw

(K'; atomic

Potassium

and

valuable

are

"

39, specific
gravity 0-865)is

life

; and hoth vegetableand animal


and
the ashes
of beet-molasse;*,

from

suint

the

in

important part

an

in its reaction

case

Extraction
of
methods

with

manufacture,

chapter.

It should

reduction

of

material
oxide
reason

So

"

also, in

extractingthis metal

everything that

almost

lower.

water.

Prooesses.

in sodium

use

to

and

be

potassium

porous
found
in

is often
of

its

it may

has

been

carbonate

therefore

suffice to refer

that

the

and

been

carbonic

receivers, and

known

to

direct

carbonaceous

potassium with

of

retorts

preceding

in the

hydroxide by

or

the
way,
those
in
to

in the

written

compound

has
instability,

same

quiteanalogous

are

and

mentioned, however,

black

the

this,by
serious

cause

explosions.
In the

absence

of

sodium, lithium,and
of the

extraction
electrolytic
identical conditions

employed
with

that

to refer to

of

with

consists of
of

an

few

metal

those

observed

mixture

alkaline-earth
methods

of the
metal.

magnesium salts,the

is effected
for

under

sodium,

haloid
It will

almost

but the bath

salt of

potassium

therefore,
suffice,

especially
proposed for

the

extraction

potassium.
Matthiessen's

the

observation*

of
electrolysis
"

mixture

that
of

potassium alone resulted from


calcium
and potassium chlorides

Liebtg'sAnn", 1866, vol. xciii.,


p. 277.

72

ELECTRIC

was

interesting
; but

in the

SMELTING

salt

advantagesobtained from the redaction


potassium chloride by the addition of the
than balanced
by the difficulties which
of mixtures
containingcaldum
electrolysis

more

are

the

always accompany

BBFININO.

the

fusingpoint of

calcium

AND

chloride.
linnemann's

cyanides.
a

crucible.

decomposition of
plateto a pointed
passes
which
is kept melted
potassiumcyanide,
depends

from

current

rod immersed

carbon
in

method*

The

in

the
upon
a carbon

temperature be

If the

surface of the bath

upper
will accumulate

remains

so

the
solid,

controlled

that

separatedpotassium

The
under the crust.
high cost of the
renders
material,however,
unnecessary
any remarks
upon
of
practical
utility

processes
reference may be made

and
have

of Potassium.

reactions,the

the

raw

the

the process.

All other

Uses
of its

the

alreadydescribed under "sodium," and


in that chapter.
to them

are

"

On

hitherto

account

of the considerable

dangerous

method

of

violence

production,

the applications
of potassium
highpriceof potassiumsalts,

remained

to be written
*

that there is practically


insignificant
nothing
concerningits use industrially.
so

Joum.

fur prakt,Chetn.,1848, vol. Ixxiii.,


p.

416.

74

ELECTRIC

SMELTING

BEFININO.

AND

phosphide ; the arsenide,gaseous and black solid hydrogen


arsenides;the antimonide, only solid black antimonetted
gen
hydrothe bismuth
black
a
compound, hydrogen and
; and
insoluble
whilst
attacked
the
silicide,
slowly
compound ;
only
of
with
acids
mixture
dilute
a
by water, rapidly evolves
hydrogen and hydrogen silicide. It is noteworthy that the
gen

direct union
at

red heat,but

dull

high

that

melted

'with carbon

of calcium
the

that

the

carbide

commences

reaction

temperature

fuses.

Calcium

resultingcarbide

sodium

to form

rises

so

dissolves

in

in

out again
potassium)and crystallises
nickel
tin.
and
cooling.
magnesium, zinc,
The
with
crystallineamalgam formed by trituratingcalcium
in an
takes up
atmosphere of carbon dioxide at once
mercury
and
and
when
the
becomes
air,
nitrogen
exposed to
oxygen
covered
with
a
grey-blackfilm; it is indifferent to hydrogen

(butnot

It

on

alloyswith

temperatures below

at

of

400** 0., but, when

nitrogen,calcium

but
fluorides,

or

alkali

metals

their iodides.

from

not

is formed.

nitride

red heat, readilydepositsthe

heated

in

an

phere
atmos-

Calcium,

at

their chlorides

from

It reduces

the

calcium

Further, calcium reacts, when


heated,
oxide, phosphorus pentsulphur dioxide,
oxide, boric acid,silicic acid,carbon dioxide,carbon monoxide,
trichloride,acetylene, ethylene,
hydrogen sulphide, boron
methane, and the compounds of hydrogen with the halogens.
It reduces
fuming and anhydrous sulphuricacid in the cold,
chloride and

iodide

sub- salts.

to

with

nitric

is dissolved

and

in the
gas,
solid
when

forming
white
cooled

is also

"

propertiesof

pure,

as

yet,

is indifferent

in

it,it decomposes

nitride

be

not

It forms

hydride.

been

monia
am-

the
a

examined),

further

ammonia.

metal, the

other

propertiesof

mind

the

later determinations

strontium, the
which

older

statements

has not

of the
as

to

produced
calcium
and
have
as
quantities
great
with
caution.
accepted
The
the
Metals.
separationof the three

of
Extraction
of the alkaline

very

(a

metal

been

"

earths

from

their oxides

or

as
compared
great difficulty
*

alkali metals.

and

to

such

metals

with

in

and

barium

in

strontium)must

attended

It

heated

presently.

Keeping

propertiesof calcium
the

acids.

soft white

will be studied

Barium.

of

mixture

when

compound (which has


to 40*" C, with aqueous

Strontium

which

by hydrated

cold, but,

the

first to

haloid

with

salts is

that of the

lytic
accomplishthe electro-

Davy
moulded
He
the
decomposition of the alkaline earths.
with
mixed
either
alone
mercuric
moistened
or
hydroxide,
oxide, into the shape of a small cup, rested this on platinum
foil,which served as the positivepole; he then poured mercury
this the negative pole.
made
of hydroxide,and
into the cup
the mercury
could
thus produced,from which
An amalgam was
"

was

Phil. Trans,, London, 1808, p. 335.

be

expelled by

it would

by

the

the

from

decomposition

had

given

and

these

cause

of these

Bunsen's

in

the

in

extraction

He

that

at

magnesium;

of

course

of

discovered

1854, Bunsen

in

previous failures.

long
laboratoryto

until,in the

continued

prepare

For

apparatus which

the

in

metals

chromium

metallic

on

his

condition.

pure

made

good results
experiments were
of

the

Matthiessen,

and

the first to

chlorides,

in
were

chlorides

Bunsen
were

such

his researches
the

metals

attempts

the
electrolyse

the

the

ot

fruitless

silicon.

and

mercury

alkaline-earth

time

According to subsequent investigationB,


Davy did not produce a perfectlypure

heat.
that

seem

metal, free

75

BARIUM.

STRONTIUM,

CALCIUM,

time

published

ditioned
followingnoteworthy observation,* which has since conof electrolytic
positions
decomthe success
of a large number
:

"

**The

densityof

relation

of

important
current

to

density.
the

volume

current

influence
overcome

constituents

"

electrode

to

its chemical

on

electrolysisthat is,the

used for

the current

area

exerts

"

The

effects.

most

power

of the

(chemical)affinities increases with this


of
Of no
less importance is the relative mass
which
the
of the electrolyte
current
through

passes."
In

the

Bunsen
treatise,

same

that

showed

sufficient

by using a

current-densityit is even
possibleto separate calcium and
barium
from
concentrated
solutions
of their chlorides,
boiling
acidified with hydrochloricacid.
As negativepole,he used an
immersed
wire
under treatment.
in the mass
amalgamated platinum
The latter was
around
stood
which
placedin a clay cell,
carbon
a
crucible,partly filled with hydrochloricacid, and set
within a porcelain
crucible,the whole arrangement being heated
in

and
the
even

water
as

bath.

The

carbon

electrolytecell.

after

few

both

used

was

as

anode

was
difficulty
experienced in
chloride
by this method, because,

calcium

of
electrolysis

crucible

Great

minutes,

the

electrode

with

covered

became

It was, therefore,
interruptedthe current.
the
the rapidlyremove
platinum wire,
necessMry
dried coating of amalgam, and then re-amalgamate it. Barium
15
in quantitiesof about
amalgam may readilybe obtained
made
barium
into a paste
grains by using crystallised
chloride,
with weak
hydrochloricacid,at a temperature of 100' C. For
these ex|"erimentsa current-density
of about 1 am|)ere
per sq.
a

crust

of lime
to

mm.

which

lift out

[645amperes

per sq.

Matthiessen's

in.]of

Experiments.

Matthiessen,t working
1855, obtained the metals

year
pure condition
He writes that

by
:
*

''

the

direct

Although

cathode
As

"

in
of

surface
a

result

Bunsen's
the

treatment

the reduction

is necessary.
of these experiments,

laboratoryin

alkaline
of the

earths
fused

in

the
the

chlorides.

is easy, it is difficult

Ann,, 1854, vol. xci., p. 619.


Poflf^.
t Liebig'aAnn., 1865, vol. xciii.,p. 277.

76

ELKCTRIC

to obtain

it from

SMBLTING

the reduced

the fused

REFINING.

AND

met"al in coherent
The

substance.

masses,

and

to

separate

for the most

depositedmetals

part rise

to the surface, by virtue of their low specific


gravity,
they have grown to globulesof appreciablesize;and there
they burn so quicklythat it is almost impossibleto collect them.
If the end of the electrode be providedwith a bell-shaped
ment
attachof glassor burnt clay,
in order to collect the metal, the latter
reduces a small quantityof silicon,
which
separates in the form
of a black powder, and prevents the metal
from
unitinginto a
regulus."
He
of overcoming this difficulty.
proposed three methods
The firstmethod, by which, however, only a very impure metal,
rather an alloy,
of a platinum
is obtained,consists in the use
or
alkaline-earth
metal
thus
wire
The
the negative pole.
as
becomes
so
alloyed with platinum, and
acquires a specific
sink
enable
it
to
to
gravitysufficiently
through the fused
high
chloride.
After coolingand breakingup the mass
the metal is
obtained in the form of largegrains.
A Becond plan is to melt together two
chlorides
in simple
chloride
is
which
double
molecular
means
a
proportions,by
that easilyvaporised metals^
produced of so fusible a nature
like potassium or sodium, may
be separated in it without
crucible
A
is used for the experiment,
volatilising. porcelain
and
if the temperature be so
regulatedthat a solidified film
forms on the upper surface of the mass
around
the negativepole,
this film,on
cooling,will be found laden with metallic grains,
which
be
readilyseparatedfrom the surrounding material
may
of the crucible
by crushing the whole of the cooled contents
under
be
in
The
metal
will
visible in the
mortar.
a
petroleum
of
small
laminse
the
amid
shape
pulverisedmass.
platesor
The
third way
is based
the
on
separation of the metal
immediately beueath the surface of the melted chloride by an
electrode consistingof a pointed iron wire, which
to
serves
surface
the
the
well
metal
that
on
as
as
remove
floating
upper
clingingby adhesion to the point of the iron wire.
By this
method
from
the liberated metal
tion
oxidais sufficiently
protected
varnish-like
film
of
molten
chloride to enable the
by a thin
seed.
to increase to the size of mustard
particles
The followingmethod
of reduction
Extraotion
of Calcium.
is exceedinglyuncertain
in operation; but when
successful it is
of
of
calcium
somewhat
capable yieldingfragments
largerthan a
of two molecular
''A mixture
weights of calcium chloride
pea.
of
with
strontium
salone
chloride, and with
equivalent

before

"

ammoniac,

is melted

constituent

has

positivepole,is
within

this

in

Hessian

volatilised ;
then

crucible
iron

placed in

is immersed

long,previouslyheated

an

to

the

narrow

red heat.

until

the

last-named
the
as

to be used
cylinder,

melted

salt

mixture,

and

clay cell,about 4 inches


The claycylinderis filled

CALCIUM,
with

the

fused mixture

same

salt,and

of

77

BARIUM.

STRONTIUM,

for the

serves

tion
recep-

negative pole,which may be either an iron wire of


If it
carbon rod.
about
the thickness
of a knitting-needle
a
or
be arranged that the level of the fused chlorides in the clay
cell is about
| to 1 in. higher than that of the liquidin the
crucible,the heating may, with ease, be so regulated that a
the surface of the liquidin the cell ;
solid crust forms only on
the crust without coming
and the metal will then collect beneath
of the

aU

at

all his

the

of the

elements, such

as

cell.

after the

however,
size of

of from

space

half

With

used

reduced

calcium

hour

an

to

pea,
found

was

"Calcium
and

to be

obtained

be

may
with

in

small

been

almost

distributed in the form of


in separateparts of the cooled and crushed slag.
metal

molten

current

in

hour.

an

had

coupleof pieces,which
obtained by this process ; and

were

the

Matthiessen

experiments,a largequantity of

obtained
once,

the walls

with

in contact

six zinc-carbon

from

nearly
may

be

Only
fused

to

always the
fine powder

globulesmore

in a
simply
greater certaintyby fusing the mixture
small
over
porcelaincrucible heated, as in ignitingprecipitates,
between
a spirit-lamp
or
lumps of charcoal,and then passingthe
from a carbon
which
current
electrode,
through the electrolyte
should
be as largeas possible,
wire
to a fragment of pianoforte
to the
only two lines long (No. 6 size),which is connected
wire
far
the
stouter
as
a
as
reaching
negative pole by
upper
of solidified salt should be
surface
of the liquid. A
crust
allowed

to

be removed
in order

form
from

that the

the surface around


this wire, which
upon
may
intervals
of three minutes)
time to time
^at
be detached in a mortar.
may
the
similar way by so stirring
with
chlorides
the point of the wire

and

crust

metal

be reduced

*"'The metal

in

may
surface of the melted
upper
for from one
to two minutes, that

glow,produced by the current


point. Or the point of the wire
first dipped into the liquidand then raised

is observed
itself,

alternations

efiect

the

is observed

arc

at

coolingand strong

of

fusion

the

around

be
at intervals,
may,
until a small electric
cause

the

of

metal

that

the

surface ; this will


heating,which should

has

been

deposited in

form.
pulverulent
''Calcium
sodium

or

calcium

of

molecular

reduced

is not

from

its chlorine

compound by
weight
of sodium
chloride, or equal
and
potassium chlorides and
molecular

potassium. By fusingtogetherone
chloride

weights

and
of

two

calcium

melts
at
sal-ammoniac, a double chloride is obtained, which
the
below
either
of
sodium
a
vaporisingpoint
temperature
or
a

potassium. If
bright red heat

such

cathode,

number

of

to

form

wire

aodium
should

will be

with

seen

[sodium]mixture

a
a

at
electrolysed
pointed ironcomparatively large globules of

carbon

only just dip into the

at

anode

the

be

and

end

and
liquid)

of
to

the

rise to

wire

(which

the

surface,.

78
where

they
be

can

will

below, and
These

part of the

it will

if it could

crucible

conditions

recommended

form

of the

(p. 9), but the fusion


accomplishedin this
yet
been

Strontium.

of

Extraotion
accounts'*^ the
difficult.

ammoniac,

so

by

positivepole,and

into

the

that

Matthiessen's

to

with

touching the

side

Matthiessen

had

are

in the cell may

which

to

The

serves

short

If the

less
it

little sal-

crucibla

is fastened

clay
the

as

and
a

very
thicker
far

with

will collect

under

thin
wire
the

as

temperature

cell is covered

strontium

be

to

placedwithin

mass

in the

beneath.

in the

mass

material, the

pipe-claytube, reaching as

projectingpieceof thin wire


regulatedthat

of the fused

latter

to

mixed

cylinder of iron
the cell is dipped a

iron

solidified

to

mixture

of nesium
magregulus has

appears

clay cell

wire ; the
is enclosed
in a

which

calcium

chloride

than

level

cell is surrounded

piece of

arranged

for the extraction

According
a

strontium

that the surface

higher

be

containingthe

strontium

crucible and

anhydrous

at

contain

way.

"

of

production

small

filled with
stand

globule

to

very

of the

not

If such
found

be

high temperature, without fusing the


calcium
might be melted to a regulus
be preferable
would
then
to any other.
process
of irregular
heatingare easilyfulfilled by using

this

crucible

bath,

burn.

surface,the

the

on

and

opinion that

of

w^^s

under

SCaOlj + SrCl^ to
crust

REFINING.

of calcium."

trace

the

the

from

Matthiessen
heat

AND

slowly circalate

removed

scarcelya

8HBLTING

ELECTRIC

be

so

of

crust

the

crust

walls) in fragments that may


much
7
8
be
or
as
as
grains. Barium, however, can
weigh
obtained
fine
only as a
powder by a process analogousto this.
The
in Gmelin-Kraut's
der anorganiachen
Handkuch
statement
(and

without

Chemie

f that

The

of

sources

metallic

barium

in

seed,adhering to an iron electrode


chloride,is founded on an
information! quoted contain no such

globulesthe size of mustard


of fused
by the electrolysis
error.

obtained

barium

statement.

Matthiessen's work.
described in the chapter on

So far Bunsen's
the

apparatus

and

suitable
specially
as

the

cases

sunk

to the

found, on
the metal

bottom, and

crucible to

itself to

strontium

it will be

greatestpart of

the
the

it has shown

production of

most

reduction.

for strontium

silicon

that
and

in

be

for

Hiller

recommends

lithium

(p. 23) as
satisfactory
Nevertheless,

is useless for
piecesof appreciablesize. In

breaking

lithium,it
the

at
separated

it has

the

there

aluminium,

that by
crucible,

negativepolehas

reduced
or

far

even

the walls
that

of
it has

323 ; and QuaH. Jounu


Chem^
vol viii.,
p. 107.
der anorganiscJien
Chemie, vol. ii.,
t Handbuch
p. 255 (Ed. 1886).
and
vol.
277;
xciii.,
Liebig-Kopp'aJahrtB"
p.
XLiebig'aAnn,, 1855,
*

Liebig-Kopp'sJahresberieht,1855, p.

1856,
Society,

berieht,1855, p. 320.

79

BARIUK.

8TK0KTIUM,

CALCIUM,

re-oxidised at the positiveelectrode owing to its having


carried forward
by the circulation of the liquidcaused by

become
been

used.
high current-density
necessarily
The method
originatedby A. Feldmann*
either to mix
He
retrograde.
proposes

the

salts of the alkali-

haloid
of

that it is desired to obtain

metal
of

several)
fused

as

or

forms.

by

mixture

deposited should
alone,

methods

which

is

salts of alkali-

consequently
a

on

the

more

than

the

and

conditions

that must

be learned

2L

3. A

no

need

to

Commeroial

The

current.

(or

one

decompose
metal

to be

oxide

as

not

of

oxides

described
or

in

applying the
electrolysis

for the

alkaline-earth
the

re-state

Scale.

publicationof the

barium.

strontium,

to

to

metals

case

as

; and

against

"

Up

Qerman

to

date

few

originalof this

was

difficult task

1. A

then

indisputablethat there was


apparently no
in
the
presented
electro-metallurgical
industry
in largequantitiesof the metals calcium,
manufacture

book, the view

[323

of the

process.

before

whom

alone, but

the presence
hitherto been

have

Sxtraction

months

of the

means

salt

haloid

Feldmann's

may

the oxide

simultaneouslyin both
sufficient explanationhas been given of the disadvantages

of the fused

by

with

either
present in the electrolyte

be

haloid

resultingfrom

there

metals

else to melt the oxide


with the haloid salts of

metals, and
electro-positive

more

the

alkaline-earth

or

regarded as
singleor double

metal, or
electro-positive

more

be

must

the

from

they were

Yet,

on

be observed

the other

hand,

in the solution

writingsof Bunsen
There
clearlyenunciated.
the

almost

all the

of this

and
are

(500,000 to 1,000,000 amperes


high current-density
645 amp.
per sq. in.]).
high temperature at the cathode.
low temperature for the electrolyte.

problem
Matthiessen,
necessary
per

:
"

sq. metre

second requirementsmay very easilybe brought


and
third.
Yet
it is
agreement, but not so the second
that
be
should
for
the
metal
under
fulfilled,
they
necessary
first and

The

into

into cohesive
depositionmust be united as quickly as possible
metal
is
liable
form
to
masses
sub-chlorides,
; finely-divided
very
and so, passinginto the melt again,to be burned
at the anode j
a
high temperature and a rapid separationof largequantities
the cathode
at
of metal
are
indispensable,and, as already
explained,both these conditions,may be fnlfilled by applying
But at the same
at the cathode.
time"
a high current^lensity
herein
lies the secret
of the technical
and
difficulty the
in the immediate
electrolyte
vicinityof the cathode must be
the
lowest
possibletemperature, or else the haloid
kept at
large globulesof metal, and so
compound will redissolve even
the
the
metal
anode
to
[asthe hypotheticalsub-chloride].
convey
"

destructive

The
*

German

action

Patent

of

fused

and

alkalinehighly-heated

60,370. [EnglishPatent 9,783,July5, 1888.]

80

ELECTRIC

salts

earth

AND

REFINING.

all materials
that may
upon
of containingvessels needs no

construction

between

much

read

having to

SMELTING

be

in the

employed

Without
the lines,it is possibleto find all
comment.

suggestionsupon these pointsin the writingsof


necessary
Bunsen
and Matthiessen, to which
reference has been made
eio

the

very thin iron cathode wire, dipping only just


surface of the electrolyte,
of necessitybe
must

frequently. The
beneath

the

stronglyheated
the second

way

of high density and


any current
of the above
requirementsis fulfilled.

by

"

other
been
of

it has

hand,

in

this

On

the

frequently

insisted upon that the bulk


be
the
electrolyteshould

maintained
low

at a temperature so
a solid crust
that,if possible,

be formed

may

The

the upper surface.


of the experimental

on

form

apparatus described
the

originalpapers,

the

whole

method

as

applying
the possibility
plantfor a

using such a
profitableinstallation on
large scale, as, indeed,
of

the

the

metal

moment

has
and

being

the

for

the
the

admitted.

themselves

At

as

of

it,completelyexcludes

authors

in

well

of

separation
perature,
high temits specific
gravity
a

very

time

than

lower

that of the
^

^^^^P^

surrounding salt,it
rapidlyto the surface and

most

of it is burned.

culty may

be

apparatus

such

rises

the

separated on
led to

point

metal

an

must

is thus

thin

increase

wire

electrodes

in cathode

necessarilyfall.
much

increased

by so
solidify,
drops become detached
through the fused salt ; and that
fallingfinds an easily reducible
the

bottom.

To

in the first German

area,

the fused salts


As

soon

as

quantity of
and
the

any
metal

quence,
has, in consetemperature at

The

specific
gravity of the
before
that,
they have time

from

to

reaches

first

"

considerable

this

that

by Hiller (p.23). But,


tween
unfortunately,the relation bethe volumes
and weights

Borchers' experimental
of the metal and
apparatus for alkaline-earth
is easilyaltered.
metal reduction (j^-scale).

has

as

described

%^^^^
Fig. 67.

diffi-

This

by using an

met

the

and
electrodes,

sink

which

counteract

while
is not dissolved
when
silicate (porcelain)
it
this evil

edition of this

tioned
Borchers, as menthe
cathode
book, gave

82

ELECTRIC

iodide

offers

described.
a

nickel

SMELTING

difficulties

fewer

The

cathode

AND

REFINING.

than

the

previously

methods

is effected at a dull
electrolysis
and a graphite anode, surrounded

58
and
Stockem's
furnace.

Figs.

red heat,

by

using

porous

59.
Borohers
and
calcium
extraction
"

Fig.59.
vessel.

The

fused

salt conducts

is maintained
the

agency

at

the

of the current, and

the

current

well.

meltingpoint of calcium
iodine vapour

is

The

perature
tem-

iodide

by

rapidlygiven o"

CALCIUM,

The

is obtained

metal

globules.

No

STRONTIUM,
in the

detailed

.83

BARIUM.

of small

form

of
description

the

white

crystalsor

apparatus is,however,

available.
New

experiments have latelybeen


Aachen,

at

in which

made

he, with

his

in Borchers'

pupil,L.

tories
labora-

Stockem,

in overcoming entirelythe difficulties in the


succeeded
of calcium,and, for the most
part, those met with
extraction

the

in

the

and
Stookem's
Caloium
Frooess.
Owing to the
of this process, the production
of calcium
is now
of
one
simplestof electro-metallurgical
tion
processes, and the produc"

of this metal
low

tion
produc-

of strontium.

Borohers
success

has

in any

desired

quantity is possibleat

very

price.

The

apparatus first used

for the purpose, as shown


in Figs.
has
itself
suitable
not proved
for the
59,
practically
very
extraction
of calcium.
It is here illustrated,
however, because
58 and
it

is

of

early type

an

apparatus

an

for

the

and

strontium.

of construction
the extraction
be

in

seen

that
sinks

to

modified

Stockem*s

The

drawings
used

space
the

considerable
established

show

of alkali metals
is

at

have

somewhat

provided

bottom.

caloium

Borchers'

in

Fig. 59 that

of

Fig. 61.

Fig.60.
Borchers

extraction

The

for

the

extraction

fumaoe

glance that

(| n.8.).

the

principles

latest form
been

of apparatus for
retained.
Only it will

smaller

cathode

collection

of
possibility

of the

is

used, and

metal

separating calcium

that
in

chloride
was
quantitiesfrom electrically-heated
the
of
the
condition
this
of
means
by
apparatus ;
the
metal separated,
however, showed that the form of
apparatus
red
moderate
not
For
at
was
a
example,
entirelysatisfactory.
the
calcium
in
the
bottom
a
heat^
bulky form,
separatedout at
the anode
and the
so that a bridge was
rapidlyformed between
the
cathode
the
On
at the bottom.
temperature,
raising
rated
sepametal quicklyre-dissolved in the fused bath in the form of

84
a

ELECTRIC

8MBLTIN6

BBFININO.

AND

aab-carbide of calcium, described by Stockem.


of calcium was
consequentlyobtained,as

The

amount

largest
proved by

was

calcium
experiments,when electrically-fused
red heat, under which
at a moderate
electrolysed

later

chloride

waa

the

conditions

from the bath as it separatedat


could be removed
raised
In order to facilitate this,the cathode was

metal

sponge
the cathode.

apparatus was worked with an open top under


the chlorine.
a good draught,no
attempt being made to recover
The
in the form illustrated by Figs.
apparatus, therefore,was
60 and
the sodium
61.
Like
apparatus, it consisted of a
cylindrical
melting vessel,composed of carbon blocks arranged
like the staves of a cask, and serving at the same
time
aa
somewhat

and

anode.

the

bottom

fluor

of

which

spar,

is

fironk

prevented

this

beneath, is stamped into


melting by
cooling chamber
The
of
consists
iron rod, and, without
cathode
an
cylinder.
a

intention

of

coolingthe rod, it

so

it with

donnect

the
It

coolingvessel.
below

average

61,

placed between
cylinderfor the

12

the

volts

support

120

to

used.

was

in

at

amperes

an

clay cylinderwas

cathode

the

of

140

shown

and

carbon

the

of insulation.

purpose
conducted as follows : ^A layerof fluor spar
process was
first stamped into the space within the carbon cylinderupon

The
was

dimensions

of the

of from

current

of

pressure

by screwing
coolingeffect fron^
heating action of

so

apparatus

an
a

to*

the

thin that any


compensated for by the

was

With

the current.
Figs. 60 and

made

any

convenient

most

it into

mains

current

than

more

was

found

was

"

claycylinderand the coolingchamber.


Calcium
then placed
chloride in the form
of powder was
Twothe fluor spar until the cathode was
covered.
on
completely
the

or

formed

bottom

carbon

three

layerof the
is viewed

the

by

rods

chloride,as

from

then

were

shown
On

above.

embedded
in

the

in
[radially]

Fig. 61, m

which

the

the calciun^

the current

switchingon

top

furnace

melted, first in the immediate


neighbourhood of th"
afterwards
whole
of its upperand
the
rods,
throughout
most

chloride
carbon

as
now

layer. The carbon rods were


removed
possiblesimultaneously,
conducted
The

the

and

current

calcium

anode, and, in

petroleum.

Much

which, however,

was

ladle,and
was

saturated

consolidated with
in the

shape

the
of

lysis.
electro-

soft

from

aid
a

at

was

the

with

the

plunged

inta

mass

once

left in this sponge,


necessarily
with chloride,contained nearly

60 per cent, of free calcium


and showed
lustre on freshly
In later
-cut surfaces.
somewhat

mass,

subject to

once

far

Chlorine

removed

was

chloride
when

at

as

which

in the
mass
spongy
evolved
of
was,
course,
allowed
to escape.
experiments,was

these

first the spongy


metal
aid of an
iron spatula or
At

the fused

from

was

separated as

neighbourhood of the cathode.


at the

immediately,and

then

white metallie
silveryexperiments the sponge
a

of broad-ended

tongs fashioned

before
gauffering-iron,

removing

it

the entangledcalcium
chloride
In this way
left ; and, at the
small proportionwas
a

the bath.

from

calcium

time, the

togetherthat the mass,


cooling,presented a quite
white lustre after it had
silvery-

bath

and

homogeneous surface,showing a
crude
been cut through. The
of metallic

in closed iron

calcium

after thus
calcium

not

but

about

triclinic

measured, partlyby

90

readilymelted

to

layer of salt left

per
pure

found

Stockem

vessels.

that,
the

on

coolingof the melting vessel,was


This
sub-chloride,probably CaOl.

the
a

belongingto
transparent red crystals
The
crystalscould not
systems.

.saltformed
or

metal, after
chloride

be

calcium, the

remelting the

of the

surface

nickel

or

contained

metal

could

calcium, and

same

welded

so

was

sponge
the
from

removal

cent

was

until but

removed
after

85

BARIU)f"

BTBONTIUM,

CALCIUM,

of their small

reason

the monoclinic

size and

be

accurately
partlybecause

while under
ination
examreadilydecomposed that, even
the
moisture
attacked
by
microscope,they were
by
air,with evolution of hydrogen. But their crystalline

they were

so

the

of the
form

and

merely

colour

of

solution

between

Strontium.

of

of

alkali-earth

"metals.

Strontium

chloride
a

that used

it should

and

results

naturallyled

an

chloride

calcium
obtained

to the

is

asoer^

in

the

of
application

great

as

order

the

that
fluid

remain

lytic
electro-

and

that

metal

separationof the
might be effected.
temperature
also

was

quired
re-

higher,

and, indeed, could

not

be

low

maintained
the

so

metal

could

somewhat

be

should

62.

floated to

be

surface

speciflcgravity

that of the bath.

The

Borchers

deposited in

lifted from

brighterthan
the

"

and

extraction

that

chloride,it separated in
their

chloride,but
not, however, be

for calcium

chloride,in

which

is not

required the
current^ensity
twice

nearly

The

substance

chloride

the

of the other

that

could

the

to the treatment

the method

The

calcium

"

chloride

of calcium
electrolysis

as

in

formula

the

to

Produotion

use

that

of calcium
presence
the crystals
of the sub-chloride.

tained,owing

of

view

calcium

The

sub-chloride.

actual

the

support

the
and

the

the

cathode;

used
form
then

in the
of

Stockem's
furnace.

form

but, at

of
a

strontium

sponge
red heat

of
electrolysis

globuleswhich

calcium

at

times

quickly sank again, since


probably but little different from
apparatus must therefore be so arranged
was

86

ELICTBIO

that

the

SHSLTIMO

coUecta

metal

on

bottom

to

minimise

to dissolve in the calciam

effected

the

in

as

coolingcompartment
of

was

is

This

Fig.

of the

with

layer of

Under
but

these

the

to

lowermost

conditions,the

little affected
the

sinkingto

used

coolingjacket was

upwards only

sible,
posof

that

as

ultimately
cylindrical

was

The

side-wall of the melting vessel ; the


at the bottom
was, however, widened, and

the

salt for the purpose.


passingthrough the

by

cathode, and projected

part of

carbon

the

cylinder.

separatingat the cathode

metal
chlorine

bottom, rested

as

salt,the

strontium

being found to be the most suitable


thin iron rod screwed
into a thicker rod

great

62.

chloride
middle

tendency

as

as

solve
to re-dis-

the

covered

course

in

"r

is, as

its

chloride.

shown

apparatus

retained

was

and

chloride,a tendency which

in the
calcium

BEFIKING.

the

cooled there, in order

anode

AKD

evolved

the

at

was

anode, and,

the crucible of cooled strontium

on

In this way, after stopping electrolysis


and allowing
were
charge of salt to solidify,
globules of strontium

chloride.
the

obtained

of all sises up to about


10 mm.
from
the slag on
account
separated

charge,the

crushingthe
be

could

contradistinction

In

of

calcium, is

the

to obtain

used

barium

is

the

to

Barium.

(whichis
that

of

means

that

in

the

on

and

sieve.
earlier

strontium,

like

very soft metal


Stockem
has made

attempts
many
in the apparatus which
had been successfully
and strontium, but so far without result.
The

separatedin

so

"

fine

of division that

state

in

motion) and so becomes


solidified charge, especiallyfrom

hydrogen

when

thrown

it,for

suspensionin the fluid

in constant

the

evolves

readily

flattened

made

found

was

softness; for,
were

by

mass

was

part,floats to the anode

most

its

statements

subject,it

of

for calcium

barium

the crushed

and
silvery-white

Produotion

of

metal

globulesof strontium

separatedfrom

literature

The

into

burnt
the

water,

the

charge

It is true
lower
layers,

probably because

the salt is

of metal ; but the


permeated with minute
particles
than
in
the
of calcium
more
case
or
sluggish
salts taken
from
the neighbourhood of the cathode
strontium
for the separationof these metals.
after electrolysis
action

is much

Beduotion

of

metals, like

the

Oxide.

The

"

oxides

of

the

alkali-earth

all the other

oxides,as stated in the first [German]


edition of this work
in 1891, are capableof reduction
oy means
of electrically-heated
carbon ; they yield no metal, however, but

only carbide
no

more

in this way.
Even
if a mixture
be used
carbon than is requiredby the equation
CaO

Ca

containlDg

CO,

is produced correspondingto the supply of


a quantity of carbide
carbon, and this carbide mixes with the residual unchanged
and without
reaction
oxide, apparently in all proportions,
any

leadingto

the

separationof

the metal.

87

BEBTLLIUH.

If the carbide

long time
and

the

be

subjectedto a very high temperature for a


decomposed and carbon is left behind as graphite^
calcium, being volatile at this temperature, passes off;
it is

up to the present time


has led to the metal
being
but

kind

it is often

hydroxide as

or

obtained.

that

the

soon

residue

of the

Metals.

air

as

The carbide will be treated


carbides of other metals.
Uses

In

been

finely-divided
rapidproductionof calcium
gainsaccess to it.

of at the end

It is obvious

"

that

of the

book, with the

the great difficulties


of the separation

this year, stood in the way


have,
alkali-earth
metals
in quantity,have

of the

which

experimentsof this

contains

until

which

found

is recognisable
by the

calcium,which
oxide

found

has

apparatus

no
so

prevented

these

There
is now,
use.
findingany practical
however^
that
that
calcium
find
at
least,
a good prospect
they or,
may
in scientific and technical work.
Calcium
is
applications
many
that
active
assistance
its
will
in
welcome
be
so
chemically
many
of the chemical
branches
industry. In metallurgyit will prove
and precipitations,
to be a very useful reagent for reductions
as
the
and
elimination
of
for
well as
sulphur
phosphorus, and
carbon
of
from
metals
also
it may
crude
and
also be
possibly
;
reactions.
It will,however, be
used
for thermo-metallurgical
useful in organicchemistry; for in its chemical
especially
perties
prometals

from

"

it is very
it is much
more
solutions

is very

"

similar to the alkali metals,but in its reactions


violent, and the calcium
passing into the

easilyseparatedout again.

CHAPTEK

VI.

BERYLLIUM.
Ocourrenoe
in

in

combination

Nature.

"

^The

of
silicates,

in

The

emerald

almost

exclusively
principalis beryl,a
beryllium with the formula
is a form of beryl that is

which

and

silicate of aluminium

double

metal

occurs

the

(BeO)3 AljOg eSiOg.


prizedas a preciousstone.
especially
Beryllium (Be*; atomic weight
Properties of the Metal.
gravity 1-64)is a lustrous,white, soft,malleable,
9; specific
and
tough metal, with a melting point approximating 800* 0.
of powder, thin sheet, ribbon, or wire, the metal
In the form
in the air like magnesium, the halogens,sulphur, "fec.
bums
Berylliumwithstands the action of water better than magnesium,
but it is equally readilyattacked by acids ; in salt solutions
it slowly oxidises with evolution of hydrogen.
.

"

-88

8MBLTINO

KLECTRIC

Numerous
Metal.
the
method
of beryl. The

of
Eztraotion
for the treatment

methods

"

of

that

little from

REFINING.

AND

are
given
fluxingvaries but

of

silicates,
being effected by

other

of

means

treated
is afterwards
The
fusion
carbonates.
there
and
the
silica
render
acid
to
insoluble;
sulphuric

with

alkaline

and

of

then
iron salts. The

beryllium,aluminium,
is then
separated,either as alum by
aluminium
fluoride by
the addition of potassiumsulphate,
or
as
If the quantityof iron
other fluorides.
with cryolite
or
boiling
small
too
neither
be
too
nor
great,it is carefullyprepresent
cipitated
by the addition of soda, with the precautionthat any
ferrous salts shall be previouslyperoxidised
by the addition of
other
suitable oxidising
chloride
of
alkaline chromate,
lime, or
results

bulk

solution

aluminium

of the

On

agent.

the

addition

further

barium

of

carbonate, or

an

of aluminium
alkaline carbonate, a precipitate
hydroxide will
be formed
which will carry some
berylliumdown with it ; but
the latter may
afterwards be separatedas beryllium hydroxide
carbonate solution to the preby the addition of ammonium
cipitate.
The remaining solution should contain only beryllium

sulphate.
of

Eleotrolysis
is

as

CompoundB.

Beryllium

little suitable for

use

as

"

^The above

other aqueous

any

tion
solu-

solution

of

that,of the
beryllium salt,and it can be readilyunderstood
be
obtained
haloid salts
the
that
can
anhydrous,only
compounds

therefore,the metal has been obtained in


solution as a sulphateby the above method, it must
be converted
haloid
other
With
this
into chloride,
suitable
'salt.
into
some
or

are

utilisable.

When,

objectin view,
by the addition

the

berylliumis

of

is then re-dissolved in

by
haloid

salt

obtained

the

earth metal
of

some

one

of

carbonate
as
precipitated

carbonate,and the carbonate


posed
halogen acid,or the sulphateis decom-

barium
these

addition

chloride

The

barium.

of

by

with

or

of

means

either

alkali-metal

an

of

or

some

solution

of

chloride

of

the fluoride ; ammonium


ammonium
is also added
this way
and is also
In

alkali

an

chloride
to

there is obtained

or

alkalior

the

mixture

or

calcium

metal,most

other

prevent

evaporated to dryness,

an

^sxceptingmagnesium chloride
other haloid salt of

convenient

berylliumchloride

is then

methods
a

other

haloid

alkaline-

chloride),

conveniently
compound

of

formation

of

oxides.

of salts that

is

fusible,

this the
and from
electricity;
be
the
in
same
beryllium may
separatedelectrolytically,
way
as
magnesium or lithium is reduced, although,accordingto
Hampe's experiments,berylliumchloride is reportednot to be
conductor.
There is practically
an
electrolytic
nothing to be
said concerningthe electrolysis
itself;both the apparatus and
the manner
of conducting the process are
in the
the same
as
Care should, however, be taken
of magnesium.
that the
case

temperature

good

never

conductor

exceeds

of

that at which

the

metal

fuses,other-

90

SMELTING

KLEOTRIC

of

fused

alloyby using a

an

made in this direction


Technical High School have
Warren's
confirmed

Process.

AND

far

so

But

laboratories

all

ments
experi-

of the Aachen

given negativeresults.
has,in

the

of the

case

given above

of the method
efficacy

the

cathode.

metallic
in the

Warren*

"

REFINING.

as

bromide,

to
applicable

general. He used for the purpose about S


by crushingand washing;
purified
kilogrammes (6*6lbs.)of beryl,
the powdered substance
with about four times
then mixed
was
with a blast.
its weight of soda and fused in a furnace worked
dissolved
After
with
the aid of supercooling,the melt was
heated
and
of
means
acid,
steam, decomposed by
hydrochloric
render
the
silica
soluble.
infinallyevaporated to dryness in order to
residue
The
from
this
then
solution
was
separated
precipitatedwith soda, after separating out the iron and
and
Aluminium
next
chromium.
tracted
exberyllium oxide were
of
from
residue
the
treatment
moist
by means
by
the
was
sulphur dioxide ; and the alumina
deposited from
solution
The
o
n
as
a
resulting
granular precipitate boiling.
filtrate from
this precipitate,
the addition
of ammonium
on
the

haloid

salts in

carbonate, yielded
berylliumcarbonate, which
with
with

lamp black
bromine in

depositedfrom
at

No

to

the

paper

as

further

information
of

to

as

from

REDUCTION

various
author

the

ways.
stated that

was

apparatus

of 8 amperes
in the original

current

given
to
as
electrolysis,

used.

The

BERYLLIUM
of

electro-thermal
the

mixed

most

the

varied

the metal.

Method

In

by

conductingthe

OF

thermic

by

distilled bromide

method

current^ensity,or
made
objectswere

Electrothe oxide

at

then

was

treated
of air, and
The metal was
red heat.

absence

in the

retort
fireclay

the

12 volts.

heated

and

Bednction.
has

means

first German

all metallic

OXIDE.

oxides

"

been

edition
were

The

reduction of

accomplished in
of this

book

the

capableof reduction

heated carbon, but also specially


by electrically
pointedout that,
that
the
of
time
althoughat
possibility reducingberylliumoxide
was
ment.
recognised,
pure metal could not be obtained by this experi-

Liebmann,t

in

his

patent

for

the

production of

be^llium

fundamentally similar to the Cowles


the first to confirm
alloys,was
process for producing aluminium
the reducibility
heated
of beirllium
oxide by electrically
the patent
carbon.
heated
He
heat (necessarily,
to a white
as
of the oxide
states,by electrical means) a mixture
specification
with a reducing agent and
the metal, or oxide of the metal, to
be alloyed,
of charcoal.
amount
togetherwith the requisite
alloys,by

method

Chemical

t German

News,
Patent

1895, vol. Ixxii.,


p. 311.
94,102.

91

BERYLLIUM.

Lebeau's

Lebeau's further experiments^ as


If
the author's observations.
sufficiently
long time in the carbon

Experiments.

to the treatment

of

"

beryl

confirm

the mineral be heated for a


of 950 amperes
crucible of the electric furnace,with a current
and 45 volts,the mineral
the
loses
greater part of its silica by
converted
and becomes
of the carinto a mixture
volatilisation,
bides
of aluminium
and silicon
and

intimate

an

beryllium,together with
which

carbide,from

and
beryllium,

If

and
for

and

dilute

acid
hydrofluoric
of 100

mixture

50

dilute acids extract

ferro-silicon

the aluminium

only the latter metal.

kilogrammes [2 cwts.1 of beryl


good powdered coke be heated

cwt.]of

kilogrammes [1
the application
of a current
of 1,500 amperes,
two
formed.
The
made
is
are
layers
layer
upper
up of varying
of
and
alumina,
quantities silica,
beryllia
by
; it is not attacked
hour, by

an

and

adds,

The lower
is,therefore,useless for further treatment.
for
the
consists
of
most
hand,
crystallised
part

the other

layer,on

siHcon, which

obtained

be

almost

by treatment, first
sulphuricacid. A method
trial
is,therefore,available for the production of silicon on an indusof
of
natural
silicates
the
the
reduction
scale,by
by
agency
with

may

acid and
hydrofluoric

carbon

then

pure

with

in the electric furnace.

Calcium

carbide

is found

to

be

convenient

reducingagent.

On

heatingfor an hour and arhalf a mixture of equal parts of


calcium carbide,using
beryland coarsely-powdered
finely-crushed
1,500 amperes for the purpose, a homogeneous, fused,
was
mass
obtained,consisting
greyish-green
chieflyof a mixture
a

of

current

of the

and

aluminium

exposure
of the

to

moist

air

carbides,into

hydroxides,from

which

This
material
on
beryllium carbides.
resolved
itself,
owing to the oxidation
powder composed of the corresponding
from

90 to 95 per cent, of the

beryllium

be extracted
contained in the berylcould,without
difficulty,
by
the agency of hydrofluoric
or
sulphuricacid.
The
observation
of Liebmann
above referred to, which, in
view

of the matter

book

and

publishedin

of the well-known

the first German

edition

of this

for the

Cowles

production
process
of aluminium
contained
was
alloys,
nothing speciallyoriginal,
confirmed
by Leb^u.t He found that on heating a mixture of
oxide, and reducing carbon for five minutes,
beryllia,
copper
witih

and 45 volts,
he obtained a brittle,
amperes
with a rose-red fracture ; it consisted of a
that melted at the temperature
silvery-white
alloy,
of 900

current

metallic,fused mass,

paleyellow,or
of

f errot

and

using
case

most

furnace,and

copper.

large
of

greater part

excess

the

The

red

formation
of carbon

double-oxide
crystalline
of the oxide
and

berylliumwill

of the copper

can

of

lium
beryl-

be avoided

by

longerheating; but in this


become
carburised, and the

will be volatilised.

*C"mpte8 Rendus, 189S, vol. cxxvi.,


t/Wa., 1897, vol. cxxv., p. 1172.

It

p. 1203.

is,therefore.

92

SMBLTING

ELBCTBIO

AND

BBFININO.

the oxide by re-meltingthe crude product in


better to remove
Perrot furnace.
The alloy thus purifiedcontains from 5 to
a
from
10 per cent, of beryllium,and varies in colour,accordingly,
The yellowalloy,
yellowto nearlywhite.
containing5 per cent,
of beryllium,may
be filed,
of polish,
and may
is susceptible
be
hammered
either hot or in the cold ; it withstands
the action of
with
affords
the air, and on
more
taining
alloysconmelting
copper
less beryllium,
1*32
that
which
containing
per
among
cent,

of that metal

Although,

possibleto
quantity of

as

is

will

obtain

gold-yellowin
be

understood

beryllium without

colour.
from

the

foregoing,it is
the small
great difficulty,

beryllium oxide contcuned in the raw material


and the necessity
for separatingthe beryl from
itvailable,
large
of
the
silica
and
render
alumina,
quantities
process so costlythat
it has hitherto found
in the arts,notwithstanding
no
application
that the properties
of the metal,and especially
its extraordinarily
low specific
for it.
a good demand
gravity,would ensure
the

9S

ALUMINIUM.

METALS.

EARTH

II." THE

PART

CHAPTER

I.

ALUMINIUM.
Oocurrenoe
found
in

nature

Nature.

in

Aliiminium
only in the

of

combined

"

Aluminium

state.

Of

i"

the

pounds
com-

naturally,the oxide forms the basis of


the hydroxide is present in
conmdum, sapphire,and emery;
the salts are
thus
cUaspore,bauxite, and hydrargillite
; and
the
the
fluoride
bv
The
by
cryolite
:
sulphate
represented
;
the
the
almn
silicates
and
sheue;
alums, alunite,
felspars
by
and
their products of decomposition,the days (kaolin,
"c.).
and
used
these
corundum
as
minerals,
sapphire,are
Among
and felspar
preciousstones, emery for polishingand grinding,
of building-stones,
and clay for the manufacture
firebricks,
Chemical
and
porcelain.
cesses
propottery,earthenware, stoneware,
of a more
less simple kind
are
or
employed to utilise
of alum ; cryolite
in
alunite and alum shale in the manufacture
that of soda and pure aluminium
hydroxide and oxide ; and the
the
in
hydroxide ; whilst
hydroxide
producing
pure oxide and
that

occur

"

corundum
utilised

alloys.
extraction

be

direct

have
made

than

in the

have

crept into

to

case

has

of

propertiesof
of

means

ments
experi-

It appears, therefore,
propertiesin greater detail

as
metals, especially

chemical

weight

2*6 to 2*7 in the


in commerce) has a white
or

structure
crystalline

by

the

years.

these

and
metallurgical

chemicallypure,
obtainable

other

aluminium.

of pure

last few

(Al'";atomic

Aluminium

process for the direct duction


proof the minerals
be
can

"

describe

of the

None

Metal.
Many
been
determined

only
during the

desirable

shows

the

of

Properties

to

Cowles

for the

aluminium
*

in the

used

was

of aluminium

when

case

many
text-books.

errors

2*58,when
sp. gr.
of the purest specimens

27;

colour
broken.

and

good lustre,and
Its melting point
with
comparative

determined
by Le Ohatelier
Its
specificheat at 0" 0. is 0-2220;
certaintyaa 625" G.
0* and
100** 0., 0*2270 (mean); and
between
at the melting
now

been

and London,
See Alyminium, by J. W. Richards, 3rd ed., Philadelphia
vol.
in
FranHin
and
Joum.
Inst.,
1897,
oxliy.,
Hunt,
1896;
of
pp. 81, 171.
*

94

ELECTRIC

point,0'285.

Aluminium
158

temperature,
so
liquid,

evolves

REFINING.

coolingfrom

on

when

calories

solid

heat

its latent

that

AND

SMELTING

258

or

of fusion

its

melting

calories

is 100

when
The

calories.

is 0*0000231,
expansion of solid aluminium
of liquid aluminium
solidification is
on
conductivityfor heat (silver 100) is 31-33.

coefficient of linear
the

and

contraction
Its

0-017.

Aluminium

is

friable

so

pulverised.*When

rolled

530"

at

that

C.

hammered

or

then

it may

in the

be

cold,aluminium

but this property is restored to it if


ductility,
it be annealed by heating it to from 400** to 500"* C, and then
The
cooling it slowly.
temperature best adapted for rolling
the
is 100* to 150* 0., and for pressing,
metal
or
hammering
the
and
certain
500* 0.
Up to a
point,both the hardness
strength of the metal are
considerablyincreased by cold
working (hammering or rolling). For example, the tensile
grammes
in the cast condition
is about
12 kilostrength of aluminium
but
tons
mm.
by
inch];
[7*6
per square
per square
cold rollingthe metal, so that it is subjected to a moderate
in sectional
the tensile strength is 18 kilogrammes
reduction
area,

rapidlyloses

its

[11*4tons

mm.
per square
from
reducing the area

20

kilogrammes per square


by a reduction from 80

1,

to

[14-9tons

mm.

inch];after

per square
the tensile
per

strength is

inch];

square

so

23*5
or

1, it is 27 '5 kilogrammes per square

to

[17*7tons

mm.

inch].
per square
electrical
conductivity of

The

Richards

100),is

t (copper

For metal

with 98*5 per cent.

,,

),

"

"

"

"

W*U

Al,

,,

99-5
99*76

"

alloyswith

Aluminium

"

"

"

...

"

"

oo

61
63 to 64

metals, and

most

.56
.

66 to 67

the

resultingalloys

Aluminium.
of very fullyin Richards'
all
with
almost
metalloids,sometimes
chemically
treated

are

the

In

cold,however,

energy.
heat, it strongly resists

temperature

it combines

the

aetion

with

it,and

to

"

"

10000
"

according

aluminium,

follows

as

and

even

of
in

It combines
with
up

to

but

oxygen,
so

able
considerred

good
at

doing evolves

that
much

heat.
Water
the

and

acid

boiling.
and sulphuricacid
and

caustic

AlumirUvm

24,

have

soda

bring it

of the

Industrie

dissolves

other

Franklin

action

on

on

it
minium,
alu-

it

slowly; but hydrochloric


It
rapidlyinto solution.

very
metals

from

English
AktiengeaelUchiift,

1896.

fJoum,

scarcelyany action
slowly attack

cold ; but
the latter very
Nitric acid is almost
without

most
precipitates
*

organicacids

in the

metal

when

dilute

Inst,,1897f vol. cxliii.

solutions
Patent

of their

16,969, Aug.

95

ALUMINIUM.

reduces

salts,and
then

of the

most

and
carbon,silicon,

of

unitingor alloyingwith

The

abundance

valuable
which

of the
be

not

the reduced

present

element.

compounds of aluminium, the


the difficulties,
metal, and, finally,
with

under-estimated,connected

decompositionof the

those

fused, even

of aluminium

excess

natural

propertiesof the

must

when

oxides

boron, any

that

material

raw

is

the

present

ful
success-

in such

number

of
abundance, sufficiently
explain how it is that the
and
of inventions
actual
or
researches,
patented),
(either
merely
of

more

less timid

or

For
which

the

have

better

been

will be desirable
groups
may

has
sug"^estions,
estimation

employed
to

consider

become

of the

almost

able.
intermin-

of the

value

processes

in the

reduction of aluminium, it
separatelythe different divisions or

which, from the metallurgicalpoint of view, they


Reduction,and Electrolytic
classed,viz. :" Precipitation,

into

be

Processes.

Precipitation

Prooesses
to the scope

of

Aluminium.

Extracting

"

of
of this book, a short account
Having regard
this
for
class
of
must
more
suffice,
prominent processes
the precipitation
metal
of one
by the addition of another is
an
operationwhich belongs to pure chemistry rather than to
the

electro-metall urgy
Oerstedt,^ in the
.

year
of aluminium
decomposition

1824,

was

the

chloride

first to

attempt

the

of

by
potassium
result; for other skilled
amalgam, but evidently without
experimenters,working according to his directions,failed to
means

obtain

aluminium.
W6hler,t however, in 1827, was
any
of
successful in reducing the anhydrous chloride
by means
difficulties
Deville
obviated
the
connected
|
potassium. Later,
with the
the

productionand
double

he further

use

substituted

potassium recommended

the

by

chloride

of aluminium

chloride of aluminium
much

and

sodium

cheaper metal

Wohler.

The

by employing
; and

instead
sodium

process

was

for the

actually
at
(first
England

in France
these lines for thirty years
conducted on
Nanterre and later at Salindres),and for a time in
of the mineral
also. In 1855 Ro8e" proposed the substitution
fluoride (cryolite^
for the chloride ; and in place of sodium, the
had been adhered to by Rose, Beketoff ||employed
use of which
magnesium. But the principalinterest at present centres in
Orabau's proces8,1I
which
is excellent in all its details.
In this

process, solutions
*

of

sulphateof

alumina

are

first treated

with

Oerstedt,Overs, o. d, Danske Videnak. Sdsk, Fwhandi., ";c.,1824-25.


t Wohler, Pogg.Ann., 1827, vol. xL, and Liebig'sAnn,, vol. liii.
See also H. St. Claire
t Ann. de Chtmie et de Physique, 1864, vol. xlix.
De F Aluminium, Paris, 1859.
Beville,
%Poffg,Ann., 1866, vol. xovi.
^JahretiberieJU
der Cfiemie,1865.
IfGerman
Patent 47,031. [EnglishPatents 14,366,Oct. 21, 1887, and
15,539,Nov. 14, 1887.]

96

ELECTRIC

in
cryolite,
of

order

to

SMELTING

The

RBFINIXO.

obtain the alaminium

fluoride,
accordingto
Al^SOJg

AKD

the

equation

Al"Fe.6NaF

entirelyin

the

form

which
fluoride,
heated
and
to
off,washed, dried,
aluminium

"

2A1,F" + SNa^O*.
in water, is filtered
incipientred heat, and is

is insoluble
an

charged into a cold vessel lined with pure cryolite.


The requiredquantityof dry sodium, in the form
of a cube or
the vessel is
i
s
hot
and
placed upon the
cylinder, now
powder,
immediately covered up. The followingreaction then occurs^
accompanied by a great evolution of heat ; but in other respects
it proceedsquitequietly:
then

at

once

"

The

AlsFe + 3Na,

Al, + Al^F^

is afterwards

aluminium

vessel,melted

found
covered

regulus,and

6NaF.

at

the

with

bottom

of the

slagof

a
cryolite^
completely fused owing to the heat of the
reaction.
The latter bye-productis available for the production
of aluminium
of fresh quantities
fluoride. Of all the chemical
this
is
the
one
which,given a cheap method of
only
processes,
into competitionwith
producing sodium, is ever lively to come
The metal obtained
the electro-chemical
methods.
by this process
has the advantage of being unusuallypure.
For a long time
alumina
Processes.
The
Beduotion
waa
held to be non-reducible ; and even
to
to this day statements

which

has

to

been

"

that
has
fact

effect

to

are

be

that

useful

"he

in

the oxide.
for reduction
obtained

by

circumstance
the reduction

from

metallic

pure

arts

is

never

only

an

to

be

text-books.

comprehension
in

This
of the

that would

form

be

obtained

by the direct reduction of


high temperature necessary
least,is most advantageously)

this,the

(or,at

the conversion
has

chemical

erroneous

aluminium

In addition
can

in the

found

probably resulted

of electrical energy
frequentlygiven rise to the

into

is either

of aluminium

heat.

assumption

This
that

entirelyor in part due to


production of the metal is really
electrolytic
agency.
due, as will be shown
later,entirelyto a reduction of the oxide
heated carbon.
o/cUuminium by electrically
The idea of heatinga material with a high electrical resistance
by a powerfulcurrent, and of placingthis resistance in the most
intimate contact) with the mixture
to be reduced
(the material
and
coming,
bebeing distributed uniformly through the whole mass
of
such
constituent
a
a
ultimately, necessary
mixture)
It is by no
unquestionablydeserves the most careful attention.
and if there be occasion
for surprise,
it
a
new
means
discovery,
of the results that have
followed the applicais less on account
tion
been
than because
of this princii)le
these results have
so
the
effected.
For
of
the
Transactions*
Philosophical
tardily
But

"

the

Phil. Trans,, 1815, vol. cv., p. 371.

98

BLECTRIG

besides

AND

BBFINING.

carbide,carbon, and

aluminium

alnminium,

which
for reduction.

SMBLTINO

be derived
inevitably

must

from

other

the carbon

purities
im-

used

a
Underlying the process, however, there was
which
has found,and will find again,
sound
perfectly
principle,
valuable applications
in its proper sphere in metallurgy.
many
the Brothers
After a long interval,
The
Cowles
Prooess.
made
Cowles introduced (in1884) a process, by which there was
available for use a number
the valuable
of alloys,
of which
perties
prohad been in part known
for a long time.
Considering
that the impossibility
of producing a sufficiently
pure metal by
the direct reduction of aJumina
with carbon
has been proved,
nate,
fortuthe invention of Oowles must
be regarded as particularly
for it consisted
in alloyingthe aluminium, at the very
with another
of its production,
moment
metal, and so avoiding
the absorption
of carbon, or at least reducingit to harmless
portions.
proBut without
any wish to begrudge to the inventors
the recognition
that is commonly awarded
them, it must yet be
that their patent specification
wide a field.
noted
covered
too
*
In the principal
patent it is stated that the invention refers to
the electric current
in which
is employed as
a class of furnace
"

the sole
was

of heat.

source

said, to

reduce

operationswith
consisted

and

ores

to

attempts
conduct

low

the

use

electrical

electric circuit that it formed

of

had

other

been

metallurgical

conductivity,so connected
an
uninterruptedpart of the

red
of its high resistance,
it became
consequence
afforded all the heat required. The
substance
to be

in

an

same.

hot, and
reduced

absorbed the
granular material,and
heat at the very placeof its production.
The conversion
of iron into steel must
undoubtedly be recognised
as
a metallurgical
operation. If then Pepys, in the year
1815, as shown
on
operationby
p. 97, accomplished such an
of
the
in an
constituent
mixture
resistance
a
as
using a
part
and thus brought it to a red heat by the applicaelectric circuit,
tion
of a powerful current, while the other constituent
of the
mixture
with
in direct contact
was
it, he was
undoubtedly
of the Cowles
working in exact agreement with the specification
patent,publishedin America
seventy years later. It was by an
applicationof exactlythe same
principlethat Depretz (p.97),
in the year 1849, placed a diamond
in a tube of sugar-charcoal,
and included
this in a powerful electric circuit,
wiUi the object
of ascertaining
the behaviour of the gem in a neutral atmosphere
for
at high temperature. Finally,it might well be claimed
Monckton
that he anticipatedthe Cowles
patent as far as it
refers to the reduction
of alumina, by his specification
published
in 1862 (p.97).
was

with

it

arc

Tn

mixed

made,

; but this invention


granulated material of high

the aid of the electric

chieflyin

resistance,or

Previous

this

thus

"U.S.A.

Patent

319,796.

99

ALUMINIUM.

These

circumstances, however,

detract from

the service which

in

can

the

Brothers

no

way
Oowles

be

said

have

to

done

in

of
introducingso simple a process for the manufacture
aluminium
alloys.
Instead
of enteringminutely into the details of the various
forms of furnace
which
Cowles
are
specifiedin the numerous
patents,it will suffice here to describe a smeltingplant on this
have been published.
system, concerningwhich detailed accounts
This plant,which
several years ago in the factory
was
put down
of the
Cowles
time
Syndicate Company," has been for some
H.P.
out of operation.* A
400
Crompton's dynamo gave a
"

Fig. 63.
current

furnaces

"

of 60
were

Cowles'

volts
built

plantfor
x

of

5,000

of aluminium

manufacture

to

6,000

and
fireclay,

alloys.
The

smelting
rectangularin crossby side in a long row, but
amperes.

were

They were
arranged side
in
were
operation one at a time, while the others were
only put
in various stages of cooling,
emptying,or charging. The current
and
from
the
to
was
conveyed
battery of furnaces by two stout
bars
along the whole lengthof the
running horizontally
copper
height above it,one of these being
plant,and at a convenient
the backs
above
the fronts, the other
of the smelting
over
chambers.
a
Running upon each of these rails was
copper
flexible
with
wire
cables
of
mounted
on
wheels,
clamp
copper
section.

Industries,1888, vol.

cxv.,

p. 237.

100

ELECTRIC

attached

of the

ends

other

the

it;

to

REFINING.

AND

SMELTING

cables

were

held

also

lower

togetherby clamps. A suitable opening in each of the


sponding
clamps permittedthe latter to be hung upon copper bars,correelectrical
which
means
in shape to the aperture, by
could be made with the electrodes.
connection
Every electrode
bundle of from 7 to 9 carbon
head
diameter, around which a cylindrical

consisted

of

cast, of
piece was
or
being produced in the furnace),
Into
under
were
manufacture).

were
(ifferro-aluminium
aluminium-bronze
(if
copper

iron
of

Fig.64.

The

"

65.

the

midst

referred

of this
to

"

Gowles

The

head

above.

The

in

rods,each 2| in.

furnace

Cowles

section).
(longitudinal

furnace

piecewas

(cross-section).

cast

electrodes

one

were

bars
of the copper
introduced
the
into

smelting chamber
oppositewalls of

through suitably laid cast-iron tubes in


the furnace.
By adjustinga simplescrew, the
backwards
and forwards,as might be
electrodes could be moved
for the regulation
In preparing the
of the current.
necessary
with a layer of
furnace
for use, the bottom
first covered
was

limed
a

frame

wood-charcoal,and
of sheet

iron

was

then
next

the

electrodes

placed in

the

were

introduced

furnace, and

the

101

ALUMINIUM*

it
space within
charcoal,whilst
chamber

charged

was

that

filled with

was

withdrawn.
the famaoe

to

empty

still left

Some

mixture

the

charcoal

frame

form

bridge

by

was
a

and

only,and

fragments of retort

space
surmounted

was

with

between

for the

of ore, metal, and


the walls of the
frame

the

carbon

then

was

thrown

were

into

the
and, finally,
charcoal,and the whole

current,

filled up with
cast-iron cover.

In

the

centre

of this

opening for the escape of gases generated


during
lit,and the
smelting operation,the gases were
led through a tube into a furnace
were
productsof combustion
in which
alumina
be
that
should
they might contain
any
of
the hearth
on
deposited. The melted
alloy accumulated
the furnace,and was
off through a tapholeplaced there for
run
the purpose.
The
consisted
intimate
of a very
slag, which
mixture
of alloy and
washed
and
to
was
charcoal,
powdered
the
residual
charcoal,the
separate
alloybeing introduced into
the fumace
with a fresh charge.
In the fumace
above
described,from 15 to 20 cwts. of ferroaluminium
or
aluminium-bronze, containing15 to 17 per cent,
of aluminium
could
bronze
be produced daily. The
rewas
melted
with
the requisiteproportion of copper
to yield the
1*25,2-5,
alloysrequired for the market, containingrespectively
5, 7*5,and 10 per cent, of aluminium, and was cast into ingots
The average
electrical power
weighing from 10 to 12 lbs. each.
to 50 horse-power hours
required amounted
per kg. [whichis
23
H.P.
of
aluminium.
A
hours
to
nearlyequivalent
per lb.]
genend view of a smelting-houseis shown in Fig. 63, whilst Fig.
64 gives a longitudinal,
and Fig. 65 a cross-section of a single
these
In
furnace.
are
electrodes,consistingof
figuresE"
there

cover

was

an

the

rods, each

9 carbon
the

opposite to
whole

The

in either
which
is

about

metal
cylindrical

blocks, M.

the

carbons, the
arrangement slides

direction

with

conveyed by the copper


clamp, Y ; and

the copper
end of the

K,

in

rod, K,

The

tube, B.

the

At

copper
in the
aid

the

part of the

forms

of

end

collar,Z, attached to
wire cables,L, which
this

are

cast

of these

blocks,
rods, K, are introduced.
tube, B^ and may be moved
the screw,
S, and the nut,
K.

The

projectsbeyond
F, serves
guide-block,

current

are

grippedby

on

the conical

is rested

in turn

which

cast-iron

which

1| ins. thick, around

the
to

mouth

keep

of
the

the

rod,

place.

Theory

of

inspectionof

the

Cowles

Fig. 64, which

"

during the operationof smelting,


rods,so
falselytermed electrodes in descriptions
into the
of the plant,are
reallyonly resistanoes introduced
first
It is they which
circuit of a powerful current.
are
heated,
and which
then
impart their heat to the surrounding charge.
By degrees,as the charge around the inner extremities of the

carbon

rods within

It is evident
from
ProoeBB.
an
the usual arrangement of the

shows

that these

the furnace

often

102

ELECTRIC

heated

rods becomes

carbon

from

Thus,

to

also

act

by
Hampe*

current

the oxygen

in the presence

admit

of copper
the
These

employed.
followingconclusions
was

S.
the

become

partly

oxides.

that

to reduce

or

oxide

copper

Deville's

led

furnace

him

the

to

"

temperature nearly equal


of copper,

by carbon
given negative

alumina
have

high temperature of
experiments have

it is certain

the

to

carbon

be insufficient to enable

to

that

melting point

reduce

of

in the

alumina

of the

the

temperature
higher than this,will also
furnace,although it is much
believe,therefore,that the production of aluminium-i

presence
electric
fail.

heating extends,
it)ds,",

the

attempts

many

though

results,even

quartz

drawn
with-

are

the heat generated by the


of alumina
alone suffice to bring about the reduction

by carbon, because

rods

of the screw,

means

part of the circuit,and

form

of the metallic

refuses to

can

''If

the

as

in the mixture

resistances,whilst

aa

REFINING.

incandescence,the

to

increasingextent,

an

burned

AND

little by little by

another

one

of carbon
particles
so

SMJCLTINO

bronze

is dependent far less upon


a
by the Oowles
process
in the electric furnace than
(chemical)dissociation of alumina
the electrolytic
decomposition of the alumina
by the
upon
current
passing through it,the earth being brought into a state
of fusion by the electric arc.
According to my view, then, the
action of the electric arc
it
is primaiily electro-thermic,but
is also distinctly
electrolytic.
*'

The

author

contrary,as

cannot
a

of the alumina

if^fluence
of

view, but believes,on the


observations,that the decomposition
with

agree
of his

result

in the Gowles

the heat

this

is attributable

furnace

generatedby

the current

sdely to the

in tfieresistcmce that.

is introduced

into the circuit ; and, further,that it is not necessary


obtainable
the
the
to employ
higher temperature
by
agency
of the electric current
in order to bring about the desired result.
It is not
of

the range
Deville's furnace

completion
such

an

of

beyond

of the

should

reaction.

apparatus

to

the electric furnace.

that
possibility

suffice for the

It is not

fulfil all the


For

if

charge

ture
tempera-

initiation

and

however,
possible,

with

that

conditions
be

the

even

placedin

one

obtain
or,

in

as

in

to
Hampe's experiment,two crucibles,and be
high temperature of one of the best of these ordinary
furnaces,the heat of the surrounding fuel will be imparted but
The temperaenclosed in the crucibles.
slowly to the mixture
ture
of the charge,therefore,
rises quitegraduallyto the melting
point of copper or to the reduction temperature of copper oxide,
and carbon shall have attained the
and long before the alumina
which
aluminium
at
could be produced,the copper
temperature
will have
the mixture.
less from
The
or
liquatedout more

then

submitted

the very

evolution

of heat

from
*

the union

Ckemiker

of copf"er with

1888,
Zeifitng,

p. 391,

aluminium,

that

103

ALUHINIUSIU

had

Hampe

hoped

would

free aluminium

(ayour

has

the

reaction,cannot

until

occur

been

actuallyproduced.
furnace are quiteunlike
those
described.
the
In
this
of
constituents
that
one
charge
just
case,
the
carbon
is to take part in the reaction
for
the
viz.,
required
reduction
is almost
instantaneouslyraised to a temperature
will
be
from
as
an
-which,
seen
experiment shortly to be
mentioned, is amply sufficient for the reduction of the alumina.
Copper or copper oxide is not essential to the reaction, but is
added
in a
simply with the object of obtaining the aluminium
without
serviceable
form
since
this
the
addition
as
an
alloy,
aluminium
with a portionof the excess
would combine
carbon
form
to
a
completely useless material, which no subsequent
refiningoperationswould purify.
some

conditions

The

in the

Cowles

"

"

Thermic

Beduotion

assertion

may

Fig. 66.
A

"

of Alumina

proved by

Arrangement

carbon

thin

fixed

be

to show

pencil,W,

between

two

the

stout

by Carbon.

The

"

author's

followingexperiment (Fig.66):

"

reduction

direct

in. wide

about
carbon

rods,K,

of alumina

and

by
ins.

1|

about

carbon.

long, is

1 to

1^ ins. in
paper bag, P,

This

pencilis passed through a small


length,filled with an intimate mixture, M, of
1^
and carbon.
is prepared by repeatedly
alumina
The
mixture
and
aluminium
hydroxide with tar. The ends
heating
mixing
of the paper
cartridgeare closed by small cork plates,and
charcoal
is packed in coarse
the whole
powder. The electrical

diameter.

ins. in

about

connections

are

now

passed through
After

the

removed,

the

made, and a
arrangement

has
cai-tridge

cooled

fritted mass,

which,

containinga

considerable

of

an

electric
of the

the charcoal powder


sufficiently,
with
pencilwill be found surrounded

the carbon

and

of 35 to 40 amperes
is
for from two to three minutes.

current

on

examination, will prove

proportionof
been

having
experiment,and,
arc

conducting circuit within

the

formed

The

is excluded

in the absence

of any

charge mixture, the

decomposition is also
electrolytic

negatived.

be aluminium

to

carbon.

is

by

possibility
the conditions

break

in the

occurrence

of

It is unnecessary

^v^^CiOQgle

Digi^edby

104

ELBCTRIC

to point out that


the charge would
With

SMITING

admixture

ah

have

AVD

REFINING.

oxide with

of copper
or
copper
to the production of

led

aluminium-

above

of the

simple arrangement
type it is,
therefore,easy to test the validityof the assertion previously
a tuficiently
made, that ffiven
high temperature all metaUic oxideg
are
capableof beingreduced by carbon.
As above explained,
it was
necessary, in order to producethe
bronze.

temperature requiredfor
of 35

current

this is
amps,
amps,
should

40

to

reduction

the

through

amperes

The

of any

of such
current

per

[3,200to 3,800
[6,500
sq. mm.
and

difficult case,

conditions,will

these

metal.

force

would

With

to

that

be 10 to 17 volts.
resistance
construct
a
in

employed
pointedout

any
that an

named

above

attempt

of

presence

an

Tests made
as

excess

for

followingaverage
calculations:
An

very

be

however,

than

current

inconvenience

and

carbon

thin

current

many

pencilsare

the oxygen
of use, even
in

through by

in the

surroundingmixture.
of carbon
rods,
descriptions
in arc-lamps(pencils^ to ^ in. thick being
this purpose),have led to the adoption of the
numbers
for general
accurate
as
sufficiently
a

the

force

oi

0-3

of 1 ampere
temperatures of these
current

ELECTROLYTIC

per sq.

METHODS

ALUMINIUM

Eleotrolysis

the

varied

6 to 10 amperes
per sq. in ] of sectional area.

THE

smaller

it is easy

data
to

must,

first minute

of
current-density

amperes

It

burned
the

of carbon

drive

necessary
carbon
pencilat

suitable

with

great

electromotive

"

to

work

to

within

the most

used

made
specially

to

become

may
oxides

with

are

of these

aid

shall be

plantsbecause

easilybroken, and
metallic

the

given OKperiment.
will lead

of

derangements

mm.

pass

pencilj

the resistance
required to overcome
carbon
a
pencil,1 j ins. long,with the productionof a
the above-named
between
limits of density,
ranging

electromotive

of the

under

to

in. carbon

the

5 to 6 amperes
per sq.
of 10 amperes
per sq. in]. A current
per sq. in.]will suffice for the most

yield a temperature which,

such

alumina,

equivalentto

effect the fusion

that

of

of

to

0*4*

volt

is

of

to
[4,000

6,500

a
through mm.
experiments,with

mm.

OF

BEDUCIlTa

COMPOUNDS.
Solutions.

Aqueous

"

In

order

to

trsce

without

of the development of the only


the history
interruption
methods
that
it is
are
electrolytic
technicallypracticable,
desirable
consider
to
separatelya whole class of impracticable
of aqueous
solutions.
inventions,which aim at the electrolysis
Just

as

be denied
*

the evidence
as

to

the

advanced

from

diiierent quarters cannot

of precipitating
aluminium
possibility

See Borchers'

Bau

und

BetrUb

elektrischer Oe/en,1897.

in the

106

ELECTRIC

With

SMELTING

REFINING.

AKD

of the batterjr,
the colour of the
than that of aluminium, closely
mating
approxiof silver ; its other properties I have not yet had time
to that
to examine"
{George Gore* Birmingham).
a

slow

very

depositedmetal

The

and

feeble

much

was

action

whiter

depositedupon the
in dilute sulphuric or nitric acid ;
plate dissolved even
copper
ent
but the aluminium
produced by Deville exhibits a totallydifferbehaviour.
The
propertiesascribed by Mr. Gore to his
metal are insufficient to identify
it as aluminium; the same
may
be said in regard to his silicon.
The
metallic
coating,which
found
the copper plate in both instances,is probably
was
upon
but
zinc,reduced from the zinc sulphatethat had formed
nothing
in the porous
clay vessel at the expense of the dilute sulphuric
acid and the anode
f
(zincplate). (/.IfickUs,)
Jeanson
salt of 1*15
solutions of an aluminium
J electrolysed
60"
of
to 1*16 specific
0.
at
gravity, a temperature
of cryolitein
Haurd
solution
an
" recommended
aqueous
chloride of magnesium or manganese.
Bertram
||proposed to separate the metal by a strong current
from

author

that

remarks

solutions

the

aluminium

chloride.

of aluminium-ammonium

J. BraunIT

(Berlin)proposed

of
electrolysis

alum

an

to

obtain

by

aluminium

the

ordinary temperature.
to be neutralised
during the reaction was
by alkali; and
alumina
of
be
to
was
separation
preventedby the addition
at

the

of 1*03 to 1*07 specific


gravity
The
sulphuric acid liberated

solution

the
of

non-volatile

organic acid.
and
Niewerth,** an
a
According
patent by Overbeck
of mixeither
tures
salts
of
of
solution,
aluminium,
organic
aqueous
with
which
aluminium
afford such salts,
of
the
or
sulphate
a

to

chlorides
The
Senet

of other

metals,

is to be

electrolysed.

last part of the


foregoing patent is also claimed
He recommends
his invention.
ft in his specification
as

the moderate

current

of 6 to

7 volts and

Next, A. Walter^ appears


production of aluminium

with

the

circumstances

"

solution

is

by

4 amperes.

a patent, accordingto which


possibleunder the following

of aluminium

nitrate

is to

be

so

but using the current


decomposed with a small current- density,
and
from a powerful dynamo^
employing a platinisedcopper
be
plate,that aluminium
depositedon the cathode in a
may
form.
pulverulent

*[Phil. Mag., 1854 (March), p. 227.]


de Pharmacity 1854 (June), p. 476.
Record
and
of Science
InduMry,

iJoiim.
X Annual

1875.

Vide

Richards'

1890.
Aluminium,
" U.S.A. Patent 228,900, June 15, 1880. Vide Richards' Alumininm, 1890.
Patent
H German
28,760.
IIComptfs Rendus, 1876, vol. Ixxxiii.,p. 854.
*"

English Patent

ft Cosmos

XX German

5,756, December

les Mouden, 1885.


Patent
40,6*26.

(From

15, 1883.
Richards'

Aluminium, 1890.)

107

ALUMINIUM.

the time that this patent was


About
published,in the year
*
there
from
the
for the
1887,
appeared a recipe
pen of Reinbold
aluminium

productionof
alum

chloride
After
the

dissolved

were

other

depositson

in 300

metals

added, and
parts of potassium cyanide

were

cooling,39

With

solution.

weak

current,

obtained

the

at

given as

aluminium

an

good poHshable
cathode.

if this

method

parts of

Even

were

mixed

with
with

anode, and,
deposit was

plate as
aluminium

50

parts of water, 10 parts of aluminium


the mixture
heated to 93** 0.
was

process

had

be

to

been

not

production of aluminium, yet, had it


afforded proof that the metal could
solution.
This special
case
cannot,
the
made
statement
at the
controverting

for the

been workable, it would have


from aqueous
be precipitated

however, be

taken

beginningof

this section.

R. de

as

Monteglas,!in

from
lytically

the first place,separatedthe iron electro-

solution

of aluminium

lead,tin,or zinc oxide, claimed


with the added
metal.

to

chloride,and, after adding

depositthe

aluminium

in

junction
con-

and
of Falk
Schaag,} the
specification
aluminium
salts of non- volatile organic acids in aqueous
tion
soluwith the cyanides of copper, gold,silver,
to be mixed
are
of the resulting
tin,or zinc,and after increasingthe conductivity
of alkaline
bath by the addition
nitrate
or
phosphate, the
from
it
by electrolytic
correspondingalloysare to be separated

According

to

the

means.

and

of patents which
Twining possess a number
have for their objectthe production of aluminium
and its alloys
After
the addition
of
alkaline
aluminates.
the
by
electrolysis
alkali and
metallic
of cyanides,or of other compounds of an
a
the
its
of
to
nature
oxide,aluminium, or one
alloys^according
of the added
is to be deposited oy the current
perature
at a temsalt),

Burghardt

of about

80** C.

and

invention
consists in a separationof
Pfieger'sg
a
nd
aluminium,
alloys,
magnesium in coherent form,
of secondary
the occurrence
which
is to take
place without
to the methods
usuallyemployed) the
reaction,if (in contrast
Nahnsen

aluminium

be cooled, and
electrolyte

solution during

Rqueoos

rise in

be
electrolysis

the

temperature

of the

guarded againstby

the

of 40** 0.

of

use

any

a separacoolingagents. Thus, at a temperature


tion
aluminium
in considerable quantities,
hydroxide occurs

of
but

4* C.

at

metallic
Rietz
*

all the

is said

aluminium

to

be

obtained

in the

state.

and

Herold|| consider

solution

of

aluminium, starch,

JtvotHert^ Jwtrnal, 1887.

EnglishPatent

t German
" German

Patent

liGerman

Patent

Patent

10,607. Aug. 18, 1886.


48,708.
46,753. [English Patent
58,1.36.

8,552, May 23, 1889.]

108

BLEGTRIC

And

be

to

grape-sugar
of alumtniunL

After

suitable

for
electrolyte

describingthe

then
The

applicationof
works

the

of the

the

view

"

In

burg

without

process
the
method
viz.,

Reduction
but

residual solution

1892, recorded the


constructional work at

who

Metal

and

describingthe

that

at

was

at
process,
Iron
piUars,which

the

time

same

of this

first account
of

its want

recorded

Pitta-

of the

Director

time

Company, published the

he

is to be

Company, in Tacony,
most
important part
from
the electro-metallurgical
point of
of depositingthe aluminium.
Iron

Tacony

Hunt,!

always

joumSs,in

Germanf

whole

1897

but

and

of the grape-sugar.

aluminium-platingto iron

but
Pennsylvania,
of

separatesout,
current

the

bars, whilst

for the recovery


American*
and

deposition
producing this
the

usingplatinum
subjectedto strong pressure, and

is to be

metal
into

be cast

to

treated

The

of

manner

solution,they state that the aluminium


in a spongy form, by applyinga strong
electrodes.

REFINING.

AND

SMELTING

success.

previously been coated thickly with


with a
covered
with
an
alloyof a little aluminium
copper, were
unfortunatelyproved to be
very large proportionof tin, which
durable for but a short time, the process used being as follows :
The iron pillars,
destined for use
in publicbuildings
which
were
coated
in Philadelphia,were
first thoroughly cleansed, then
had

"

with

to
copper
alkaline
copper

the

bath,

bath
electrolytic
minate

in
The

water.

the

the

thickness
and

of

1*5

afterwards

were

containing sodium
proportion of

25

of

temperature

employed
current-density

mm.

transferred

to

produced, but,

as

an

80 amperes

per

already stated,

the

and

55* C.

about

was

metre

square

alloy

[7'4 amperes per square foot].Under these conditions an


of 25 per cent, of aluminium
and 75 per cent, of tin should
been

an

alu-

sodium

and

stannate

bath

was

in

75, potassium cyanide, and

the

[0*06inchl

have

did

coatingformed

prove to be permanent.
It is unnecessary
to criticise these processes,
made
proposals
by Gomer8" and Marino. ||
not

The

opening statement
that
hope whatever

no

to

attempt
solutions.
of

our

obtain
The

successful

extraction

present knowledge,

of

Aluminium.
aluminium

in
"

were

are

the
The

there

gained by

be

an

aluminium,

of

be

aqueous
in the state

accomplishedby

the

of aluminium.

Electrolysis
first

of

Fused

experiments

concerned

with

the

in

Ck"ni.
the

duction
pro-

electrolytic

Iron Agt, 1892, Feb. 25, June 2.


t StaU und Eisen, 1892, Noe. 7 and 14.
Franklin Inst.,1897, vol. cxliv.,pp. 81 and 171.
X Joum.
" English Patents 7.205, April 11, 1894 ; and 14,327,July 25, 1894.
20,354, Oct. 24, 1894.
IIEnglish Patent
*

is

of
electrolysis

the

only

can

compounds

Experiments
of

by

to

later

other

that

confirmed

be

laurels

any
aluminium

of fused
electrolysis

Early
pounds

only

can

and

10^

ALUMINIUM.

unsuccessful.
decomposition of the oxide, but were
made
by Davy* in the year 1807, after he had
decomposing the alkaline hydroxidesby the same

process.

were

in
The

Davy had at
command^
experimentsf
afforded
of
aluminium.
him an
iron and
Working with
alloy
vessel charged with an atmosphere of hydrogen, he employed
a
A
the followingarrangement:
connected
platinum plate was
to the positivepole of a voltaic batterycontaining 1,000
up
with
couples. This platecarried a layer of alumina moistened
and
kneaded
water
closelytogether. Into the upper part of
introduced
iron wire which
this mass
was
an
was
joined to the
The
became
wire
of
the
instantaneously
negative pole
battery.
heated
to a white
heat,and fased at the point of contact with
both whiter
The
metallic mass, after cooling,
the alumina.
was
brittle than iron.
On treatingit with acid a solution
and
more
obtained
from which alumina
could be afterwards
was
separated.
the
first
to accomplishthe electrolytic
Bunsen} was
separation
from its fused compounds,using for the purpose
of aluminium
he had
the
of
designed for the reduction
apparatus which
double
magnesium (p. 3), and adopting the readily fusible
of aluminium
chloride
and sodium
as
electrolyte.But, as the
metal
in
form
at the low temperature of
separated pulverulent
salt to the mixture
the fusion, he gradually added
common
of
the
the
until
the temperature at
during
experiment
progress
raised almost
last was
to the
melting point of silver. After
the
found
metal
in
was
largeregulinesphericalmasses,
cooling,
which
could be melted
into a regulus by projectingthem into
alumina

resisted

his

action

They
succeeded

the

bat

of the

it is not

current

which

improbable that

later

"

fused

salt at

common

white

heat.

experiments was despatchedto the


Annalen
"ditor of Poggendorff^s
on
July 9, 1854; and only a
few weeks
later,on August 14 of the same
year, H. St. Claire*
laid his thesis on
minium,
Deville
metals, treating especiallyof alubefore the French
Academy of Science.
Bunsen's

DeTille's

text-books

of these

acconnt

As
statements
Process.
to the effect that Deville
"

unnoticed, that portion of

process
to his

with
exf"eriments"

which

adduces

French.
*'

Up

obtain
"

his

given in the

here

of

crept

into

left
intentionally

the thesis which

has

many
Bunsen's

reference

Bunsen's

reasons

form

have

magnesium apparatus and


for modifying the arrangement
is
literal translation from the original

||
to

the present time it has appeared to me


solutions by means
from aqueous

impossibleto
of the gal-

aluminium

PhQ.

Tram,, 1808, pp. 1 and 333.


Trans,, 1810, p. 16.
X Pogif'Ann., 1854, vol. xcii.
iAnn. de Ckimie ei de Phys,, 1854, vol. xliii.,
p. 27.
'Y PkU.

II[This translation is taken from Deville's

original
paper.

"

Translator.]

110

ELECTRIC

AND

SMELTING

RBFININO.

believe in the absolute


now
battery; and I should even
of doing so if the brilliant experimentsof Bunsen,
impossibility
had not
in the productionof barium, chromium, and manganese,

vanic

shaken
convictions.
However, I am compelledto say that
my
all the processes of this kind which have been publishedrecently
have given me
in reference to the preparationof aluminium

only negativeresults.
of which
Every one knows the beautiful process by means
Bunsen
has produced magnesium by decomposing magnesium
chloride with the aid of the galvanicbattery. The illustrious
professorat Heidelberg has opened a way which may lead to
results that will be interestingfrom
points of view.
many
of
there
be
the
can
no
However,
applying
hope
batteryto the
of aluminium
direct decomposition
chloride,which is a substance
'"

that does not

fuse,but that volatilises at a low temperature; it ia


therefore,to find a compositionfor the metallic bath

necessary,
that shall involve
aluminium
have

found such

sodium,

and

the

the

of

C,

and

which

is

sodium.

introduced

from

which

aluminium,

into

of
is

sufficiently
high

temperatures above

fulfils all the

substance

the

required conditions.

porcelaincrucible,which
compartments by a plate
and
of biscuit porcelain,
of a battery
decomposed it by means
of five elements, using carbon
electrodes,the crucible being
in
heated, and the temperature being increased continually,
order
that the charge might be maintained
in the fluid condition
1

this

feature
a
necessary
This chloride,
which

fixed at

remains

although it is volatile at

fusing point of

material

the

productionof
by

185**

fusible at about

fusible

be

can

of aluminium

the extraction

temperature,

use

electric current.
depositedby
in
the
chloride
of aluminium
substance
double

alone

imperfectlyseparated into

was

as

it became

two

graduallyless

and

less

fusible; but

the

Arrived

of aluminium

not exceeded.
was
fusing temperature
this point, I stopped the experiment,and, after lifting
out
the apparatus to
the electrodes,1 heated
the diaphragm and
of the crucible a
a
bright red heat, and found at the bottom
which
rolled
of
and
exhibited
was
to
was
aluminium,
regulus
its
March
It
the Academy
18o4.
at
was
20,
meeting on
accompanied by a considerable quantity of carbon, which had
preventeda notable portion of the luetal from uniting into a
This carbon
resulted from
the disintegration
of
mass.
sinj^le
the very dense sample of retort carbon that served as electrode ;
electrode was
and as a result of this action the positive
entirelyin spiteof its thickness,which
able.
eaten
was
away
very considerThis disposition
of apparatus (as used
for
by Bunsen
at

magnesium) was

to which

the
is
2

not

as

process
follows:

parts of

I have

The

aluminium

aluminium

chloride

"

in the

convenient
been

case

led,after

of aluminium

; and

experiments,
many
bath is prepared by weighing
and adding to it 1 part of marine

Ill

ALUMINIUM.

Bait

the

in

porcelaincrncible
in with

sets

dry powder.

of

state

to abont

heated

of

evolution

The

200'' C.

heat, and

there

whole

is mixed

Combination
results

in

shortly
very

fluid

mixture, which is the bath used for the decomposition.


"
The
apparatus [Fig.67] consists of a glazed porcelain
of precaution,
is placed within
(P) which, as a measure
somewhat
mounted
a
larger fireclaycrucible (H); the whole is surcrucible
with
slot
a
cover
(D) pierced
(L) through
by a
which
is passeda wide and stout sheet of platinum (K) to serve
as
negativeelectrode,and with an aperture in which is tightly
the latter is placed
fixed a well-dried porous cell (R). Within
bottom
The
rod of retort carbon
a
(A) as positiveelectrode.
be kept at the distance
cell should
of some
the porous
of
crucible

centimetres

from

crucible.

that of the celain


porThe
porcelain

cell are
the porous
level with the
filled to the same
ide,
chlorfused aluminium-sodium
crucible

and

and

the

after the

apparatus

described.

manner

then

electrodes are
and the current
the

with

Aluminium
sodium

some

platinumplate,
togetherwith some

chlorine

chloride

aluminium

gaged
disen-

is

cell
in the porous
thus produced which

are

is

the

chloride upon
and

The

introduced

is passedthrough

apparatus.

deposited

is heated

fumes
are

by introducingdry

powdered

marine

salt at

stroyed
deand

vals
inter-

into the porous cell. This


salt is transported
to the negative
the
along
operation,
pole during
the

with

for

small

are
(two are actuallysufficient)
required
which
feeble
ance
resistchloride,
presents only a

of elements

number
to

aluminium.

Fig.67." Deville's apparatus


reducingaluminium.

decompose
to

the

the electric current.

platinum plateis raised from time to time, as it becomes


charged with metallic and saline deposit. It is
sufficiently
of salt is rapidlybroken, and the plate
allowed to cool,the mass
"

is

The

replacedin

the circuit

The

crude

material

detached

from

the

clay
porcelaincrucible enclosed within a firethe mass
is treated with water,
crucible.
After cooling,
chloride ; and a grey
which dissolves a large quantityof sodium
is re-united
into a regulus by
metallic powder is left,which
double
chloride
of aluminium
successive
several
fusions,adding
and sodium, if necessary, during each fusion.*'

electrode

is fused

in

112

ELECTRIC

SMELTING

AND

REFINING.

Although the

and Deville for extracting'


processes of Bunsen
been
aluminium
could not have
carried into effect on
a
mercial
comthat
stood
the
difficulties
to
in
basis,owing
many
way,
their

work

be

must

present methods"
Practical
"

said

Obstacles
researches

laid the

have

to

to the

was

not

has

shown

that

that

carbon

rods

almost

to

cathodes,appear
produced by the

of

aluminium

onr
pounds.
com-

Electrolysis of

proved
adapted to alnminium
perfectly

Deville's

foundation

of fused
electrolysis

viz.,the

the

the
Chlorides.
of carbon
cathodes

use

redaction.

crucibles,when

or

melt, so great

is the

Experience
employed as
disintegration

metal

An
mountable
insurseparated in their pores.
this
of
is
found
u
se
practical
plant
the
in the chemical
action of
and
electrolyte
depositedmetal
of
which
the
material
structed
apparatus might be conupon
every

obstacle to the

; and

suitable

no

has yet been

substance

found

for the

which
to
are
melting and electrolysing-vessels,
and
with
haloid
salts
of
used
the
aluminium.
externally,
Both the fused salt and the metal
itself absorb
so
ties
impurimany
in this way. during the electrolysis,
that the valuable properties
aluminium
of the reduced
are
destroyed. The ordinary
become
and plumbago crucibles contain
silicates which
fireclay
reduced
the
and
the
latter
with
is
contact
metal,
separated
by
manufacture

of

be heated

thus

contaminated

with

this

With

silicon.

property

is

ciated
asso-

slightresistance to the action of melted


Porcelain
haloid compounds (excludingthe fluorides).
vessels
above
the faults of the
not only have
crucibles,but are very
and costly,
whilst they are only to be had in small sizes.
fragile
Crucibles of compressed carbon
are
so
porous, that they cannot
be heated
externallywhen filled with a liquidsubstance, unless
are
they
protected by an outer coating of an impermeable
material.
Finally,there are no metals,which could be practically
and that are
applied,that are sufficiently
refractory,
yet
neither liable to attack by the electrolyte,
of
nor
capable alloying
that

with

of very

aluminium.

The

productionof

pure

aluminium

has failed,
owing to the

by

these

of suitable

want

methods,

fore,
there-

for the

materials

melting vessel.
The

of Deville's

Teaching

Deville, in

brought

the

forward

notice, but

treatise
deserves

have

been, by

enunciates.

He

to

metallic
with
to

suggestionthat

that

to

and
which

to

of

reason

there

be

those
objects,
especially

aluminium

maintain

by

aluminium-sodium

has

known

important
the

than

it appears
principlethat it

conditions

under

which

be coated
of copper, may
of his process.
In this case, in order

means

constant

"

reference

better

the

describes

Experiments.
has
been
made"
hitherto almost
escaped

Bonsen's

made

proportionof

chloride

aluminium

bath,he recommends

in

the

use

the

fused

o/anodes

114

SMELTING

ELECTRIC

made

5. Cathodes

is

6. There

no

oould

carbon

qf
of working at

conditione

AND

REFINING.

that time known

material

known

be

not

employed

(p.113).
is suitable

that

Jbr mdting
compounds

of aluminium
vessels to be nsed for the electrolysis
when external heatingis applied.
the

This, then, was


nineteenth

of the

The

century.

last obstacles

the

later,by

thirty years

almost

of affidrs at about

condition

the

under

solution

of

the

middle

were

removed,

the

difficulties

Before
under
the fifth and sixth heads.
mentioned
passing to
the methods
to mention
at present in use, it will be advisable
of the
proposalsand experiments which, to
separatelysome
could not possibly
judge at least from their originaldescriptions,

lead to the desired

result.
Processes.

Impraoticable

by
process,*

which

First

"

melted

mixture

these is Gaudin's
among
of cryoliteand
common

and
decomposed by the current into aluminium
That
of Elagenbuscht scarcelyrequires criticism
fluorine.
with
to be electrolysed
clay,melted with suitable fluxes,was
salt

to

was

be

of zinc ; and the zinc


alloy by distillation or

the addition
the

from

specifiedin Berfchaut's

process
with that

invented

decomposition of
without

by

was

The
refiningprocess.
i
dentical
practically

is

patent |
Faure's

Deville.

apparatus (1880)for

chloride may

aluminium

to be removed

afterwards

by

also

be

passed

the

over

comment.

Graetzel's

but
patent " describes a process that is well known
referred
It
in
cal
chemito
quiteimpracticable. is,however,
many
bat as being
being not only sound in principle,
somewhat
It
examined
be
operation.
must, therefore,
The inventor
than would
be otherwise
more
carefally
necessary.
chlorides
fluorides
melted
in the
to
or
electrolyse
proposes
apparatus shown in Fig. 68. The melting vessel,", is made of
material, and is
porcelain,stoneware, or similar fire-resisting
direct
of
action
the flame by a metal jacket.
protectedfrom the
vessel is a cathode
Within
the inner
of metal, preferablyof
text-books

as

in actual

aluminium

; whilst

the

anode

is

carbon

rod, K,

enclosed

in

porcelaintube, G, provided with openings, ^, below and an


a current
During electrolysis
escape pipe,p, for chlorinoiabove.
of reducinggas is circulated
through the fusion chamber, B, by
means

of the

tubes, 6^

force

required,as

and

o^.

In

order

to

reduce

the

motive
electro-

strengthof the
impoverished,there are
introduced into the inner vessel,G, besides the anode, but quite
are
independent of it, plates or rods, M, which
composed of
alumina
and
carbon.
The
is to
carbon
equivalentweights of

bath,

which

would

well

otherwise

as

to maintain

the

become

MonUeur
voL zi.,p. 62.
(See Richards' Aluminium, 1890.)
SeietUiJique,
t English Patent 4,811, 1872.
(See Richards' Aluminium, 1890.)
: EngUsh Patent 4,087, 1879.
Patent 26,962.
" German

115

ALUMINIUM.

with

combine
latter
carbon

the

of the oxide, whilst the metal


of the
oxygen
into oombinatioD
in the bath.
the
Unfortunately,
the
desired
not
result, but only serves
to
give

passes
does

introduce

impuritiesinto

aluminium

the

condition
become
these

pure,
in that

but

the

it

the

be

it may

case

of the aluminium

survived, of

electrolyte.In

must

separated
well

cathode, the

be

is at

in

asked

to

the
what

obtain
molten

would

claymelting vessel,or,

separated aluminium

of

order

itself?

The

if

duction
intro-

the
reducing gases
of
aluminium.
After
the
electrolyticdeposition
foregoing
left for criticism.
'remarks,there is but little of the invention
Lest, however, it should be said that those who were
tempted
this apparatus, were
to repeat the experiments with
unskilful
so
that they failed to recognise
be
its advantages,it should
added, as an especiallysignificant
his

Magnesium

did not
for

process

superfluousin

capacity as
Hemdinger

of the
manager
und
Aluminium'

Fabrik^

least

Graetzel

fact, that
himself^ in

the

his

use

obtaining

own

minium,
alu-

but that of Beketoff


consisted
p. 95), which
the reduction
of cryolite

(see
in

by means
applied
process
but the

of
for

magnesium.
a

patent

in various

countries,

applicationwas
to

the

He

for his

best

of

fused,
re-

the

Fig. 68.

"

Graetzel's

aluroiniam

electrolysing-vessel.

author's

knowledge, everywhere
exceptingin England.
The
although
by fioguski-Zdziarski,^
process brought forward
has
the
workable
in
not practically
manner
described,
yet some
in connection
with certain later patents. Cryolite,
interest
or
suitable
and
with
aluminium
mixed
other
is
fluxes,
compound,
melted
in a wrought-iron or plumbago crucible,heated
in any
of the crucible is placeda
At the bottom
convenient
furnace.
which
aluminium
metal
is to be alloyed with
; and, during
metal
while
the anode
this
forms
the
is a
cathode,
electrolysis,
The
fluxes actually
rod dipping into the fused bath.
carbon
substances
which
the
contain
must
can
electrolyte
forming
the
whilst
with the fluorine separatedat
anode,
readily combine
Mixtures
should
also
be
rich
aluminium.
in
as
as
possible
they
obtained
these
be
requirements may
by fusing
answering to
carbonate
other
with
of soda
aluminium
or
compounds
cryolite
in
similar
with
other
carbonates
a
behaving
or
potash, or
way
*

EnglishPatent 3,090,FeU

1}, 1884.

116
in

flaorine.

respect to
silica when

remarked

When

ideas

The

contain

give

mixture

(AloOj) is employed,
sufficient to
flux should

the
some
general remarks
upon
of the current, and the injuriousness
in the metal
mixture, it is further

After

present
^*

"

the

expressed in

Farmer*

this

the

patentee

thus

well known

been

in

revives

in

quantity

In this

than

do

the

case

of most
unworkable.
those

practical
reasons,

alternative

an

aluminium

of

amongst

and electrolyse
even
is to serve
melting-vessel

The

used

he

must

of

potash,or soda, or both."


undoubtedly
patent specification

are, for

(as

proposes
compounds) to mdt
open

oxide

an

for oonsideration

matter

vessels.

flux

of carbonate

inventions,which

other

of

easilyfusihle combination.

an

consist

more

REFINING.

AND

the action

and
expenditure
of

SMBLTING

BLECTRIC

the

year

other aluminium

aluminium
also

1885

chloride

idea which

an

in

cathode ; and

as

had

long ago as 1808.


searchingfor a patent,has not forgottenthat
aluminium
chloride is easilyvaporised under
tions,
ordinary condiand therefore proposes
of
to accomplish the electrolysis
so

in
Grousilliers,t

this salt in closed


which

vessels

under

pressure

"

method

of work

is

obviouslyimpracticable.
%
sight(butonly thus) Grabau's patent specification
would
by the use of cooled electrode cells,to afford a
appear,
of preventingthat absorptionof impuritiesby aluminium,
means
which
is so troublesome
fused salts are electrolysed.In
when
explaininghis process, Grabau givesthe followingexample: In
chloride
the electrolysis
and sodium
of a fused bath of cryolite
it is known
that chlorine is evolved
at the positivepole,and
aluminium
in the liquidcondition at the negative. But
since
melted
is capableof attackingevery known
fire-resisting
cryolite
and non-conductingmaterial, this electrolytic
only
process can
i
n
the
be appliedwhen, as is rendered
possible
present process,
the affected parts of the apparatus are protectedfrom the action
of the fused salts or the separatedconstituents
of the bath, by
the use
of an
insulatingand resistingshield. In Fig. 69 is
At

first

"

shown

description.The
firinguntil the bath

iron

latter should
is made
a

and

shape of

be used

by

in

r* and

water

outlet

or

pipe

trough,C,

of the melted

melting vessel,A,
thoroughlyfluid ;

in

the

is heated
and

process under
by external

the

level of the

The hollow
metallic cylinder,B,
be at X X.
double walls,through which, for coolingpurposes^

as

r^ the

is

use

then

with

fluid such

for

suitable

arrangement

an

is

aluminium

coolingthis
leaves

it

by

be circulated,
air may
r
walled
doubleAnother

employed
which

as

reservoir

separates.

The

being

the

vessel,in

inlet
the

for the

reception
liquidor gas to

the walls
vessel enters the space between
r^. In consequence
of the coolingaction

"U.S. A. Patent 315,266.


Patent
t German
34,407.
Patent
X German
45,012.

[English Patent 8,478,July 14, 1886.]

117

ALUMINIUM.

producedby

this
the

solidifies over

portion

circulation,a

of

the

surface

cooled

the

of

whole

melted
of

salt

the

cell,

collectingvessel,C, and of the tubes, and forms at


is not capable of
these placesa non-conducting crust, which
aluminium.
the
fused
salts or by
beingattacked either by
Grabau starts from the assumption that only those parts of
in
come
vessel containingfused cryolite,which
sn
electrolyte
lead to the introduction
contact with the separatedelements, can
If this were
of impurities
into the bath and metal.
true, he
the
difficult
have afforded a solution to
almost
would certainly
He can
aluminium
of
electrolytically.
problem extractingpure
the
solved
almost
to have
question,
only be said in that case
B, of

the

Fig. 69.
because he
the

does

not

cathode, with

will have

"

which

the
specification
of
separated particles

in

state

doubtful

cell apparatus.

's cooled

the

his

intimate

into the most

to come

appears to be
it is shown
in

Grabau

whether, by

the

be

of

aluminium

Further,it

contact.

use

Fig.69, the chlorine would

nature

of the anode

cell

as

removed.
efficiently

The author's experienceis that a largeproportionof the chlorine


which rises from the anode, tends to float on the surface of the
fused salt,
and to approach the walls of the vessel,and there,by
contact

with

impuritiesinto the bath, and


But putting these imperfections
resultingaluminium.

iron, to

hence into the

aside,the

introduce

author

has

mixtures of aluminium

salts

in iron vessels without

both

or

never

double

the

bath

succeeded

in

electrolysing

salts,containing fluorine,
and

the

metal

taking up

118

8MBLTINQ

ELECTRIC

much

The

iron.

ground

is in

such

objectionto

of

Lossier'*'

durabilityof iron yesaels when


itself both a proofof this assertion

alone

used

of

want

for these processes

BBFININO.

AND

processes.
the present

has

time, patented

to

up
electrolytic
separation of

aluminium

pure

and

from

the

aluminium

silicates.

unpatented process of Rogers,{ which


melted
at electrolysing
cryolitewith a cathode of molten
and
Here
is used initially^
lead
of
and sodium
an
alloy

Richards
aims
lead.
this

t describes

an

of the sodium.
expense
Company, of Milwaukee, which

separates aluminium
Aluminium

American

founded

in 1887

Winkler, "

A.

have

his
with

met

borates

scarcelybe

"

less

even

work

than

success

of the

one

of aluminium

with

latter process
Daniell ft has
of fused

it with

the

oxides

of

numerous

from
itself

could

"

has

seen

ever

use

bath

lyte
electro-

as

of aluminium
a

an

and

chloride

of the haloid

salts

metals. IT
electro-positive
Cowles.**
patentedby
lysis
unlikelyapparatus for the electromore

proposed an

chloride

aluminium-sodium
the

production of

; and

aluminium

even

combines
chloride

by

method.

Wohler's
Diehl

of the fluonde, ALFg


11 patents the electrolysis
chloride
prepared by a specialmethod, using sodium
fusion

the

has also been

plant for

his

zinc,with

or

afterwards

;||and

latter metals

The

of

nature

did

the

fluoride

barium, strontium, calcium, magnesium,


of

who

anyone

of the double

mixtures

first of

the

boron.
recommend

wiUi

granted to Feldmann

Patents

stated

were
made, but as the
electrolysis-vessels
used
of alumina
he
as
were
electrolytes,

proposed seriouslyby

of Wohler's

account

not

separationof pure aluminium


borate
aluminium
from
even

predecessors.The
of fused

Gorlitz,has

borates

phosphates and
must

process, appears,
the erection of a small experimentalplant.

of

of which

material

was

however, to have

apply this

to

itself with

contented

The

the

at

and

carbon

NaF,

in

the
the
uselessrecognised

electrode.

Having
(p.112) he substitutes for them, at a later
which
date, others consistingof ferro-aluminium
to
are
(AlgFe),
take up aluminium
until they contain
the
during electrolysis
of 13 to 20
equivalentof AlgFe. He works with a current-density
a

of such

ness

cathodes

amperes
per square inch.
the richer alloyis removed

again used

is
*

German

as

Patent

The

tt German

it German
1889.

Patent

of aluminium

heating,and

the

contained
residual

in

Al^Fe

cathode.
31,089.

X Proceedingsof the WiacoTmn


Patent 45,824.
" Oerman
IIGerman
ITGerman

by

excess

t Richards' AlumirUum, 2nd Ed., 1890.


Natural
History Society,April, 1889.

[EnglishPatent 12,575,Sept 16, 1887.1


**
50,370, 1889.
EnglishPatent, 11,601, 1890.
Patent
50,054, 1889.
[EnglishPatent 4,169, March 9, 1889.]
Patents
59,406, 59,447 ; and English Patent
813, Jan.
16

Patent

49,915, 1S87.

119

ALUMINIUM.

Other
known

inTentions,the
or

details

of which

have
impracticable,

are

been

previously

either

were

made

recentlyby

more

and

Berg,* Dixon,t Oraetzel,t Diehl,"Faure,||Case^lT Goooh


Waldo,** Roger,tt and others.
Saooessfol

attempta

Bedaotion
made
to

were

produce the
compounds, which

of the aluminium
the

Prooesses.

of electrical

conversion

"

heat
were

Some

twenty

years ago
for the fusion

necessary
to be electrolysed,
by

within

energy

the

melting vessel

this way, the key to the successful solution of the


The productionof heat by the agency
found.
problem
of electricity
was
attemptedin two ways : either by introducing
the electric arc
into the melting chamber
the mass
to be
or

itself;and, in

has been

heated,

as
by includingthe electrolyte

or

in the

resistance

electric circuit.

Only the latter way has proved economically


successful ; but some
attention
be devoted in the first case
may
and arrangements which have for their object
to those processes
the

decompositionof

electric

Are.

The

"

of aluminium

of

of Aluminium
electric

of the

zone

by

Compounds

the

Eleo-

arc

and

here available,
are
electrolysis
yet the temperature
when
is unnecessarilyhigh for the end
a
sought,even
is employed; and, moreover,
this excess
of heat is
arc

concentrated

within

very small
of aluminium

for the extraction

arc

in the

too well for the purpose


serves
even
Although the two requiredconditions

extraction.

heating

small

compounds

arc.

Decomposition
trio

aluminium

The

area.

of the electric

use

be considered
must, therefore,

extravagant.
The

impulse to
by Sir W.

furnace, of which
been

made

to

this

use

some

of

account

an

will be given after reference has


description
of the earlier experimentsand proposals.

tem|"erature obtainable

The

of heat is traceable to the publication


of his electric smelting

source

Siemens

in the

electric

arc

seems

to

have

first utilised in

experiments made by Depretz. In a note


Academy of Science,of December
17, 1849,|t he
describes the behaviour of a small retort of sugar charcoal (of
with
formed
about jV^nchdiameter)within which
the arc was
The
itself
served
the aid of a carbon
retort
as
positive
point.
been

the

to

French

electrode.
Johnson's

Prooess.

smeltingof
March

ores

22. 1853.

the electric

arc,

"

German

EnglishPatent

Patent

was

"

somewhat

patentedby
The

which

ore
was

was

later

J. H. Johnson

mixed
caused

with
to

invention

for the

"" in England on
and placed in

carbon

play

between

two

large

56,913, 1889.
[Cf.EnglishPatent 2,002, Feb. 6, 1890.]
Patent
t Oerman
16,794, Oct. 24, 1889.
58,600, 1890.
Patent 62,853, 1891.
Patent 62,907, 1892.
||German
S German
irU.S.A
Patents 512,801-512,803, 1894.
"*U.S.A.
Patents
[English Patent
527,846-527,851, 528,365, 1895.
Patent
tt German
20,615,Oct. 17, 1894.]
83, 109, 1895.
"" English Patent 700, 1863.
K^Comples
Rendiia, 1849, vol. xxix.

120

ELECTRIC

; the

electrodes
and

slag.

thus

ore

These

SMELTING

AND

became

fused

and

fell into

substances

two

converted

into

metal

receptacleplaced to
furnace,they were

suitable

of

receive

REFIKIKO.

a
them, where, by means
kept in the fluid condition until the metal had separated from
the slag(compare Gerard-Lescuyer,
tion
specificap. 125). The same
contained
different appaalso a description
of a somewhat
ratus.
The
include
electrodes were
to
two
as
an
so
arranged
between
filled
them.
The
and
hollow
with
was
angle
upper was
the ore to be reduced, which
wards
to be graduallyimpelled forwas
with
it
In
connection
this
a
screw.
description, is
by
interestins: to examine
a sketch
(Fig.70)which is taken from an
English patent specification

In this
the

Oowles.*

H.

of

EE
figure,

are

iuto
electrodes,

upper of which
is fed by means

funnel,and
the

"o

the

the

ore

of

passes to
of

neighbourhood

the arc, while the fused


neath.
products pass out beIt is not impossible
named
that the Johnson
in the above

patent

only the agent

was

for the

real

inventor, for the

first

part

of the

above

descriptionwould
apparatus which

an

described

Pichou

by

suit
was

in

is
year 1853, and
considered by Andreolif
the

Fig. 70.

"

Cowles'

furnace.
ore-smelting

be

to

first electric

the

smelting furnace;
which
in
is
shown
is
reproduced from
71,
Fig.
apparatus
sketch.
O
carbon
rods
O
are
Here,
gripped by
original
holders,A A, x x are the conductingwires,T T are screws
advance

the

carbons

smelting hearth

chimney.

In

this invention

applying it was
The

with
then

was

out

"

Electric

furnace

little that

was

KngUsh

for

new.

Patent

question;
sightof.
Furnace.

"

but
Sir

EnglishPatent

the

to

of
possibility

William

showed

refractorymaterials
It was
not
proposed

4,664, 1887.
:

the

furnace, M

of the
lost

never

Siemens

electric

the

the

N is the
is masonry,
beneath
and
L
is the
it,
grate placed
of
state of technologythe practical
use

into

the

this

to

Siemens*
in

use

principle

it for

t Indmtrtes, 1893.

2,110, 1S79.

the

122

ELECTRIC

SMELTING

RKFININQ.

AND

the two vesaels


placedin a metallic case, H, the space between
conductor
of
with
other
bad
filled
charcoal
or
being
powdered
heat.
such as is
A
rod of iron or platinum,or of gas-carbon,
used for electric lightpurposes, is passed through a hole in the
bottom
in order
For

that the

of

means

whilst
iron

within

coil of

The

is drawn
which

arc

it is

measurement;

that

it

freelyin

move

can

offers

which

magnetic force by
is
solenoid-coil,

the hollow

balanced

by

freelyalong the beam,

determined, and,

within

vertical

the

iron

electric

the other
positive,

AB.

The

limits

resistance

imposed by the
slidingweight to

Hence

arc.

negativeelectrode
whilst

increased

an

sink

to

diminished

resistance

of the

nected
con-

the

leads the

arc

the

greater depth within

to a

resistance

is

negative,pole of

the

to

cylinder

G,
counterpoise,

of the
is fixed, by the shifting
The
end
solenoid-coil
the
of
one
requiredpoint.
the

plane

of about

total resistance

of power
to

pended
sus-

the centre

B, supported in

copper or other good conductingmaterial,


end, B, of the beam, a hollow cylinderof soft

be moved
is

beam,

wire, S, which

into the

may

of the

of

stripof

fastened

so

50 ohms.

any

uniform

of

be

end, A,

to the other

is

source

is

should
the

from

is also bored

of the crucible

cover

be passedthrough it.
negative electrode may
if
a
used, possible, cylinderof compressed

this electrode

carbon, which

by

The

of the crucible.

crucible,

the

counterpoiseto press
coil,whereby the length of the
cylinderdeeper
the
is increased
until
between
arc
equilibrium is restored
This
the
is
of
forces.
automatic
highest
opposing
regulation
importance,for without it the temperature in the crucible would,
a

the iron

the

on

causes

in the

hand, diminish,while, on

one

diminution

in the electric resistance

melting would

the other

sudden

produce not only a

hand,

increase

the sudden

during the

of the materials

ance
in the resist-

It is essential
of the arc, but probably also its extinction.
the satisfactory
performance of electric fusion, that the

to

substance

positivepole of the arc,


because, as is well known, heat is generatedat this pole. This
with metals
only, for
arrangement is evidentlysuited for use
it
is
to provide an
nonconducting earths or gases
necesssry
indestructible
positivepolewhich is also capableof beingmelted,
and so of forming a layerof liquidat the bottom
of the crucible.
The heat accumulates
the aid of a mediumvery rapidly. With
sized (36 Webers
crucible
8
ins. deep,set in nonconducting
a
*) dynamo
heat
be
white
in
less
material
brought to a
may
than

quarter of

half

consumption

an

stream
*

hour, and
from

was

be translated

the

the

lbs. of steel may


commencement.

negative pole,the

electrode,or

of cold water

[The Weber

it may

an

hour

of the

water-cooled

a
a

form

"

"

it within

should

to be melted

is made

amperes.

check

in
the

[Siemens]usea

of copper
through which
This consists of a
to circulate.
tube

the old electrical unit of


"

author

be melted
To

Translatok.]

quantity ;

in the above

pl"oe

123

ALUMINIUM.

simple copper cylinder,closed


a

caoutchouc
to

aerres

The

tube

into it

convey

Fig. 72.
A

common

best

coke

is
'

metal

Each

tube

electrode
crucible

to

the

cold

by
guided by

steel furnace

air

by

or

pair of
from

uses

the

English

of

is made

electrodes,A

cooled
is

from

is taken

(Fig.73)

Of
patent specification.*

lower

of water.

stream

adjoining sketch

whilst

end, and containing


the bottom, and
nearly

the

at

reaches

which

carbon,

water,

R,
rollers,

2^

as

in

r.

of the

to 3 tons

regenerativecrucible furnace

of steel

melted, a
per ton
1 ton, and
used in cona
nection
regenerative gas furnace when
with an open
The
electric
about
12
cwts.
hearth, only
furnace
therefore approximates to the regenerativegas furnace

only

in respect of fuel economy.


has the following
the former
But
advantages: 1. The temperature attainable is theoretically
"

unlimited.

2. The

charge

3. The

atmosphere.

is melted

process

Fig. 73.

"

Siemens'

can

in

be

modified

conducted

reached

limit

is very
which
is

of

temperature

high,because

in

the

much

without

electric furnace.

and under
the
preliminarypreparation,
Even
when
4.
using
experimenter.

materials, the

completely neutral

direct

supervisionof the
ordinary refractory
be practically
may

the
that

electric

furnace

the

stance
sub-

being heated is hotter than the crucible,whilst


ordinarymelting processes the temperature of the crucible
exceed that of its charge. Although the electric furnace
must
not
supplant the ordinary furnace,yet chemical reactions
may
in

of the

most

varied

kind

be
may
hitherto

in

future

carried

unattainable.
aid,and at temperatures
found
trials
with
this
practical
apparatus, it was
of steel could

be

completely melted

in

course

that

hour, and

an

with

on

In

20

its
of
lbs.

9 lbs. of

platinum in a quarter of an hour, whilst copper which had been


than
90 per cent, of its weight
packed in carbon dust lost more
volatilisation.
by
The
Kleiner-Fiertz
Eleotrio
Fumaoe.
Although the fur"

"

EnglishPatent

4,208, 1878.

124

ELECTRIC

SMELTING

AND

REPINING.

justdeBcribed were not expresslyintended for the treatment


ideas
the fundamental
compounds, they embodied
the arc furnaces which
have since been
proposed and experimentally

naces

of aluminiam
of

tried

example, from

for aluminium
the

extraction,as

followingaccount

of the

for
be seen,
may
the
construction
of

Kleiner-Fiertz

aluminium
in which
fluoride was
to be
furnace,'^
treated for the separationof aluminium.
The electrodes of the
74 and 75) dip into a vessel,B, lined with
clay
apparatus (Figs.

'

Fig. 75.

Fig. 74.
The

Kleiner-Fiertz

aluminium

furnace.

The negativeelectrode,
aud bauxite.
K,
cryolite
is capableof adjustment in a vertical plane,and the positionof
the positive
poleis controlled by a weighted lever and a solenoid,
its movements
by a piston,I, plungbeing limited and checked
ing
difficult
It
and
above.
is
into a liquid,
to
placed
say what
has
that
of
Siemens.
The
over
advantage this arrangement
far behind
of the method, no
doubt, remains
practicalsuccess
that anticipatedfor it by the inventors ; but it is not possible
and

filledwith

German

1886, and

Patent 42,022, 1886.


[Compare EnglishPatents
15,322, Nov. 24, 1886.]

8,531 June 29,


,

125

ALUMINIUM.

work
with any material,which^ although
imagine continuous
fying
has
to
melt,
comparativelyeasy
ample opportunityfor re-solidiof the heat of the arc
at so
owing to the concentration
An
immediate
material.
small
cold
in
to
a
point
proximity
much
the
would
current
be
more
frequently
interruptionof
into the charge,
necessitated by the freezingof the electrode
than by the decompositionof a sufficient quantity of the double
to

fluoride in the bath.


Electric

Grabau
apparatus for
The

melting

Furnace.
reduction

or

the

arc'*' have

not

removed

with

the

Kleiner-Fiertz

of

exhibitingthese

appearance

The

degree.

material

of the

surface
and

this

pole

for the

the

reduction

plant; indeed, they


disadvantagesin an even
is introduced

melted
the

crucible

by

tion
connec-

have

the

higher

beneath
of

means

the

tubes^

one

the

in

under

material
to

be

added

either
with

associated

is to be

tinuously,
con-

alone,

alloyedwith

The

alloying-metalat
time

is made
The

the current.

kept

at

notch.

The

the

fused

mass

height
overflow

an

illustration

descriptionof

detailed

apparatus

need

it.

to conduct

constant

of

means

or

metal

the

same

by

in

specificationwhich

patent

is

of

means

difficulties described

in

mass

forms

illustrated

are

that

to

by

and
process
the
electric

of the
passage
tions
modificaVarious

current.

allow

fused

mass

be

Grabau's

"

not

The Gerard-Lescuyer
electric furnace.

Fig. 76.

and

"

this

be

given

here

for

the

already

reasons

indicated.

apparatus (Fig.76)
Gerard-Lescuyert affords a very good illustration of the
Instead
of mixing the
in 1853.
furnace
patented by Johnson
before submittingit to the action of the arc^
with carbon
ore
The

Furnace.

Qerard-Lesouyer

The

"

of

he moulds

it into bars

with

the aid of pressure, and


carbon, and tar, and then

with

copper, alumina,
electrodes for the productionof the

arc.

In

other

in admixture
uses

these

as

respects the

described by Johnson's
specification
(p.120).
process is sufficiently
References
Fumaoe.
Willson
to Willson's
The
I process
of producingaluminium
are
frequentlyto be found in technical
"

literature.

But,

by

the

light

of

his

patent specifications,

Patent
Patent
t German
German
48,040, 1887.
44,511, 1886.
t U.S. A. Patente 430,463, June 17, 1890; 492,377,Feb. 21, 1893. English
Patente 4,757,March 17, 1891 ; 21,696,Nov. 28, 1892 ; 21,701,Nov. 28, 1892.
*

126

ELBCTBIC

could

alnminiam

Kleiner-Fiertz

AHD

SMELTIHO

EEFININO.

redaced

scarcelybe

because,like
profitably,

others,be employs the electric arc for heating


and electrolysis,
which is both costlyand extravagant. His first
furnace was, at least,so far unlike that of Siemens' that he had
introduced an arrangement by which
reducing gases (or carbon
powder and the like)might be injectedinto the arc,* in order
and

extent
action to some
electrolytic
; but it is less
the points of novelty exhibited
by his later
easy to discover
A
B
is
carbon
in
set
A,
crucible, (Fig.77),
apparatus.
masonry,
and
is connected
by the
metal
plate,6, to o^ which
is joined up to the electric
to

assist the

lead.

carbon

forms

the

other

is

joined by

to

"7,

by

rod, C,

pole, and

the

holder,

screw-threaded
which

c,

spindle,

vertical

ments
move-

be

it with

imparted to
may
aid
the
of the hand-

wbeel, h.

The

reduced

be

much

80

material

is mixed

carbon

to

with

that

it

not
can-

the

actuallyfuse; yet
inventor

ing
expects the result-

metal

to

liquate from

this

excess

that

from
it may
be withdrawn

time

of

carbon,

so

time

to

through
d. From
later
tap-hole,
i
t
publications appears that

the

Willson

obtained

carbide, and
the process
The

the

The

Production

of

of the

furnace.

Willson
a

Melting

as

metallic

metal,

he used

in

it

Electrolysis

of

Aluminliim

fused

Fig. 77."

not

Com-

of
Currents
by
for
high
Density
very
Temperature
by the Heating

pounds

that, in
perfectlywell known
accordance with the laws discovered
by Joule, electrical energy
in passing through any
conductor
is converted
in
or
entirely,
into
heat.
conductance
the
of
The low
liquidconductors
part,
with
known
in contrast
that of simple conas
ductors,
electrolytes,
Action

Current.

necessitates

"

the

It is

use

may

[EngUeh

very
be
electrodes

if the
former, especially
this
and
current
great depth ;
substances
refractory

of

is indeed

be fosed

Patent

and

9,361, June

strong
not
so

for the

current

immersed

to

powerful,that

brought

into

17, 1890.]

the

any
even

liquid

127

ALUMINIUM.

of the
by the heat generated. Thus the whole mass
daring electrolysis
;
electrolytebecomes
very nniformly heated
the localisation
and this is a great advantageas compared with
the arc is employed.
of the heat when
The
introdnction of this principle
Hiroiilt Frooess.
The
of alnminium
the extraction
not
possibleas a
only rendered
hitherto
superable,
inthe
solved
but
difficulty,
mann"cturing process,
for the construction
material
of finding a suitable
all aluminium
At the present moment
of the melting vessels.
of baths, which
make
works
are
use
kept fluid by electrical
the
first
but
the
almost
and
only inventor who, so far,
;
agency
of
of this method
has
given in his patent a good specification
French
is the
working, accompanied by clear illustrations,
he
his
In
[German] specification*
engineer, Paul H^roult.
his invention
describes
a
as
''process for the production of
action of an
the
aluminium
heating and electrolytic
alloysby
condition

"

electric current
with

which

on

the

the oxide

English patent, which


**

An

was

improved Process

aluminium, AI2O.,and

taken

and
different,

is somewhat

of

shall

aluminium

covers

for the

be
out

alloyed"
in the

name

the metal

[The title of the


of

Henderson,

thus
largerfield ; it runs
minium
Preparationof Aluminium, Alua

"

by Electrolysis."]
Alloys of Aluminium
method
of heating will be sufficiently
The
explained by the
was
following descriptionand sketch of an apparatus which
Swiss
the
MetallurgicalCompany,
actuallybrought into use by
at Neuhausen,
the Alnminium-Industrie-Aktiengesellschaft,
now
other
of
shows
iron
78
Switzerland.
or
in
a case
metal, a,
Fig.
below
and open at the top, and provided with a thick
insulated
lining of carbon plates.A, which are held together by some
carbonaceous
cementing-medium, such as tar, treacle,or glucose.
also be a good
The
of which
the case, a, is made
material
must
Bronze,

and

conductor;

and

in

order

to

ensure

the

most

intimate

contact

lining.A, and the


hence
and
obtain
the
to
side
of
inner
a high conductance,
case, a,
it as a shell
be
made
with
the case
by
casting
advantage,
may,
will then produce
the lining; the cooling of the mass
around
of copper
to a are
the desired effect. Attached
a number
pins,
the
electrical
least
with
the
which
conduct
a',
possible
current,
resistance,from the negative leads to the basin or crucible,A.
the ends of the positive
In the crucible are immersed
electrode,B,
close
laid
which
either
rods composing
the carbon
are
together
filled
be
that
small
must
a
or
separated by
up with
spaces,
between

the

oonductor,

outer

such

as

of the

surfaces

copper

or

carbon.

carbon

At

the

upper

ends,

the

taken
of which were
and American
The French, English,
Patents, some
of his collaborators (Schweiz. Metallurg.Gesselsch.,
in the name
Patents
French
turn) or of his patent agent, Henderson, were"
175,711,
Apra 23, 1886, and 170,003,April 16, 1887 ; EngUah Patent 7,426,May 21,
1887 ; German
Patent
47,166, Dec. 8, 1887 ; U.S.A. Patent 387,876, Aug.
14, 1888.

cot

I^y-

128

ELECTRIC

carbon

held

platesare
from

chain
be

electrode,B,
The

will.

with
with

the

Figs.78

and

SMELTING

may
lower

AND

REFINING.

the frame, g, which (issuspended


of the eye, e, so that the whole
into place,or raised or lowered
at

togetherby
by

means

brought

frame, h, attached

to

the

the necessary
for making
clamps or screws
lead
the
from
dynamo. With the
positive

79.

"

The

H^roult

aluminium

and

in

furnace

is vided
proconnection

electrode,B,

in

exception

section,
longitudinal

plan,

of the

the electrode,B, and necessary


for its
space, i, around
free vertical movement,
the melting chamber
is closed entirely
the
has
graphiteplate,k, which, however,
by
openings,n, for
the

introduction

of materials

to

the

furnace.

Channels

are

cut

lining.A,
apertures,n, and these
channels, m, n, provide also for the escape of ^ases generated in
the furnace.
The
movable
the rim, o',
plates,
o, provided with
in the

and

the

to

correspond with

handle, o", serve

to

cover

the

the

openings,n, during

the

130

ELECTRIC

SMELTING

this process is intended


for the
aluminium-bronze.
especially
From
first

director

of

prematurely

was

in

memoir

which

he

that
was

had
the

the

pure

Kiliani

"

so

Aluminiumof

commenced,
Gesellschajlf

Fig.80.

by

laboured

successor

manufacture

productionof

dedicated by
the
Neuhausen
removed

alloys,

aluminium

to Kiliani,the
Regelsberger'^

Aluminium

death

from

the

Works,

who

field of

work

be ascerit may
tained
successfully,
which
Aktiengesellschajli

Industrie'
the

Scfwoeizerischer
after

soon

aluminium

H^roult's

REFINING.

AND

by

aluminium

MetaUurffischen

its foundation
process

furnace for small

in

worked

1888,
out

to

by

installations.

aluminium
place of H^roult*s
alloy process, which
had
It is much
to be regretted
previouslybeen used there.
with
the
of
mention
of the
that,
Regelsberger's
exception
fact

in

that

Kiliani's

the

process
already owned

agreed

is extracted

in America

in

the

principle with
Schweizerischer

that

of

Metal-

by
patents
lurgischenGesellschaft,nothing further has been made known
concerningKiliani's work in this direction,which without doubt
has done excellent service in the development of the aluminium
industry. Publications relatingto aluminium
commonly state
that

the metal
^

Zeiischr.

under

the Hall

fur Elektroc?iemie,
1895, vol. i.,p. 528.

patents,

131

ALUMINIUM.

and

Europe under

in

is,however,
Hall

the

of

edition
Hall

of this

and

under

and

Minet

hook,

Minet

or

described
the

dispute

have

described

hoth

were

worked

ment
state-

criticisms

that

certain

in

systems
the

works

does

factories
The

operation.
in

unworkable

as

which

out

processes
patents, the author

in their

working adopted by

This

Minet.
Borchers'

in the first German


processes, as made
the American
in which
patents of C. M.

statement

of these

and
with

variance

processes
conditions.

industrial

other

direct

the Minet

If Hall
those

of H^roult

those

at

may

differ from
not

wish

have

one

present

question

of

method
be

cannot

to
or

said

to

differ in any way


in the fundamentally important points from
that of the H^roult
but at that time
no
published
process;
the
of Hall
other
than
in
those
accounts,
patent specifications
and

Minet,

found
his

opinion on
previous opinion

workable.

In

and

known,

were

his

the

Borchers

these.

only

stilladheres

Nevertheless, he
the

that

first

obviously could

industrially

not

are
processes
the
inventors
place,

to

be allowed
may
of their patent

words
in the actual
to
speak for themselves
here given,together with reproductions
which
are
specifications,
of the original
drawings.
in the
received
The
Hall * was
first applicationof Oh. M.
Patent
it

was

and

Office of the United

States
the

divided,and formed
400,664 of April 2,

July 9, 1886 ;
patents 400,766

of America

on

basis of the two

1889

(the day

that

the

patent

was

granted).
Hall's

American
herein

described
its oxide
fluoride

Patent,
relates

to

by dissolvingsuch
salt of

the

400,766.

aluminium,

The

"

"

reduction

invention

of aluminium

from

containinga fused
reducing the aluminium
as
through the bath, substantially

oxide
and

electric current

by passing an

No.

in

bath

then

In the accompanymore
fully described and claimed.
Aereinafter
ing
drawings, Fig. 81 representsa sectional elevation of a form
of apparatus applicablein the practiceof my
invention, and
and
Fig. 82 is a view partlyin elevation
partly in section of a

modified
"

In

form

of apparatus.

practiceof

the
of

the

my
aluminium

crucible, A,

the

fluoride

solution

invention

I prepare

bath

by fusmg together in
of aluminium

the

and

for the
suitable

fluoride

of

than aluminium
metal more
electro-positive
as, for example,the
^these salts being preferably
flaoride of sodium, potassium,kc.
mingled together in the proportions of 84 parts of sodium
fluoride and 169 parts of aluminium
fluoride,representedby the
"

"

formula, Na2Al2Fg.
consists in
alaminium

fluoride is

adding

to

fluoride.
to secure
*

convenient
the
The

in the

method

of

forming the

mineral

bath

cryolite^f of its weight of


^
object of thus adding aluminium
bath the proper
relative proportions

[Compare EngliBh Patent 5,669, April 2, 1889.]

132

ELECTRIC

SMELTING

of the flaoridAs of alttmiQium


added

alumina,
and

the

electric

or

is

other

solution.

preferablyhas
oxygen
released

at

fv?ien it
electrode

18

the fused bath

of aliiminium, in sufficient

D,

suitable
the

By

connected
of

source

bath

fused

an

electric current, which


4 to 6 volts,
of about

force

positiveelectrode,C, and aluminium


of
the negative electrode,D, which, on account
aluminium
for other
metals, is formed of carbon

may

be

is

the

at

desired

is

ties,
quanti-

of
by means
with
a
dynamo-electric
and immersed
electricity,

of the

action

electromotive

an

is released

of
affinity

To

being dissolved by the


passed through the solution

C and
suitable electrodes,
in the

sodiam.

alumina

current

machine

and

the oxide

or

REFINING.

AND

to

prodticepure

formed

of

B^^i

The

(duminium.

the

(/)

positive

carbon, copper, pUUinum,

other

or

mV^y

p
Pig. 81."

Hall furnace, U.S.A.

The

suitable material.

When

graduallyconsumed,

and

formed

of carbon

therefore

must

formed
of copper an
; but when
This
the surface of the electrode.

to time
over

Patent, No. 400,7d6.


the

electrode,C,

be renewed
oxide

from

is

time

coatingis formed

coatingserves

to

protect

further
destruction by the action of the
electrode from
interfere
but
does
not
materiallywith the conducting
oxygen,

the

of
qualities
'*

and

On

the electrode.

account

of the

also the corrosive

of
affinity
action

the aluminium

of the

for other

metals,
materials,I prefer to form

133

ALUMINIUM.

the

protectthe

cruciMe

This

placed in

%8

iron

as

"

be

employed

may
the conductor

the

as

negativeelectrode,as
negative pole of the

the

from

shown

In order

be

of lithium

may
; as, for

sodium

the bath

render

to

may

electric
to

such

generator

lining.

fusible,fluoride

portion of the fluoride of

the

fluoride

by

of

molecular

sodium,

weights

fluoride

placing
dis-

the
fluoride,

parts of sodium

26 parts

contains

combination
resulting

in

parts of lithium

26

Thus

shown

more

fluoride

of lithium

substituted.
42

for

example, for one-fourth

equivalentamount
be

solvent

or

substituted

N^,

at

lining,A',
Fig.82,

carbon

(Fig.81),the

electrode,D

beingsuitably(!)connected, as

126 parts
for every
and
338
fluoride
])arts of

fluoride

of lithium
sodium

aluminium

fluoride.

While

I consider

"

carbon

B, and
placedtherein,
temperature as

lieu of the

"In

of

^and

salt.

common

an

by

"

auit"ible fumacef

sufficient heat to fuse the materials


such materials fusingat approximatelythe same

"

steel

or

of the alaminium

the action

from

same

A'.
lining,
to
subjected

of metal

melting pot, A,

or
crucible,

and

fluoriilesof sodium

proportionsof

the

and

aluminium,

of the fluorides of sodium, lithium,and


hereinbefore
alnminium
stated,are best
such
purpose,
within
varied

the

adapted for

be

may
limits without

materiallyaffectingthe
the

of

bath,

operationor

function

in

proportionswhich

fact,any

found

proportions
certain

suitable

be

may

down

in
to

the

gravity than
suitable

means

bottom

or

Modified apoaratus, Hall Patent, No.

Fig.82."

the

at

480,766.

collects

then

drops

bath, which
aluminium, and

is of

the

of

molten

the

The

employed.

globules,and

be

may

it is reduced
aluminium, as
negativeelectrode,is melted and
thereon

as,

the bath

specific
by
after being

removed

poured out, and

be

may

can

lower

be

picked out."
patent^external firingis expresslyprescribed

cooled the aluminium

in this
Clearly,
heating of

for the

cathodes
claims

are

make

stillfar from
any

it

and

its contents,
of work.

for this method

that the inventor

is to

be

of

Patent, No.

throughout with
solvent

combination, which

400,664.
"

for the
may

be

In

this

both
preceding,
alumina

termed

carbon

These

two
was

be fulfilled in
of

in the extraction

ase
practical

the

and

at this time

that must

recognisingthe conditions

agrees
another
expression,
This

crucible

quiteevident

aluminium.
Hall's American

**

the

recommended

process which

which

be

can

specification,
in idea

and

is first proposed:
fluoride
the * double
"

134

SMELTING

ELECTRIC

AND

REFINING.

and
potassium,'is preferablyformed by mixing
fluoride and 116 parts of potassium
together169 parts of aluminium
such proportionsof the ingredients
fluoride,
corresponding
to the formula
K^Al^F^. A variation of these proportions
within certain limits producesonly immaterial
changes in operI
believe the
for
of my
ativeness
now
example
(as
as,
process
fact to be),a largerproportionof potassium fluoride increases the
time
alumina, but at the same
capacityof the bath for dissolving
aluminium
whereas
lessens its fusibility,
a
largerproportionof
fluoride renders the bath more
fusible,but decreases its capacity
alumina.
for dissolving
of aluminium

"

Fig. 84.

Fig. 83.
The
**

The
be

may

Hall

combination
rendered

Patent, No.

funiaoe, American

of the fluorides of aluminium


more

fusible

and

its

Fig. 85.
400,664.
and

potassium
capacityfor dissolving

by the addition of lithium fluoride,


may be increased
partialsubstitution thereof for potassium fluoride" as, for
of the fluorides of aluminium, potasexample, the combinations
sium,
and
lithium, representedby tlie formulae KLiAljFg or
effective as regardstheir capability
for dissolving
are
KgLigAl^Fjg,
alumina, and are quitefusible."
The
in the annexed
apparatus, shown
Figs.83, 84, 85, to be
used in conducting the electrolysis
is then
described :
The
above-described
the
bath
or
solvent, is
crucible,A, containing
to melt
placed in a suitable furnace^ B, and heated sufficiently
alumina
or

'^

"

135

ALUMINIUM.

the

bath

ie.^ to approximatelya low red heat.

"

and

D, having
machine, or other

suitable

with

connections

suitable

electric

of

source

into the bath, and a sufficient amount


The
is dissolved by the
alumina

inserted
therein.
action

electric

the

of

negative electrode, D, and, being melted,

dynamo-electric

bath,
sinks

placed
by the

and

down

from
departure in this case
inasmuch
described
in the previousspecification,
as
from
excluded
carbon
here
is
use
expressly
containing
the anodes,and copper
or
platinum is recommended
There

is

the

notable

the

in

As

carbon

last

patent, the

addition

steel,

at

the

to

the

as

the

practice

any mcUericU
in preparing
as

it

tute.
substi-

possibleto

lining,

iron

to

is

copper

4.

or

tioned
men-

material

for the

suitable

holds

inventor

A', ofthe crucible (Figs.


83, 84, 85) as cathode.
In

then

are
energy,
of alumina

oi the crucible."

bottom

use

electrodes,

is reduced

aluminium

current

The

ble.
cruci-

An

electromotive

force

of

still

suffices

volts

to

for

the

current.

Hairs

American

Patent,

No.

400,665."

the
speci6cation
of the previously
use
or
patented solvents
is
claimed
diselectrolytes
In

this

being unnew
recipe
given instead,and it
as

saitable.
is

accompanied by the
description of a new

is

The

apparatus.

Fig. 86.

an

viously
preformed

alkaline

of

metal,

becomes

action
electrolytic

does

any

or

black
the
a

not

result from

of fluorine from
or

dark

alkaline

free

hence,

named,
This

double

the

substance

bath, as

been

fluoride of aluminium

necessary,
a continuous
and

minium
alu-

time.

This
fluoride

is

the electrical resistance

when

in

some

of

efficient after

separated; but a
the bath, apparentlyfrom
(!),which interferes with

increases

change the bath after


is circumvented
difficulty

to

in
same

fluoride

less

of aluminium

fluorine

no

of the

found

for

removal

is formed

constituent

action,and
electrolytic
it has

furnace, American

double

the

"'

being subjected to
change

Hall

Patent, No. 400,665.

patented bath,
and

The

"

the

calcium

employing
use

the

salts

of the same."

followingway:
is used, having a

"

"A
com-

136

formula

positionrepresentedby the
is formed
by 169 parts of
fluoride

calcium

AND

SMELTING

ELECTRIC

This

CaAl^Fg.

fluoride

aluminium

fluor spar,

or

REFINING.

in

unite

fluoride

fluorides

The

forming

double

and,

of calcium

alone.

of

representedby

calcium

While
there

out

process,
my
fluorides of the

the

closelyresemble
quite,as well as
double

employed.

the
.

which

fluorides

carrying

been

furnace,2, and subjectedto sufficient heat to


Electrodes,3 and 4; formed of carbon^when

which
if not
the

successfully
are
placed

mentioned

vessel, 1, arranged

or

double

Thus

alumina.

crucible

in

used,
almost,

may
and
answer

above

fluoride

and

CagAisFi^has

formula

either

than

of similar
be

the

than

double

CaAl^Fg

dissolvingthe

for

The

carbon-lined

the

in

of

salt

use

formula

named,

one

bath

prefer

large number

metals

same

fusible
the

to

with

aluminium

fusible

more

believe,more
the

are

and

calcium

fluoride

as

constituent

of

being

alumina

prepared by saturating hydrated


artificially
hydrofluoric acid.

parts of

7b

fluoride

aluminium

the

composition

to

fuse the

in

the

materiaL

is
pure aluminium
electric generator,

connected
to a suitable
are
deposited,
If an
machine.
-electric
a
alloy be desired, the
as
dynamo
the
it
with
of
metal
which
negative electrode,4, is formed
Alumina
in the form
of
aluminium.
is desired
to alloy the
other
of
oxide
suitable
bauxite (!),
aluminium, or any
anhydrous
form of alumina, preferablythe pure anhydrous oxide, AI2O3,
(The decompositionof the oxide
artificially
prepared.''
"The
other
in
solution
is described
as
specifications.)
to

be

in the fused

of alumina

of the double

bath

fluoride of aluminium

apparentlyheavier than the metal aluminium, and


rises after being reduced and floats
hence this metal,if unalloyed,
it is liable to loss by oxidation
to the surface of the bath, where
it
with the air or with the positiveelectrode,where
in contact
action ; hence, when
is subjectedto a strong oxidising
reducing
the crucible,1, is provided with a cover, 5, provided
aluminium
and the
with openings for insertion of the electric conductors
with
and
from
the
of
a
6, of
crucible,
partition,
gas
escape
from
side
carbon
to side of
extending down into the bath and
electrodes."
and separatingthe two
the crucible,
that
for a moment,
it will be seen
Neglectingthe electrolyte
this devious path has after all only led back to Bunsen's original
calcium

and

is

apparatus.
Then, again,"As
from
of

time

the

double

by

the

fluoride

to

of

the
the

operationcontinues, the
the

bath
double

from
the

specific
gravity of
to

calcium
in the
above

aluminium,

combination.
described

fluoride

of

the surface

bath

be

may
salts lighterthan

it of other
and

is removed

cover

removed

aluminium

The

addition
of

will sink

aluminium

weight

and

to time

bath.

lowered

addition

the

that

so
.

of about

potassium

the

the
pure
the

Thus, by
two-thirds

and

its

aluminium

138

SMELTING

ELBCTRIC

Hall's

American

protects the
"fluoride

of

Patent,

AND

No.

"

followingproposal:
calcium,
parts;

^^^
(Na^AljF^j)'

parts;
the

'1his

400,667.
A

"

234

REFINING.

the
cryolite,

fluoride

of

final

bath

suitable

patent

consists
845

aluminium,

of

fluoride

double

parts,

about

of a suitable
3 to 4 per cent, (more or less)
by
chloride.
Alumina
is then added
chloride"
to this
".^., calcium
saturated
sufficient
in
foim
to
a
bath, preferably
quantities

weight,and

Electrodes

solution.

are

then

formed

bath, the negativeelectrode

the

inserted

of carbon

being
positiveelectrode

aluminium
The
is desired.
pure
formed
of carbon or other suitable

in

when
may

be

(!)material."

and impossiare
here, then, repeated the possibilities
bilities
have
and patented previously,
which
been described
so

There

Fig. 88.-

Aluminium

furnace

used

by

the

PitteburgReduction

Company

(Richards).

that

there

is

from
to be extracted
these specificanothing new
tions
it
be
unless
the somewhat
altered compositionof the bath
and of the electromotive
force required,which
varies from
4
These
volts.
8
the
which
the
to
criticisms in
were
patents to
the German, 1891, edition of this book were
applied,criticisms
to

which
The

the author

author

whether

to

still adheres.

leaves it to the

self
impartialcritic to decide for himin Fig.88 (which is,according

the apparatus shown


Richards, that used by the

namely, the PittsburgReduction

owners

of the

Company)

has

Hall
more

patents
in

common

"

139

ALUMINIUM.

the apparatus described

wiUi

above

in the

patents

or

with

that

of H^roult.

patent (1893) granted

later

to

will be referred

J. B. Hall

subsequently.

to

Installation
[Practical

Hall

of the

The

Pittsburg
Company have put down a very large installation of
the Hall plant at their Niagara works, where
it is now
in full
read
based
on
a
operation. The followingdescription,
paper
before the Institution
to
of Civil Engineers,seems
by Hunt*
Process.

"

Keduction

indicate,however,

modified

extent

some

to
process have been
since the publicationof the specifications

that the

details of the

above.

quoted
The

consist

of

up in
of each

series.

tanks
electrolytic
and

carbon,

is riveted

to

electrical

connected

are

the

outside

connection

either

with

iron

troughs
A

stout

trough, and
the

anodes

lined
copper

serves

of the

with
bar
make

to

adjoining

of the
the
trough or with
negative conductor
generator,
or
(the
according as the trough occupies an intermediate
fore,
thereThe
tank
end
the
in
series.
itself,
negative)
position
with
cathode.

bar,
the

which

fused

aluminium
any
The anodes
are
is

that

it may
contain, acts
rods suspended from

carbon

the vat, and


these carbons

placed above

electrolyte
; as

are
are

as

the

a
copper
immersed
in
partly

graduallyconsumed

be
with them, they must
in contact
by
oxygen
in
this
It
is found
lowered
from time to time into the bath.
is approxiinstallation
that the weight of carbon
thus burned
mately
liberated

the

not

are

reduced.
The carbon linings
equal to that of aluminium
and should (with the iron contaiuingaffected,
appreciably
for several

pots) last
The

depends

process

dissolved

alumina

in the

guidance

months

in the

selection

in continuous

on

decomposition of
electrolytic
The
followingrules for
solvent have been laid down
by

the

fused
of

use.

bath.

although they will for the most part be self-evident


have carefully
read the present chapter,they may
to those who
be quoted here :
be fluid
1. The solvent,with its charge of dissolved ore, must
low
in
order
the
to obtain
at a comparatively
temperature,
proper
reduced
the
aluminium
allow
and
sink
in the
to
to
conductivity
Hunt,

and

"

bath.
2. The
at

sol vent

must

be able to

and
dissolve,

to retain in

solution,

least 20 per cent, of alumina


at the working temperature.
of the solvent must
3. The (thermo-chemical)
heat of formation

be

auch

the
"

that the latter will not

be

more

readilydecomposedthan

dissolved ore.t

Trans, Inst. Civ. Eny., 1896, vol. cxxiv., p. 208.


t [The electrical pressure
theoretically
required for the dissociation of
alumina
is 2*8 volts, whilst that for the fluorides of sodium, calcium, or
aluminium
is 4 volts or more].

140

BLECTBIC

4. The

8MELTINO

AND

REFINING.

specific
gravityof

less than

metal

circuitingby
the

between

the solvent,when
aluminium, in order

of fused

that

the

floatingto

electrodes,and

top and

avoid

to

molten,
to

the

short-

prevent

forming

be

must

bridge

minium
re-oxidation of alu-

at the surface.

5. There
to

be

must

solid

no

and infusible)
bye-product
(insoluble

clogthe pot and to prevent (electrical)


continuity.
6. The molten
solvent with its dissolved ore
be
must

conductor

of

7. The

good

electricity.

solvent

have

munt

corroding action

no

nascent

on

aluminium

the metal at the moment


of deposition).
on
(t.6.,
of
the
bath
evidentlybe varied very
composition
may
without
considerably
sacrificing
any of these conditions;but the
mixture
most
commonly employed is said to consist of 677 parts
The

of aluminium

of sodium

251
fluoride,

and
fluoride,

of calcium

234

fluoride.

In startingthe process, the ingredientsare


either
tanks
in separate vessels and transferred to the electrolyte
selves
themin the molten
condition,or they are melted in the tanks

fused

with

aid

the

prepared,pure

constantly renewed

metal

the

of the

bath

siphon

or

by
be

must

salts with

the metal.

the anode

carbons

need

care

the

not

be

the

trolyte
elec-

time, as

to

of

means

it

from

accumulates,

ladle,in which

little

as

is withdrawn

aluminium

time

case

possibleof the

as

the alumina

that both

and

all the

because
possible,

as

care

molten

will pass into the bath ; and


in character,they
electro-positive

is very
into the

part

reason

reduced

enter

be taken
The

commerce.

is thus

should

present in them

in the

salts used

various

is

the

from

by

then, since aluminium


most

bath

supply
that
so
deposited,

It is necessary
should
be as pure

foreignsubstances
will for the

the

the

about

to withdraw

taken

and

20 per cent, of the dissolved


The
of the bath is kept below 982" C.

operationis
either

added,

contain

temperature
continuous,and

bottom

When

current.

is
the

as

always

may
The

oxide.

of the

alumina

preparationof
be

such

may
of this is that

as

are

the

The

metal.

same

and
electrolyte,
sold
in
commonly
impurities(such as

the

negative
electrolead,zinc,and copper)present in them are more
silicon,
than
eliminated
and
are
by
aluminium,
completely
With
depositionwithin the first two days of use.
care, the
that
solvent should
renewal
at
so
only require
long intervals,
the
first
be
after
two days the only impuritiesthat can
present
in the aluminium
and
lining,

from

derived

those

are

the added

from

the

anode

carbon

and

alumina.

given as to the cost of working,


as
nor
employed. It is simply stated that,
0*7476 lb. of aluminium
is the equivalentof 1000
theoretically,
of energy requiredto reduce
hours, and that the amount
ampere
No

information
satisfactory
to the

actual

1 lb. of the metal


course,

is

on

the

is

current

from

alumina

is about

assumption that

746

5 H.P.

ampere

hours.
hours

This, of

yield0*554

141

ALUMINIUM.

and that the


(seetable,p. 9 of previousedition),
volts
8
2
dissociation
is
for
electricalpressure
; so that
required
of 746 x 2*8 watts, or
28 volts (i.e.,
of 746 amperes
a current
x
In practice,
Al
lb.
0'"')54
of 2*8 KH.P.) should
yield
per hour.
lb.of aluminiuDi

is "very nearly approached." It must^


that the heating of the bath is efifected
has thus
to supply
electric current, which

says, this
however,be remembered
the author

of

the
alumina
to the temperature
sufficientenergy
to raise the added
of heat from
the
loss
the
of the bath, as well as to make
good
and
that
there is
and radiation ;
whole apparatus by conduction

by means

also adds to the


in the circuit,which
resistance to be overcome
the
Even
utmost
elasticity
by allowing
consumptionof power.
it would
seem
to the expressionquoted in inverted
commas,
Addecmade
been
since
have
that considerable advance
must

by the Hall process as 1 lb. Al


gave the yield obtained
stated it to be 1 lb. per 16
Richards
since
and
22
KH.P.,
per
E.H.P."
Teanslatob,]
Frooess.
Now, as to the Minet patent,
The Minet-Bernard
brooke

"

subjectedto
which
might
standiugs,
which

was

similar

prevent misunder-

To

criticism.

arise from an incorrect comprehension of


it
may be stated that Minet's and Bernard's
newspaper accounts,
first put into operaMinet's process was
tion
processes are identical.
Bernard, and the patents are
at the factoryof the Brothers
of these gentlemen.
taken out in the names
made
for a patent* was
The first application

in

in

England

plete
sought ; the comprovisionalprotectionwas
in
with
was
January,
drawings
presented
specification

July,1887, when

accepted on February 17, 1888.


thus :
Among the salts of aluminium, some
in order
and
others are volatile,
while
fusible,
1888,and

latter

The

was

**

are

"

slightly

very

that

runs

lytic
electro-

an

salt to be
be produced
action may
which
should be in a particular
state of liquefaction,
electrolysed
salts. Thus the
is very difficult to be obtained
with aluminium
is too volatile,while
chloride of aluminium
aluminium is not fusible enough.
"It has

fluoride

the

to
alreadybeen proposed,as regardsthe first,

it with the salt of another

which

it

metal, and

to

thus

in order

to

extract

form

and
fixity,

little

more
a
imparts to
low temperature
at a relatively
subjected

current

the

that

it is essential

the aluminium

to

the

combine

double

allows

it to

action

therefrom.

of

salt
be

of the

But

the

double salt thus formed


that is to say, the double chloride
of aluminium
^is an^ exceedinglyunstable
and of sodium
body
which is handled
rise
it
and
to
with difficulty,
gives
extremely
"

"

noxious

vapours, hence
extraction of aluminium

therefrom

commerciallyfor the
by electrolysis
; in all cases
used

occasioned.

great losses are


**

be

it cannot

It has been

sought to
"

render

it still more

EnglishPatent 10,067,July 18,

fluid
1887.

by mixing
v^Te^

it
^
-

Digitfecy/^ff

142

ELECTRIC

of
quantities

small

with

(double fluoride
then

being

SHELTING

of

fluoride of aluminium
is volatilised

to

and

of

sodium,

than

is contained

the

in

sodium,

which

double

the

the fluoride

either
largerproportions,

in the

of

form

double

salt,the fluoridenot
but being
invention^as a.flvas,

as

flux, but

sodium

and

which

they

aluminium

when
without

state

obtained
=

bath

the

Electrodes.

"

in

Their

comprises the
anodes

carbon

anodes
iron

sodium

compounds

to

employed
of

proportions
10, chloride

"

cathodes,or

fluorides
to

those

of sodium

40,
of
be

For

carbon

; for aluminium

employed

50
as

of
in

of

(or

accordingto the state


the following
deposited,
pure
anodes

aluminium,
and

copper

bronze, red-copper

carbon cathodes
or
copper
carbon
anodes
and
cathodes.
be

80

be

can

and
or

graphite may

or

or

general cases.

(castiron) cathodes

even

of

may
vary
is to be

metal
and

and

cryolite;for instance, fluoride

nature

most

salt of sodium

there

different

in

the aluminium

aluminium,

that

35, fluoride of sodium


55 parts.

"

either carbon

chloride

mixtures

found

double

artificial

understood

be

are

"

in which

50,

to

cryolite,
may
in the followingproporelectrolyte
tions

an

of aluminium

flux)

metal

as

20

Cryolite
It must

in
"electrolytes

iron

60 parts.
natural
or

such

aluminium,
used, not as
parts.

its maximum

melted

other salt.

with

of sodium

"

in

"

chloride

It reaches

is found

Very good results are


any
followingproportions: Fluoride of aluminium

the

other

in the bath.

of aluminium

mixed

being

or

of

decomposed by

is

formed, in

or

contained

fluoride

or

chloride

which
will be subjectedto the
principalelectrolyte^
that the
current.
Experiment shows, moreover,
aluminium
increases with the proportionof fluoride of

aluminium

list

body

of the

yield in

'"

cryolite

the

as

action

with

of

even

sodium); this latter

former,

in the form of
being employed,accordingto their

singlesalt

the

and

the double chloride


of sodium (cryolite),
and
fluoride
the
of aluminium,
extent,
great

has,therefore,been

aluminium

tised

of

and

fixed

more

bath

"A

sodium,

and

(?).

current

of

REFIXING.

adopted solelyas a flux. Now, experiment shows


be passed through a bath composed of double
current

that if the

is

chloride

of aluminium

chloride of aluminium

which

AND

without

for

ferro-

In

short,

distinction

as

-electrodes.
"

The

metal
in

cases

the

as

crucible

be

of

earth,of plumbago, or of
refractory
and
(iron,cast-iron,red-copper,platinum,and the like),
where
an
alloyis required the crucible itself may serve
cathode,or

may

as

the anode.

"

the other
platinum,which is unalterable but costly,
bath
the
of
chloride
sodium
metals are attacked
of
(mixture
by
and
still
have
further defect,that is
and fluoride of sodium),
a
to the direct action ofihcfl/xme,
to say, that,when theyare
subjected
too
to
or
high a temperature, they allow the bath to filter
through,hence a considerable loss results.
"

Besides

143

ALUMINIUM.

With

'*

to the

89 and

the

arrangements

drawings,such

accompanying
90 show
a generalview

manner

that the bath

defects

of the

are

obviated.

arranged

tanks

filter through.

cannot

reference

described,with

hereinafter

Figs.

in such

It is sufficient for

this purpose
a
to provide the metallic tank, a b, outwardly with
thin brick wall.*
The
bath is prevented from
becoming dirty
in consequence
of the metal of the tank
of two
entirelydifferent arrangements

beingattacked by means
accordingas it is desired

to obtain

alone.
an
alloyof aluminium, or pure aluminium
''First arrangement, Fig.89.
of aluminium
For the formation
alloys. The tank is made of the metal which forms a component
the carbon
anodes ; a 6 is the
part of such alloys. A A are
metallic

tank

operation,and

serving as
fast

as

cathode.

aluminium

as

beginning of the
produced by electrolysis.

At

is

the

Fig. 89.

Fig. 90.

Bernard

there is formed

furnace.

(Minet) aluminium

the

layer,a, of
ciently
alloyis suffiin
rich
aluminium, the metal formed anew
electrolytiAs shown
in Fig. 89, the
callyruns to the bottom of the tank.
bottom of the said tank is slightly
inclined,and is provided with
a tap-hole,
T, which allows after a lapseof time, determined
by
the
withdrawal
of
the
fused
of
aluminium
means
experiments,
containingsmaller or greater portionsof the metal forming the
tank,which is not a defect,as the objectto be attained was the
formation of an alloy.
Second
the formation
of pure
For
arrangement, Fig. 90.

the aluminium

on

inner

surface

of the

be obtained.

alloy to

When

tank

this

*'

aluminium.
cathode or
*

Let

cathodes.

be

the

The

anode

or

cathode, 0,

[Thiswall is stated in the French


the vesselfrom the coke,fireemploy td to

anodes,
is

and

arranged

C
in

be
a

the

small

as
being used to protect
specification
it to a red heat.
hiring
Translator.]
"

144

ELECTRIC

8MBLTINO

AND

BBFINING.

crucible,d, placedupon a plate,e, these two apparatus being


formed
of fused alumina, or fluoride of calcium, or of carbon
blocks,

cathode.
and

6 is the
The

in the tank

current

tank

which

is connected

resistance,r, interposedbetween
tank
is sufficiently
great so that

metal

the

metallic

with

the

the

cathode

the

derived

represents only a small portionof the whole

10

the inner
to form
cent.). It serves
upon
of
and
of
the
metal
an
aluminium,
alloy
forming the said tank, which alloy protects the latter,and is
The
metal
which
posited
is deonly feeblyacted upon by the bath.
in the crucible,
d, in this arrangement is nearlypure.
ascertained
the
and
Having now
particularlydescribed
current

(5 to

surface

of the

per
tank

**

nature

of my

is to be

performed,I

*"

The

said

invention, and
declare

hereinbefore

in

that what

described

what
I claim

process

the

manner

same

is :

for the extraction

upon

and comprising the


by electrolysis,
of pure
extraction
the characteristic
or
aluminium,
alloyed
features of said process being :
bath where
fluoride of aluminium
^'1. The
of a metal
electrolysis
of
the
is
double
state
or
a
a
single
salt) used, not
(in
as
a
flux, but as the main electrolyte,
being subjectedto the
a

largescale

of the current.

influence
*'

2. The

avoid
**

of aluminium

of

use

brick

coveringfor the

tank

metallic

as

so

to

the filtration of the bath.

3. The

of the tank

use

alloyof aluminium, or
alloywith the metal

an

"4.

The

use

of

at

as

of
production

for the

destined

least of aluminium

an

form

to

the tank.
constituting

derived

cathode

current

on

pure aluminium.
and
of fused alumina

the

tank

when

it ia

obtain

requiredto
'^5. The

use

of

carbon

of fluoride

plates,and

of calcium
of the

foundation

which

the successful

extraction

(or

crucible

blocks)for the formation


servingfor the productionof pure aluminium."
The above specification
oflers no suggestionwhatever
bath is to be heated
electrically,
althoughthis forms

that the
the

of aluminium

very
is

upon
the contrary, it is much
more
clearlyexplainedthat
the crucible is to be protected
externally
by masonry againstt?ie
action of flame. The use
in the
is excluded
of carbon cathodes
based.

On

arrangement

here

electrolysis
by
not thought of
was
The

out.

weight,not

The

described.

the

criticisms

use

above

only to the

of aluminium

feedingof the
compounds,

at the time

alluded

Hall, but

to

that
to

the

bath
such

patent

apply therefore

the Minet

was

during
as

mina,
alu-

taken

with

full

patents also.*

[Ithas been stated by Gh^nevau


(vol.i.,p. 55), that,in applying the
90

in the BtmiA de Physiqueet de Chimie


Minet
process at St. Michel, Savoy,
with
chloride is
70 per cent, of sodium

of cryolite
mixed
charge,bauxite and aluminium fluoride being introduced during
The electrical pressure
electrolysis.
requiredis 7*5 volts for each bath,
and
the out-turn
is equivalent to 0*88 oz. of aluminium
per horse-power
per

nsed

as

cent,
a

hour. "Translator.

146
time
with
the

carbon

for the
that

succeeded

not

apparatus constructed

an

liningwas
decided

therefore

as

had

Borchers

AND

BMBLTINe

ELECTRIC

walls
to

is in the

to

furnace

melted

within

be

producing pure aluminium


according to this description;
in

he
of disturbance, and
always a source
work
entirelywithout one, and to arrange

of the

midst

of the

to

be
it

from

the

zone

of

of the

made

them.

furnace

Fig. 92." Borohers' aluminium


distance

REFINING.

Since
was

the

clear

extraction

material

same

of

source

that, at

heat

certain

apparatus.

fusion,the coolingaction

of the

air

surrounding the apparatus (or of a specialcoolingdevice,such


a water
jacketsimilar to those which are so frequentlyused
in metallurgical
certain sufficient
a
work) must leave unmelted
thickness
of a lining composed of alumina
or
cryolite.The
constructed
details of the first furnace
the
author
these
on
by
in
lines,and still built by the firm of E. Leybold's successors
follows
are
as
:
Cologne,
(Fig.92)
as

"

147

ALUMINIUM.

An

crucible,T, with

iron

alumina

(F) with
compound.
and

bottom,
bo

cooled

or

steel

into

it is screwed
of

means

water

inner

the

nearly to
R,

serves

ternally
in-

bottom, B, is lined

fusible
di"Bcultly
is let into

plate,K,

The

by

chamotte

other

side tube, E, introduces


ing
tube, X, reach-

narrow

of

the

aluminium

lining of

the

tube, B, which may


copper
A
other
suitable medium.
or
whilst the
the water for cooling,
the

top

as

an

escape pipe. The tube,


K, and, through it,the
steel plate E, which
acts

as

cathode

beginning

the

of

periment,
ex-

in

put

are

connection

the

at

the

with

conductingcable,
of the
N, by means
clamp, V. The carbon
main

rod.
anode
with

; it is connected

the iron

which

U,
plate,

of

by means
clamp and

an

iron

an

iron rod

is screwed

plate.The

the

the

forms

A,

into

current

is suppliedthrough the

rod,P,

copper

and

the

sleeve fixed

copper
above-mentioned
the
rod.

The

metal
at

on

ulating
accum-

the bottom

of the crucible

during

the

is

run
operation
through
tap-hole,S, into

offat intervals
the
the
the
the

mould, G,
gases
anode

through

while

evolved

Fig.93.

"

Modified

at

Borohers*

aluminium

furnace.

escape

the

for the
openings in the cover, D, which also serve
of the charge of alumina.
admission
The
lated
crucible,T, is insuP by a chamotte
from
plate,I. The lining,F, in spite
of its solubility
in the bath, is sufficiently
protectedby the
the walls of the
cooling action of the air playing around
crucible.
For
of
operations
long duration, and with a high
further
ducing
current-density,
protectionmay be afforded by introcoolingarrangements into the lining.
The

above

furnace

can

be

used

even

with

current

of about

148

ELECTRIC

But
50 amperes.
the coolingof the
within

the

shown

in

designed
also
of

use

material

The
then

until

it makes

quicklydrawn

back

little cryolite
is next
with the aid of a spoon.

of the

wall of the

with

contact

far
sufficiently
thrown
Here

When

arc.

furnace

had

prevent

the

furnace.

lining
placewithin the coolingjacket.
i^
anode
is exceedinglysimple. The

of this furnace

use

afterwards

furnace

into

stamped

first lowered

in

stronger currents.'"' This


to
cooling jacket, intended

reachingthe metal

was
cryolite

carbon

substituted

were

conductance,

always be kept
blocks, arranged aa

cannot

with

sheet copper

fused

limits,cooled

thermal

high

cathode-block

metallic

Fig. 93,
for

to its

since,owing

desired

REFINING.

AND

SMELTING

on

it

the

to

for

an

has

in the

furnace

hood
neighbourwith

covered

become

it is

be struck.

to

arc

floor of the

the

quicklymelts

cathode

cathode, and

the

be rapidlyfilled up
the fused charge,the melting chamber
may
with cryolite,
the anode being graduallyraised meanwhile, until
it is removed

by a space several centimetres


wide.
Alumina
in prois now
sprinkled into the electrolyte
portion
first a
metallic
aluminium
but
is
at
as
separated out ;
of the oxide
with advantage,since
be added
slightexcess
may
when
in this way,
the current-density
is not
too
high, the
the anode
and the fused charge is improved.
between
contact
fused salts with
It has been observed that, in electrolysing
a
when
furnace
the
is too
or
hot, the
high current-density,
immediate

from

contact

In

cathode

the

the

between

the

and

anode

this

evolved

the

melted

is

mass

anode

in such

case
impaired.
gases are
it with
a
quantity and at so high a pressure as to surround
of
the
continuous
which
current
can
layer
only
gas, through
the
formation
short
Thus
of
of
the
number
a
arcs.
by
pass
heated
fault
and
the
becomes
is
accentuated,
unduly,
electrolyte
if,as in the electrolytic
especially
separationof aluminium, the
anode
is constantlydiminishing in size,through the
carbon

at

evolved
This formation
of the oxygen
at its surface.
of
in
and
the
increase
is
an
advantage
consequent
temperature,
arcs,
at lecture
in the laboratory,
or
desirable
demonstrations, where it is unaction

work

to

with

because
quantities,
with

cooling jackets around

purposes

it is obvious

question,and
that
the

large apparatus

it facilitates the

no

that

heat

the

that

this

conditions

the

fluidityof

But

for

industrial

is out

costly system
of working must
be
is not
required to

produced which
the electrolyte
and

is

use

walls.

considerahle
very
of smaller
apparatus

or

of the

metal

that

of

so

the
chosen

maintain
is

being

separated.
Process.

Bradley's
on

large scale

"

The

conditions

will be

reverted

to be observed
to

hereafter.

See ZeiUchr.furMJUktroeJiemie,
1898, vol. iv.,p. 523.
Gold- und
Silberscheiaeanstalt
suppliedby the Deutschen
at Jrrankf ort-on

-the-Maine.

This
vorm.

in tions
operaBut first
fumaoe

i"

Rossler^

149

ALUMINIUM.

it will be

well

to

certain

examine

interestingpatents

which

in America, in 1883, but which


applied for by Bradley,'*''
were
granted to him only at the end of J 891 and the beginning
of 1892,and were
first publishedas a patented process in 1896.
The
most
interestingportion of these descriptionsis as
were

follows

:"

''Hitherto

by subjectingthe

on
a

before
(i.6.,
other

fused

or
crucible,
the temperature

condition

gas)attacks

of the

it has
is

gas liberated in the


the material of which

is that the
the consequence
destructive fluxingaction takes

treatingalmost

the fact that


but

'

the

in the

even

action,the

mere

sufficient to

make

case

fluoride

process
the crucible
is

in

mode

the

case

the

in
of
of
and

of aluminium
crucible

of reduction

itself,
(fluorine

composed, and
quicklydestroyed. This

place to

is

greater or

less extent

greatly aggravatedby
subjectedto heat from without;
exert
do not
materials which
a
fluxing
material,and

any
crucible
of

with

fluxes

or

this

that,in

found

been

crucible

in

heatingfurnace

with

crucible

double

unites

ore

in

current

high to keep the ore


sufficiently
is encountered
the greatest difficulty

preventingthe
working the process, for
which
especially,
cryolite
and that the

of the

action

is

; but
destruction

sodium, the fused

the

to

ore

carried

been

process! has

this

refractoryvessel,placedin

where

melted

1883)

mechanical
it almost

is

is

action

of

impossibleto

the

external

prevent

the

heat

is

cracking

of the crucible.

object of my invention,therefore,is to dispense


with the externsJ
applicationof heat to the ore in order to
In order to accomplish this object,I employ an
keep it fused.
of greater strength or
electric current
intensity than what
be required to produce the electrolytic
would
decomposition
in a state of
other
substance
maintain
a
nd
I
the
ore
or
alone,
of the current
fusion by the heat developed by the passage
the electric
melted
the
invention,
so
that,by my
through
mass,
of
distinct functions,one
is employed to perform two
current
melted
these being to keep the ore
by having a portion of its
electrical energy
converted into heat by the electrical resistance
offered by the fased ore, and the other being to effect the desired
the heat, being prodecomposition,by which means
duced
electrolytic
at exactly the point
in the ore
itself,is concentrated
where it is requiredto keep the ore in a state of fusion.
consists in dispensingwith
feature of my invention
Another
the crucible for holding the ore, and in employing a body or
heap of the ore itself to constitute the vessel or cell in which
the reduction takes place,
is not destroyedby the chemical
which
The

"

main

"

action of the fused

ore

and

the

gas

liberated,and which, there-

Patents 464.933, granted Dec. 8, 1891 ; 468,148,Feb. 2, 1892;


473,866,April 12, 1892.
ttThiaquotation is from U.S. Patent 468,148." Translatob.]

*U.S.A.
and

150

ELECTBIC

fore,admits

being

SMELTING

continuous, notiiing^
process being perfectly
the
the charging of fresh ore
fast as
as

of the

requiredbut

reduction

goes on, either


walls of the heap itself.
'*

To

enable

describe

it

aluminium

others

from

its

Upon a hearth
heap or body of

ore

the

without

from

out

carry

my

ore

other

or

or

proceed to
of

the extraction
material

suitable

piled
shape

is

in the
pulverised,

less

or

more

to

sides

the

process, I will

particularcase
cryolite.
*

from

or

one

of brick

"

to

appliedin

as

REFINING.

AND

cavityor basin is excavated in the top


of the heap to contain the fused portionof the ore which
is to be
the
In order to fuse the ore at
treated electrolytically.
start, I
take two electrodes of a suitable material, such as already used
effected by an external
in like processes where
fusion has been
to the
two
furnace, and connected, respectively,
poles of a
of
electric
machine
other
or
source
current, bring the
dynamo
said electrodes into contact, separate them sufficiently
to produce
of

truncated

and

cone,

Fig

Fig.95.

94.-

Bradley'saluminium

smeltingfurnace.

then thrust them


electric arc, and
into the ore lyingat the
the ore
fuses by the
bottom of the cavityor basin,where
soon
an

heat

of the

and

arc

becomes

conductingelectrolyte,
through

the electrodes continues


from
The
to flow.
which the current
exist
there
is
to
of
as
soon
as
a
conducting
course, ceases
arc,
the electrodes,
between
and the passage
liquid the fused ore
then takes placethrough the fused ore by coudncof the current
"

"

tion,and

heat

the

is

producedas

it is in

incandescent

lamp.
merely used to melt the ore in the beginning,and the
is kept melted
ore
by incandescence,so to speak,the metallic
aluminium
being gradually deposited at the cathode and the
fluorine gas being set free at the anode
so
long as the ore is
The

arc

is

maintained
started

order

in

state

of fusion.

the electrodes
that

the

metal

As

soon

should be moved
set

free

at

the

electrodes
fluorine set free at the anode."

short

In

an

circuit

this

between

the

as
a

the action is

little farther

cathode
or

be

shall

figuresnot reproducedin this

apart,in

not

attacked

paragraphreferenoe letters,here omitted, are

to two
specification
original

properlj
form

by

given

volume.

the

in the

151

ALUMINIUM.

In

Figs.94 and
Fig.94, 2 is

95 show

two

the

of

of current

source

heap

of the

forms

piled

ore

on

7 and

with

connected

smeltingarrangement.
plate,7 ; 5 is a

carbon

with

electrodes,4

the

and

4' ; 3 is the electrolyte,


the electrode,
from which
4',may be
after
is
remoTed
the process has fairly
started,as it only required

produce the arc initially


required to beginthe fusingprocess.
95
shows
the
furnace
without
the electrode,4',and its
same
Fig.

to

conductor.
The
between
4 and 7.

arc

and

Bradley's process
others

in

they
of

simplicity. In
with

agree
of

at

necessary

and

is, in

this

case,

apparatus undoubtedly

struck
all

surpass

principle

Borchers'

furnace

first

struction
con-

method

working.

A patent
Famaoe.
of Kiliani's,*
who
at
specification
Kiliani's

Uie time

"

which

at

Director

was

Industrie

it
the

of

granted

Aluminium^

scribes
AktiengeseHschaft^dealuminium

an

was

furnace,but

nothing of the lining of the


melting hearth, or of the arrangement

says

of the cathode.
The

columns, a (Fig.96), support


tended
is invessel,6, which

the

for the
the
vessel

the

by

generator

and

trolyte;
elec-

of the

cathode

below,

with

fusion

this

enters

makes

tion
connec-

negative pole of
the

conductor,c.

the

The

piece,d, carries the arrangement


for givingsupport and motion
to the positive
electrode,e. Within
the sleeve,c^, is the anode
spindle,
which
in
vertical
section
has the
/,
cross

form

of

rack,

with

the

so

engage
latter being actuated

that

it may
pinion, ^, the

by

the

Fig. 96."

worm

Kiliaui's furnace.

and

wheel, h h\ in connection
with the handwheel, h^. The teeth and notches in the spindle,
which
/f take the form of rings and grooves respectively,
are
the
whole
cut round
of its circumference, so that if turned
thus be
in any positionact as a rack, and
upon its axis it may
still in gear with the pinion,g,
is
A worm
wheel, k, so keyed
to

on

the

spindle,/,

direction of the
*

Gennan

20. 1889.]

Patent

bore

that

of the

the

latter

wheel.

50,508, April 21, 1889.

is free
The

to

move

in the

wheel, k, gears

[EnglishPatent

into

6,745, April

152

c'

Figs. 97

to

b'

101.

"

v'

B'

Schindler's

c*

aluminium

furnace.

QqIc

154

ELECTBIC

material,which, on

same

be

SMELTING

enclosed

within

mixture

of

the bath

is

KBFININO.

of its want

account

shell.

iron

an

AHD

aluminium, sodium,

and

The

inventor

of

which

chlorides,in

lithium

replenishedat the expense

in the anode.

mtist
durability,
is
fused
electrolyte a

The

of the alumina

contained

also obtained

has

moderatelytaii^position,
/(oetoryresults (!) by omitting the alumina in the anode comand adding it direct to the bath instead.
His "new
method
He treats
of producing alumina
is also worthy of note.
aluminous
material with sulphuricacid,and heats the resulting
thus breakingit up and obtainiog
hydrated aluminium
sulphate,
^

the oxide

taken

Aluminium

of

Eleotrolysis

Sulphides.

^Two

"

patents

were

productionof aluminium
the
aluminium
by
sulphide dissolved in fused
alkali-metal chlorides; but the process is only of interest from
the theoretical standpoint. Both
granted on the
patents were
same
day (Nov. 18, 1890). The patent which received the
Germany
of
electrolysis
in

out

earlier

number

mainly

with

taken

in

addition

alkali-

trated

by

the

converted
allowed

to

AljO,

alkaline
motive
The
mixture

carbon

aluminium

metals,

poly-

with

the

oxide

or

sulphidesof aluminium

**

3C

white

38

being

reaction

the

oxide

illua-

into

SCO.

experiments on the
the sulphidewithout
and

of alumina

mixture

con-

the

carbon

clay retorts, and was completely


into sulphideby means
of sulphur vapour, which
waa
thus
for
a sufficiently
:
long period,
operate
to a

heat

NaeAl^S,

describes

sulphides.A
in

"

sulphide so

3C

chloride,and

be

3S

obtained

could

SCO

then

be

by
electrolysed

AVV
dissolved

current

in

of low

fused

electro*

force.

Aluminium
which

is

'

IndiiUrie

brought to

electric current, in
necessary ; or hy external

of the
be

sulphides"r

aluminium

in excess,
double

metals,

account, | he

Al^O,
The

other,

followingequation:

of other

agency
heated
was

the

"

of the

version

of the

alkaline-earth

alkaline-earth

or

later

the action

heated, forms

SNa^S
In

that,"by

sulphur and

of

is concerned

Indtutrie-Aluiengeaell'
advantages accruingfrom the use of thia

alkali- and

the

hydroxide,when
and

Aluminium-

the

claims

and

sulphide,while

the

of

name

sulphides of

Bucherer,*

to

production of the

sehaftt sets forth


electrolyte.
Bucherer

for the

granted

was

the

the

in 1890

required for the


*

use
AktiengeselUchafi

state

which

of

case

heating,when
current.
electrolysing

similar

fusion,either by
an

E.M.F.

of 5

means

volts ia

only 2^ to 3 volts will


Oast or wrouglit-iron

German
Patent 63,995, Nov. 18, 1890.
Patent
t German
68,909 [?63,999],Nov. 18, 1890.
X Ze\t9chHft fiirangetoantUe Uhemie, 1892, p. 483.

155

ALUMINIUM.

Teasels may
be
is claimed as a

It
thej should be lined with carbon.
this
of
this
that
neither
specialadvantage
process
effect upon
the
liningnor the carbon anodes has any prejudicial
with
them
materials which
and
here
into
contact
are
brought
;
that on
this account, besides
effectinga considerable
saving
of carbon
The

the

in

aluminium

used, and

various

of the

parts

apparatus,

very

pure

is obtained.
of the

sulphide electrolyteis so remarkable,


that it is a matter
for regret that at present no advantage can
be
taken of it,because up to the present time no sufficiently
cheap
been
invented
has
method
for the production of aluminium
the one
on
hand, that the
sulphide. It must not be forgotten,
and on the other,
metal may
be obtained
directlyby electrolysis,
that the sulphide must
the pure oxide,
first be prepared from
whilst as Bucherer
himself
pointsout, there is scarcelya purely
chemical reaction
known
which
requiresso great an absorption
of heat as that above
described
Al^Sg + 300).
{M^O^ + 30 + 3S
the
of
the
from
Finally, author, speaking
experience many years
in the manufacture
of alkali- and alkaline-earth
metal sulphides,
points out that the production in gross of pure aluminium
and
the
sulphide,or of the double
sulphides of aluminium
metals above
named, is an exceedinglydifficult ]"roblem. With
the means
the possibility
at present available on a working scale,
of introducingthe electrolysis
of sulphides for the manufacture
of aluminium
is bound
up with the solution of this problem.
Many processes have since been patented for the production
of pure
aluminium
sulphide,or for the lessening of the cost
of electrolysis
introduction
the
of sulphides into molten
by
aluminium
baths {cf,Blackmore, Peniakoff,and
others)
; but it
will suffice to touch very lightlyupon
In the same
them.
way,
there
other
which
it is quite unnecessary
to
are
processes,
of the
describe,that have been patented since the appearance
behaviour

last edition
valuable

papers
of aluminium

into the

this

book.

have

been

of

method

condition.

The

these, the

former

can

of

Bauxite

none

of

Treatment

already been stated that


production of aluminium

pure

is obtained

Two

methods
process,

hand,

several

very

short

are

used

bauxite

furnace
reverberatory

and

the

Cryolite.

minerals

used

in

their

employed
cryoliteand
the
from

flux

or

bauxite.

"

It has
in

natural

bauxite.

solvent

the
Of

for the

The

cryolite
a less pure
specimens ; or
since the greater part of the
electrolysis,

impuritiespresent would
older

are

as
chiefly

serves

which

be

can

materials

raw

be used direct in selected

eondition after

other

publishedrelatingto the management


and
these have
works,
given a very clear insight
of working on the largescale.

Preliminary

alumina

the

On

in

pure

thus

be

for the

separatedout

preparationof bauxite.

is calcined
until the

first.

in

admixture

with

chargebegins to sinter

In

soda

the
in

together.

156

KLECTBIC

this

Bj
And

latter

aluminium
then

can

alumina

extracted

be

is then
soda

the

it has

by

the

The

into carbonate.

filtered,
washed, and
anhydrous oxide by roasting. The

form

also

of

verts
recon-

hydroxide,after

aluminium

been

The

water.

in the

dioxide, which

of carbon

use

with

treatment

the clear solution

separatedfrom

hydroxide by

pure

REFINING.

AND

the iron present is converted


into insoluble oxide
sodium
into
aluminate, which
lijdroxide

means

the

8MELTIHO

dried, is converted

into

the

introduced
the H^roult

was
process, which
the
alumina
department of
by Bayer, is employed in
before
Works.
the
Sutherland'*^
has described

Institution

of Mechanical

in

the

Company,
The
and

Lame

of
fiugineersthe application

Harbour

British

of the

Works

the

obtained

was

followingaverage

AlumiDium
oxide,
Ferric oxide,

from

the

composition

Titanic

56 per
3

....

"

3
26

Two

Lancashire

feet

in

which

is

id thrown

cent.
"

12

acid

100

serve

boilers

80-H.P.

an

steam

,,
"

"

of 7
pressure
engine, the exhaust

at

long and
atmospheres.

26 feet

about

used, each

are

diameter, working

steam

appliedto the heatingof the evaporatingpans.


and the crushed
are
employed for pulverising,
on

meshes
to the linear
the calciner and returns

sieve,with

Antrim,

"

Water,

These

of

County

Silica,

this cess
proAluminium

in Ire and.

bauxite used

had

newer

four

delivers the fine

from
tegrators
Disin-

material

inch, which

the coarse
to
particles
material to the disintegration.
The object of calciningis to destroythe organic matter
tained
conin the bauxite,and
the iron completelyinto
to convert
but
the
is
at the lowest
peroxide (Fe^O^);
roasting conducted
of the alumina
possibletemperature in order that the solubility
be impaired. The
iron tube
not
calciner consists of an
may
33 feet long and 3i feet in diameter, lined with fire-brick,
and is
.providedwith a fire-grate,
dust-chamber, chimney, and coolingtube.
Both
the calciner and
mounted
the cooling-tube
on
are
tion
that they can
be rotated, and are placedat an inclinarollers,
so
of 1 : 25.
The
about
feet
30
is
long and 2^
cooling-tube
feet in diameter, and
of cold
is cooled while in use by a current
air passing through it. The calcined material
is conducted
by
a

spiral conveyor

until
inch.

the

to

has

The. fine material

is carried
*

material

in trucks

away

Transacttoji

Inst,

1896, vol. Ixii.,p.

291.

second

passed a

sieve

is collected
as

may

of MtchanicaX

where

crusher

be

in

it is

pulverised

per linear
receiver,from which it

of 30

meshes

required.

Engineera^ 1896, and

Etigineering,

157

ALUMINIUM.

The

bauxite

solution

so

of 1*45

prepared is now
speciticgravity at

treated
a

with

pressure

caustic

of from

soda

to

atmospheresin iron pressure kiers of about 11 feet in length and


5 feet in diameter, with
walls about
^ inch thick. The steam
used

heating is passed into an outer jacket,and in a short


time brings the charge (3 tons) in the inner cylinderup to a
is maintained
for from two to
pressure of 5 atmospheres,which
three hours, the mixture
being constantlystirred throughout.
The mud
is then discharged(by its own
pressure)into a tank
placed at some
height from the ground. It is here diluted
until its specific
gravity is 1*23, and is then allowed to run
into filter-presses.
Each
contains
50 compartments
filter-press
The
measuring 2 feet 6 inches x 2 feet 6 inches x 1 inch.
and
clear
for
is
filtrate is not
therefore
use,
yet sufficiently
in lead-lined
passed through a filter of wood-pulp contained
wooden
feet
6
feet
3
feet
10
broad,
tanks,
long,
deep, with a
sieve of |-inch mesh
supported inside on a ledge about 6 inches
from the bottom.
The sieve carries about 50 lbs. of wood-pulp
previouslybrought to the condition of a thin paste by boiling
for

The

clear

sieves of this kind

Two

with water.

liquoris

pumped

are

superposed.

into vertical

and

cylindrical
about 20 feet high and
decomposing tanks, built of iron plates,
13 feet in diameter,provided with agitators. Instead
of being
treated here
with
carbon
of
dioxide, as by the old method
for
the
solution
stirred
hours
in
36
is, Bayer's process,
working,
with pure aluminium
hydroxide from a previouscharge. In this
is precipitated
;
way about 70 per cent, of the dissolved alumina
the depositis allowed
the
a
nd
clear
solution
is run
oil*
to settle,
The
into another vessel.
hydroxide mud is pumped into filterunder
filled
of 5 atmospheres.
which
are
a final pressure
presses
now

The

press cakes are washed


is dischargedby means
of

The

cakes

the hearth

are

is 20

calcined

would

in

take

water

reverberatoryfurnace, of which
wide, heated by producerlong by
is expelledat a low temperature, the
water
a

6 feet

feet

gas. Although the


alumina
is heated
to
oxide

in the press, and the admixed


while still in situ.
air-pressure

1,100* C, since, if

this

were

in store, and

not

done,

would

then

the

be
again
unsuitable for electrolysis.
The
dilute caustic soda liquorsare
concentrated
in a threechambered
vacuum
evaporator,until they are again brought to a
of
1
able
'45,at which strengththey are again servicespecific
gravity
The
condensed
from tho
for treatingfresh bauxite.
water

evaporator,

as

water

up

well

as

the

dilute

for the dilution

presses, serve
of caustic soda, whilst

the

wash-waters

of the slimes

condensed

water

from

and

the

filter

of the solutions

is also available

for

the boilers.
feeding
The electrolysis,
The Indostrial
Electrolysis of Aloinina.
of aluminium
in the earliest experiments,
oxide is again,as it was
"

158

BLBCTRIC

lined

in iron vessels

conducted

AMD

SMELTING

with

carbon.

able for the fused charge TarLes with


used up to 2 feet 6 inchesby 5 feet.
of

current

8,000

the internal

be

amperes
may
of the bottom

area

of

REFINING.

The

space

avails

to be
current-strength

the
With

dimensions

these

used, which, reckoning only


the vessel,correspondsto a

[650amperes
per square metre
earliest accounts
of the H^ult
process

of 7,000 amperes
current-density

foot].The

per square

the

described

of

use

bath

containinga

very

largeproportion

and, in consequence,
requiringa highertemperature
the
then used was
said to
and
now
used,
current-density
metre
23,000 to 25,000 amperes
[2,150to
per square

of alumina
than

is

be from

2,300

amperes
to

is

Aluminium

H^roult

Company

used)
replacethat which

system
to

necessary

at

depositionof
electromotive

aluminium.
used

force

of the bath

give it as 9 to 10 volts.
voltage required for the
the

the

this could

be

On

the other

too

high,with

where

"

th^

3 to 5

as

;r-^.

the

fact that

the

alumina

^^

0-24

volts,whilst

^^"]

is

96,537/

perhaps possiblethat,under favourable


difference of potentialof 5 volts may
be observed
is
but
it
be
to
electrodes;
hardly
expected that
attainable as an average
in practical
work.
resMiing
difference of 9 volts is certainly
hand, a potential

approximately 2*8,it
between

of the

in the

Having regardto
decomposition of

(calculatedformula,
conditions, a

as

is

others

from

Works

in Scotland

is added

tomary
cus-

proportion
decomposed in the electrolytic
The publishedstatements
to the
as
obtained
and
are
current-efficiency
favourable
the
accounts
give
tial
poten-

The more
very discordant.
the
terminals
difference at
the

Foyers

was

added

(accordingto

of the Aluminium

alumina

is

formerly it
was
cryolite

employed, to which

now

given by Wallace,*

account

British

bath
cryolite

flux,

an

use

foot].Whilst
per square
bath of alumina
to which

is

the low

of 7 '5 volts with

current^lensities

used.

now

An

average

of 7,000 amperes
current-density
per metre
and
of 90 per
a
current-efficiency
[650 amperes per square foot]
cent,
probably represents the results in actual work on a large
scale.

From

be

this it may

be calculated

that at least

1,400 EH.

P.

order

of aluminium
to produce a yield of 1 ton
which
a
hours,
twenty-four
figure
per
agrees
with that given in the last edition of this book
as
very closely
having been calculated from the experimental results obtained
machine
The
with
author
a
capable of giving only 2 E.H.P.
had at that time determined
that about " kilogramme [1'47lbs.]
be
in twenty-four
be
1 RH.P.
to
depositedby
expected
might
must

applied in

day

hours.

Hence

of

little less than

1,500 H.P.

yield 1,000 kilogrammes of aluminium


since quoted as obtained
whilst the figures

to

vary

between

1,400 and
^Joum.

1,600 E.H.P.
Soc, Chem.

would
in

necessary

twenty-fourhours,

from

for the

be

same

Ind., 1898, p. 308.

works'

practice
output. As

159

ALUMINIUM

above

explained,therefore,it

tion of

1,400 H.P.

for

an

output

a
conaampof 1 metric

twenty-fourhours.

ton per

The

probablethat

is most

be reckoned

must

been

progress that has


and
for electrodes,

the

made

in the

manufacture

low

of

bons
car-

temperature scarcelyhigher
possibleto maintain the bath under
the modem
make
it possible
conditions of low current-density,
the artificial coolingthat,under
other circumstances,
to dispensewith
Uian 750* C.

at

"

was

and the
to

which

"

it is

to

necessary

the metal

maintain

alumina-,
cryolite-,

or

preyent the contamination

of the

and
electrolyte

impuritiesderived

under

cathodes

carbon

or

carbon-liningof the

furnace,and
of the metal

materials
of
depositionby
The
which these portions of the apparatus were
made.
special
need
that
there
be
is
not
now
used, provided
cooling
appliances
check

to
nothins;

the free circulation

the dense

Indeed,with

carbon

of

from

the

of air around

high

thermal

the

apparatus.

conductance

now

used for the crucibles,it may


be necessary,
at least in the
even
the metal
upper portionsof the side walls,to interpose between
tivity,
lininga layerof material of low conducsuch as fireclay,
or
magnesia,or masonry.
The cryolite
the largescale exactlyas it is in the
is melted
on
small experimental apparatus. On
the small
scale,however,
and especially
of demonstration, it is seldom
for purposes
sible
posthe process long enough to obtain sutlicient
to maintain

walls and

the

carbon

metal to render it necessary


the author has not referred
the

of the smaller

use

to

tap the furnace.

usaallybest to let the contents


break the globulesof aluminium
is,however,
the crucible

this account
ing
in describ-

of the

furnace
of the

out

plant,it
then

cool,and
solidified

mass.

It

that, with a largeplant working on


industrial
in
conditions,the metal collecting

of the

furnace

must

be

run

suitable

off from

time

to

through a
tap-hole,exactlyas is customary with
furnaces
for the smelting of metals ; and
metallurgical
manner

is
to

self-evident

under

longruns

On

this part of the process


such a
apparatus. With
to

time
all
the

stood
conductingthis part of the process is so well underthat there is no need to refer to it further here.
the
On
of

other

hand, it is not at first sight so


of
aluroininm separatesat the bottom
for the

numbers commonly quoted

gravitiesof

the

two

materials

as

would

readilyunderstood
why
bath of fused cryolite,
a
representingthe specific
lead one
to predict the

contrary.
The

is given as 2*7,and
gravityusuallyof aluminium
specific
3.
J. W. Richards
as
has, however, experimencryolite
tally
determined the densities of the materials employed both in
the molten
condition and
after cooling. The
results,which
sufficeto explainthe apparent anomaly, are given in the following

that of

table

"

160

ELECTRIC

SPECIFIC

OF

REFINING.

COMPOUNDS.

ALUMINIUM

most

both

on

the industrial

possibleto lay down


of aluminium

the

and

the

experimentalscale^
tion
followingconditions for the extrac-

:
"

successful

1. Tlie

AND

for
AliimiTiinm
traction.
Exfavourable
comparing the foregoingaccounts of the extraction

On

"

of alaminium
it is

GRAVITIES

Conditions

The

SMELTING

extraction

of

aluminium

by electrolytic
pounds
comonly possiblewhon anhydrous fused aluminium
in
used.
the
Bunsen
are
(Determined by
year 1854.)
in a fused bath undergoing
2. The
proportionof aluminium
be maintained
constant
electrolysis
by the addition of
may
aluminium
oxide during the process of electrolysis.
(Ascertained
Claire
Deville
the
in
1854.
St.
by
year
J
3. The
heat required to melt the charge is produced by the
aluminium
used
for electrolysis.The
current
industry is
described
of working, which
in
founded on this condition
was
in 1887, and
of H6roult
in that of
the patent specification
the
which
in
was
1892,
although
published
patent itself
Bradley,
The temperature of the bath is
had been applied for in 1883.
is

means

750"

C.

4. The

above

condition

(3) makes

it

possibleto use an iron


compounds (alumina or,

melting vessel,lined with aluminium


or
carbon, and kept cool
better,cryolite)
5. For electrode
metal

or

carbon

either

materials

blocks

there

are

on

the outside.

available

"

For the

ccUhodcy

arranged that they are so far cooled,,


other coolingmedium
(preferably
water),
the addition of any impurity to the
so

by air or by some
that they do not cause
aluminium
deposited; for the anode, carbon blocks,which, if of
largesize,must be built up of smaller blocks or platesof similar
material.
6. The

be

of hovizontal
amp. per sq. ft.]
Wallace's paper, 1898.)

S650
From

should
current-density

7,000 amperes
sectional

area

per sq. metre


of the bath.

potentialdifference required,allowing for drop of


potentialowing to the resistance of the conductors and to con7. The

162

ELECTRIC

AND

SMELTING

REFINING.

1897, preliminariljapplied water-power


to the

H.P.

extraction
electrolytic

3,500

equivalent to

process.

Reduction
PiUtkurg

Company have
Niagara Falls,where
the Company is atilising
If, as is probably the
10,000 H.P.
and power, including
case, a part of this is employed for lighting
The

American

been
latterly

the further
use

works

of the

completelytransferred

to the

of the metal, about

treatment

6,000 H.P.

remain

for

in

electrolysis.
Finally,the British

Company, which was the last


the manufacture, when
to commence
employing the full power
of the plant available at the Falls of Foyers (Scotland),
uses
about
5,000 H.P., which
is, however, exclusivelyapplied to
the
since
w
ork,
electrolytic
Oompany possesses a separate
electrode
factoryat Greenock, and a rollingmill at Milton.
The steadily
ium
of Aluminitun.
Uses
increasinguse of aluminand
valuable
chemical
its
is due
to
physicalproperties.
The fact that the strengthof the metal is but slight,
and rapidly
diminishes
the metal is heated even
but slightly,
militates
when
against the extension of its use as a material for construction,
of its low specific
concerning which, on account
gravity,great
hopes had been raised,after the difficulties connected with its
had been overcome.
manufacture
But
it is not yet universally
that
aluminium
is
of the cheaper metals.
now
one
recognised
If,however, its specific
gravitybe taken ss unity,and its price
the pricesof equal bulks of other metals
be compared with
for
Aluminium

"

which

aluminium

Qould

proportionsgiven in the

Aluminium
substitute

in the

in

one

way

or

other

be

substituted,the

followingtable will be obtained

form

of sheet

for copper,

wire

and

tube

"

is used

as

brass,bronze, zinc, and silver,in their


varied applications.The
most
used
wire has been successfully
in many
The sheet is employed
placesfor electrical conductors.
for cooking-and table utensils,preserving-pans,
articles of military
equipment, combs, brushes, bicycle components, and in
bookshelves,
place of wood in ship-and waggon-building,
book-covers,
and
coffins,

the like.

ALUMINIUM.

The very considerable shrinkage(1*7to 1*8 per cent.)of the


metal during solidification was, at first,
to the use
a hindrance
of aluminium
for castings.To obviate this a small percentage
of a so-called hardener
was
added, such as, for example,copper,

nickel,zinc,manganese,

tin,chromium, titanium,tungsten,or

vanadium.

so

Aluminium

in the
alloyedis sometimes known
States as uickel-aluminium.
In the Paris Exhibition of
and art- wares
1900 there were, however, cast-goods
busts
(e.^.,
made
of St. Olaire-Deville and Wohler) satisfactorily
of pure
difBculties are now
obviated
aluminium.
The above-mentioned
and
used for
in
the
moulds
by using largerunners
rising-heads
the castings.In meltingaluminium
for castingno fiux should

United

be added.

If this is attended

to, there is no

fear of the metal

from the carbon of the crucible,


from
or
taking up impurities
the silica of the claythat is mixed with the graphite,
provided
that the temperature is not allowed to rise too high above the
meltingpoint of the metal. But if the metal be overheated,
in the absence of fluxes,
it will take up both carbon and
silicon from the walls of the crucible.
of
Owing to the porosity
the vessels used for meltingthe metal, the fuel employed for
heatingthem should be as free as possiblefrom sulphur. For
is best,but a pure coke containing
this purpose wood-charcoal
but little sulphurmay be substituted ; and natural-gas
is sometimes
even

States.
dissolves
Aluminium
used in the United
readily
and
the
such
a
t
as
hydrocarbons, temperatures
nitrogen
gases,
but little above its meltingpoint; and nitre is added to the
before pouring. This is done
to expelthese gases shortly
to 50 kilogrammes
by wrappingthe nitre (aboutan egg-spoonful
moistened
of
of
in
a
writing-paper,
[1cwt] metal)
piece
throwing
and
it into the crucible after removing the latter from the fire,
down
the
it
bottom
of
the
to
quicklyforcing
pot so that^ in
risingto the top,it must pass through the whole depth of the
metal.
A brisk action is set up, and, duringthe periodof this
reaction,all the dissolved gases are expelled.The charge is
into iron or sand
poured at as low a temperature as possible
and risingas above
stated,with largerunners
moulds, provided,
metal

heads.
Aluminium

used for table- and cooking-utensils,


are
castings
instruments,
baths,surgical
parts of electrical apparatus
with
5
this
case
usuallyalloyed
(in
per cent, of copper, and as a
such parts of machinery for use on
substitute for brass),
bells,
board shipas are not requiredeither to be especially
strong or

sides of

to be
are

heated,and

not

intended

as

to

for wood, for supports which


carry great weight,and for sheathingand
a

substitute

in ship-and waggon-construction.
plating
used in the preparation
of alloys
Aluminium
is very largely
;
made
with 2*5,5, 7*5,
are
thus,for example,aluminium-bronzes
The direct production
of these
and 10 per cent, of this metal.

164

BLKCTBIC

SMKLTINO

alloysbj the simultaneoiis reduction


compounds, as formerly carried on
been

now

metals

in

do

To

place at

this the

using
castingof
is

this kind

the

aluminium

; after

lifted out

absorptionof

the

to

after

is

there

that

heat

the

the

the

crucible

quantity of
momentarily cooler,

aluminium

considerable

very

for the

desired

becomes

by

above

is melted

copper

crucible

The

in

fire,and

as

evolution

it fuses ;
of heat ;

be
and if the crucible is still in the furnace it must
taken
The
off the surface
charcoal
is then
removed.

metal, and
first to

the

charge is rapidlystirred

it into

run

bars which

two

prepared direct
they are required.
plumbago crucible,

recommended

are

the

of the

is added.

aluminium
but

precautions

as

copper
process, has

best

are

which

is first melted

copper

same

seized,or

owing

at

and

Cowles

in the

question,alloysof
constituents

the

of aluminium

present pricesof the

the

abandoned, since,at

the

from

REFINING.

AND

quickly
the

of

poured. It is best
as
required for

and

be re-melted

can

casting purposes.
A

of alloys besides
large number
the public during the past

very

brought
an

of these

account

reference

must

be

years,
to works

aluminium

based,

are

treating
magnesium
placed upon the

iron, copper,
lower

their

the

formation

upon
chemical
action

the

upon

termed

not

for

alloyof

Quite recentlyan
magncUium has been
market, and this alloyis of specialinterest.
The applications
of aluminium
in the castingof

and

been

but

ten

made

of aluminium.
specially

have

bronze

before

of the

other

of aluminium

metal.

metals

alloys,but

metals, such

Many

as

and

nickel,possess the property of alloyingwith


oxides
(FeO, CugO, NiO) ; hence, in smelting,
melting them, contact with the air or with other

or
refining,
compounds
oxygen

leads

the

to

i'ormation

and

solution

of these

the other hand, their complete removal


is
on
although reducing substances, such as carbon,
If such
silicon,or sulphur,may also be present in the metal.
metal
be now
a
poured, the outer skin of the casting will
and
then
will be set up in
a considerable
first,
solidify
pressure
enclosed
the liquidmaterial
within
it ; this pressure facilitates
the oxygen
the reaction
(otherwise very sluggish) between
carbon, silicon,sulphur,and the like
compounds and whatever
lower

oxides, and,

difficult

may
have
in

be
no

the

even

formed
which
gases are
tend
of escape,
therefore
to produce cavities
of dissolving
Then, again, this metal has the power

present.

result

is that

and

means

metal.
other

The

gases

also,as,

for

example, hydrogen and nitrogen.

added
oe
quantity of aluminium
before
ladle
pouring,or
casting
ingot moulds, the substances which give rise
If

small

either
above

in the

described

are

amount

of aluminium

smaller

than

would

in

part
added

reduced
to cast

correspond to

and

in

such

to

the

metal
in the

difficultiea

part separated.

iron and
the

to

afterwards

amount

cast

steel is

of ferrous

The

alwaya
oxide

165

ALUMINIUM.

to be reduced.

also

But

not

as

only this

but other

oxide

it is evident

impurities

that

the aluminium
simultaneously removed,
difluse
to
very rapidly through the iron, and
in so doing to exert
a
powerful reducing action on the oxygen
with
which
it comes
in contact;
"x"mpounds
and, further, it
that the heat generated by this reaction expedites the
seems
reactions which
otherwise
would
have
on
comparatively
gone
slowly after the outer crust of the metal had solidified. In this
the cast metal is purifiedso rapidly before the commencement
way
of solidification that the time required for solidifying
is
the
to
reduced, and, in consequence,
or
separation
any tendency
of constituent
liquation
alloysis lessened,and the homogeneity,
In the iron foundry
density,and tensile strengthare increased.
the amount
of aluminium
used is commonly 500 to 1,000 grms.
fl'lto 2*2 lbs.]per ton ; in the open-hearth process it may be
50 to 150 grms. [1J to 5 J ozs.]
; and in the Bessemer
process for
are

is able

inormal

80

runs

metal, more
tendency of

per
the

or, for under-blown


grms. [2^ to 7 ozs.^
If too much
aluminium
the
be added

200

to

ton.

''pipe" will be increased, whilst a


minium
of aluopposite effect. An excess
also causes
of carbon.
a separation
In the so-called
galvanising (zinc-coating)
process, and in
the brass foundry the r6le played by aluminium
is rather that of
for checking the oxidation
of the
a reducing medium
or
a means
than
that
of
Hunt
that
500
states
an
charge
alloyingagent.
ingot

to

has

the

addition

moderate

"

"

in the form
of a 5 to 10 per cent,
grms. [1 lb.J of aluminium
is
aluminium-zinc
used
of
ton
zinc,whilst,accordingto
alloy
per
2
addition
of
of an
Kichards, an
kgrms. [4^lbs.]
alloyof 4 per

aluminium,

of

cent,

of 10 tons

with

Finally,aluminium
separation

is used

of their oxides

dec).
manganese,
which
refractorymetals, such
high temperatures
the

aluminium
with

zinc,sufiSces

in the Goldschmidt

Goldschmidt

In

of

of difficultly-fusiblemetals

reduction

the

by

96 per cent,

for

bath

of the latter metal.

case

and
of

by

in the
its

process for the


condition
molten

{cf,chromium,

means

has also introduced


as

be

iron,can

by
process
obtained
at very
a

to welding and
appliedespecially

iron, a

is

and
lighted,

the whole

of the heat

mixture

of

oxide

ing.
solder-

of iron

and

the

iron,charged
resultingreduced
the
generated by
reaction,is allowed

the

It is obvious
jointto be soldered or welded.
of obtaining high temperatures is applicable
conditions
under
in which
other means
of heating could only be
with
for
such,
applied
example, as the welding of
great difficulty,
the
or
railway rails,
repairof machine parts,without dismounting
to

run

this

the

whole.

Price
an

to

on

that

method

of

Aluminium.

"

This

table,taken from
interesting
MetallurgicalSocietyand of

chapter may be concluded with


fort
the publicationsof the Frankthe Metall-Geselhchafu
showing

166
the

ELECTRIC

variations

produced

AND

REFINING.

the

price of alaminium
manufacturing scala
in

on

8MELTIKO

CHAPTER

was

first

METALS*
PRASBODIDYMIITM:,

LANTHANUM,

CBBIITM,

it

II.

CERITE

THE

since

NEODIDYMIITM.
in

Oooiirrenoe

Natiire.
and
as
cerlte,

silicates in

compounds
been

haye
for
are

of the

used

rarer

in the

contained

become

more

compounds
still very

costly,

found

phosphates
those
metals,especially

compounds

of

the

that,in

in nature
Since
of

as

the

thorium,

of incandescent

manufacture

gas mantles
of the cerite metals ^which

in
quantities

readilyavailable
so

are

in monazite.

in considerable
of metals

metals

earth
the

lightingpurposes,

These

"

for

use.

The

these

metals)have

separationof

the

cerite group
is
by chemical means
later experiments in the extrao-

the

THE

tion

of the

metals, the

manufacture
direct

GERITE

reduction

to

of oxides

mixture

materials

incandescent

of

167

MBTALS.

salts left from

or

has

without
electrolysis

or

the

submitted

been

attempt

any

at

separationpreviously.
Cerium, Ce,

Cerium."

of

Properties

the

best-known

metal

than

weight 138, and the specific


gravity
harder
somewhat
is
an
iron-greycolour, soft,being
lead,malleable, and readily rolled. Its fusing point is

about

800** C.

of this group,
6 '73.
It has

has the atomic

combining with the heavier


produce dense alloys. In solid
copper or
piecesit offers considerable resistance to atmosphericinfluences ;
but, on heatingthe fragments,they exhibit the various tempercolours of polishedsteel.
trary,
Finely-powdered cerium, on the conthe
metal
oxidises very rapidlyin the air,and, on
filing
or
or
shaving it with a knife,the detached filings
scrapingstake
burn with a brilliant light. Fine wire made
from the
fire and
of
that
metal burns with a brilliancy
exceedingeven
magnesium.
Cerium
in the form of powder causes
only a slow decomposition
Most

noteworthy

metals, such

of water

iron,to

introduced

when
in the

of

is its power

us

induces
liquid,

noted

the

of salts dissolved
presence
livelyattack. This property

into

it,but

be

in connection

very
with

the

the

oxides

production of cerium,
and with the possibility
which ma/y ecuUy arisenof obtainingthe
metal in ptUverulent
at too
form, ounng to the rise of an electrolyte
dissolves
diluted
low a temperature,* It
acid^,
very easilyin
but only to a slightextent
in cold concentrated
sulphuric or

should

nitric acids.

reduces

Cerium

which
metalloids,

metals

of most

and

in regard to its
property worthy of remark
the
metal
and
of
to
alloys.
applications
refining
making
Lanthanum, praseodidymium, and neodidymium agree with
in very many
of their properties.
cerium

1.

is

BXTB

ACTION

OP

THE

METAL

BY

ELECTBOLYSIS.
The cerite
of the Cerite
Metals.
intermediate
those of
between
group

Electrolytio Deposition
metals

appear
and

to

magnesium
salts which
is well

would

form

aluminium,
be

understood

be obtained

in

"

in

likelyto

that

none

regard to
come

into

the behaviour
use

of the chlorides

for

of those

It
electrolysis.

of these

metals

can

the

anhydrous condition
by evaporating their
solutions in water, since decompositionalways occurs
on
drying.
the
of magnesium chloride, if a chemically
case
But, as in
or
potassium,
equivalentquantity of the chloride of sodium
is an
*ThiB
exact
reprint from the previous edition of this work.
Muthmann, Hofer, and Weiss have, however, re-discovered,in the year
1901,that for the separationof cerium in the molten condition the electrolytemust be hot, ana in the neighbourhood of the cathode ver"' hot.

168

ELECTRIC

together with
the

of

SMELTING

evaporated to
without
decomposition. The
double chlorides
fused
easily
will be found

to conduct

have

safe,with

relytoo

the

the

then

may
contains

the

be

fused

metals, and

But

well.

metals

be

comparatively

alkali

of the cerite and

obtain

to

then

residue

dry

melt

tion
solu-

the

chloride may

didymium

or

the electric current

been

easy
magnesium and
group,
or
by direct electrolysis
not

REFINING.

chloride,be added,

little ammonium

cerium, lanthanum,

dryness,and

it may

AND

although
magnesium

of the

lithium, almost absolutely pure, either


by electrolysisfollowed by fusion, it is
methods
of productionhitherto described,to

duction
purity of the separated metal, if its resomewhat
than
been effected in quantities
greater
tory.
in the small porcelaincrucibles of the labora)"o8sible
that
Bunsen, Hillebrandt,
is,indeed, very improbable

much

the

on

has
be

would

It
and

who

Norton,

the

were

obtained
electrolysis,

by
They employed
BuQsen*:

reduce

first to

that

product
followingmethod,

the

the

cerite

was

which

metals

from

free

iron.

devised

was

by

"

The

molten

of the
decomposing vessel in which the electrolysis
chloride was
after
the
to be accomplishedwas
arranged

fashion

of

Grove's

Grove's

element.

battery contains
ordinary Hessian
filled with

the

The

crucible

fused

outer

plate and

zinc

of about

the

in

cell,which

sulphuricacid, is
100

c.c.

here

an

capacity,
[31fl.ozs.]

equivalentweights of sodium and


i
n
which
serves
a cylinderof thin sheet-iron
potassium chlorides,
as
positiveelectrode in place of the zinc of Grove's cell. The
across
internally,
cylinderis 5 cm. [2ins.]
high,and 2-5 cm. [1in.]
and terminates
in a stripwhich
must
as
a conductor, and
serves
the cylinder
not
be either soldered or riveted in place. Within
is a clay cell of the best quality,
9 cm.
[3^ ins.l high and 2 to 2*6
cm.
[f to 1 in.]wide, in which is placed the chloride to be
in this to
decomposed. The negative electrode is immersed
about two-thirds
of the depth of the cell ; the electrode consists
of

as

thick

of

mixture

thick

of which
iron wire, the end
thinner,and round its end is twisted a
as

horse-hair,which

beyond the stouter


claypipe-stem is
only

the fine wire

in contact

with

pieceto

is filed down

somewhat
piece of iron wire about

which

it is attached.

now

drawn

so

the end

projectsout

at

the fused

In the reduction

chloride

of such

15

projectssome
far

the

over

[y^ ^^]

mm.

piece of

of the

wire, that

thicker

clayand

comes

that is to be reduced.

chlorides

as

are

easilyconverted

into

be
by the action of water vapour, the fusion must never
in
flame.
Even
the
of
a
heating of
by means
gas
less readilydecomposed, it is better to avoid
chlorides that are
that they evolve
the use
of gas flames,since the water
vapour

oxides

effected

*Pogg. Ann., 1850,


t A

about

vol. civ.,p. "33.

piece of this wire,


1^ grains.]

cm.

long, weighs about

4 mg.

[1 in, weighs

170

SMKLTIKG

BLECTBIC

The

of the
double
chlorides
described may quite easilybe
which
the

either
cathode.

BEFIKINO.

AND

and

oerite

alkali

above

metals

crucible,
serves
as
(or is in direct electrical connection with)
(See Magnesium^ Figs. 9 to 12). In such an
in
electrolysed

iron

an

a
[77*5sq. ins.],
sq. cm.
Cerium
of 50 amperes
be used.
and 6 to 7 volts should
be
separates out first in the molten condition if the electrolyte

experiment,wiUi

cathode

area

of 500

current

hot, otherwise in a pulverulentform, as indicated in


suiliciently
the previousedition of this work.*
Ic is by no means
impossible
that the metals of the cerium
might be separated from
group
and the
another
since lanthanum
one
by fractional electrolysis,
if
they da
didymiuinmetals tend to depositafter cerium, even
has separatedout.
not
down
until the whole of the cerium
come
The
maintained
in the fluid
metals
less readily
are
didymium
condition than is cerium, and they usuallydepositin the pulver*
ulent

condition.

in the
Stookem'8
Experiments
These
undertaken
w
ere
exi)eriment8

that

at

was

time

pupil of

of Hillebrandt

Dr.

and

of

Beduotion
in 1900

by

with

Cerium."

Stockem,

who

repeatedthe

He

Borchers.
Norton

L.

modified

form

periments
ex-

of

and
the chloride
apparatus ; he then proceeded to electrolyse
also the oxide, dissolved
fluorides (both of
in chlorides and
"

metals)after the
of the H^roult
manner
using the current employed for
process
maintain
the
to
electrolysis
temperature of the bath; and finally,
he employed an
externallyheated apparatus with the object of
An
the
improving
by Borchers.!
process already described
Borchers
for
experimentalapparatus similar to that adopted by
aluminium
of electrically
reduction
used for the electrolysis
was
fused salts ; but instead of the ordinary cooled carbon
blocks,
iron wire
an
employed as
terminating in a fine point was
cathode.
metal
This
at
first,and
apparatus yielded molten
the cathode-wire was
attacked.
but slightly
Soon, however, the
cerium

and
itself,

of aluminium

and

the alkali

"

area

of the cathode

surface

longer heated

was

no

of

the

metal; and

to

the

had

increased

temperature

latter

then

so

much

above

that

the

separatedout

the wire

melting-point
only in the

reverted to the
powdery deposit. Hence, Stockem
that
of externallyheated melting vessels,
and thus ensured
use
the charge, or
and
that portion of the
at least the cathode
hot enough for the
charge immediately surrounding it, was
metal
to remain
fused
the
operation. A conical
throughout
vessel tapering to a point was
used in placeof the cylindrical
and
slightlytapering melting vessel commonly employed for
could
magnesium reduction, because a higher current-density
form

'

of

Borchers'

2nd Ed., 1895, p. 155;


Electronietallurgie,

Electric Smeltinff

and

Refining,1897, p. 166.
of L. Stockem,
t Diploma work
at Aachen, June
28, 1901.

presented

at

the Technical

High School

THE

GERITE

171

METALS.

be
could
applied at the cathode, whilst the anode
The
and
the
r
educed
that
at
enlarged
point.
current-density
provided with a coolingpart of tlie melting vessel was
upper
jacket lined with a clay or magnesite cylinder,so that there
should be no
danger ot iron dissolvingfrom the walls of the
apparatus into the fused salts and, by subsequent reduction,
passing into the cerium.
A paper*
Experiments.
Ignthmaim,
Hofer, and Weiss'
metals
the
the
and
Weiss
of
reduction
on
Hofer,
by Muthmanu,
the
cerium
of a very noteworthy
ot
gives an account
group

be

then

"

advance

in the utilisation of the oxides

the views

expressedin the

in their
with

introductorypart

authors

entirety.
such
electrolytes,

fused

the

in

The

first week

earlier work
since

long

of their

Technical

Aachen

as

have

studies

field

same

"

the

in
have

made

established,
although

of the

disregarded

have

facts

rediscovered

work

recognitionof such

the

detracted
in no way have
would
the authors in this research.

accepted
experiments
by students

laboratories

thus

rendered

the service

from

if

even

be

the

Again, they
and

metals,

cannot

described

commonly

are

School.

High

in the

of these

by

apparatus too small and complicatedfor


their purpose,
whilst the Borchers
apparatus tried by them was
discanied
as
being insufficiently
compact, as requiringtoo much
in use.
material,and as being too inconvenient
They do uot,
which
Borchers'
form
of
however, say
apparatus they employed;
Bunsen's

found

They

later part of their account


they refer to certain earlier
Borchers
assumes
cryolite,
experiments in which theyelectrolysed
but

in

aa

that

they

refer to the

must

form

of

which

experimental furnace

being constructed for this purpose.!


by side drawings (Figs.102 and 103)
of his furnace and of that used by Muthmann,
Hofer, and Weiss,
and
found
A
them
be
to
by
satisfactory. single description
will suffice for the principal
parts of each form of construction,
made
of sheet copper,
A
double-walled
:
namely
water-jacket,
closed at the
surrounds
the melting space, which
almost
is
cathode
bottom
The
is surrounded
cathode.
by the carbon
which
the
fills
by non-conducting material,
space between
up
he

described

had

He

therefore

in 1898

as

places side

"

and

the

copper

carbon

rod

projectingdownwards

it

Such

furnace

for

their

materials.
a

of

The
form

smaller

alumina
of small
*

into

authors'

apparatus

larger the
carbon

furnace.

size

vertical

above.

in the author's

tory
labora-

furnace

of
electrolysis

appears,
So far

then,
as

only
dectrolysis

to

the

fused

be

of the

this type oj furnace is concerned^


is the
apparatus, the more

within

in
cryolite

surfaces

is

from

the

students
by new
experiments in the

of Borchers*

anode

The

vessel.

is used
first

dissolved in

the
use

of the

walls

to
cooling-jacket

be

der Chemie, 1902, vol. cccxx.,


AnnoUen
Liehig^s
p. 231.
t ZtitBchri/t
Jiir Mektrochemie, 1898, vol. iv.,p. 523.

recom-

172

ELECTRIC

mended

on

has never,

the

the

RSFININQ.

and

grounds both

of economy
the uee
however,recommended

electrolysis
of cerium
On

AND

SMELTING

the

as
cfdoride,

contrary, in the last edition

safety.

Borchers

of cooled ccUhodes for the

appear to believe.
of this book'"' he spoke "of
authors

which
possibility,
easilyarise,of obtainingthe metal in
may
at too low a
pulverulentform, owing to the use of an electrolyte
from
conclusion
the
Yet
the
draw
authors
same
temperature."
their own
experiments,
whilst
disregardingthe
made
statement
by
the

The

in 1895.

Borchers

tained
ob-

results

following
by

Muthmann,

in
sxe
Hofer, and Weiss
all respectsnoteworthy.

Purifiof Fhoscation^especially
phatic Ores and Crude
and

Treatment

Oxide.

"

material

the

was

able for the

Fig.

102.

"

Section

of Borchers'

furnace.

Fig. 103."
man,

dioxide

Oerium

avail*

author's

Section

ex-

of Muth-

Hofer, and

Weiss'

furnace.

periments,and
it.

the

dificultyin converting this compound

chloride is well

cerous

The

substance

known

have

worked

into
with

attacked

by nitric or hydrochloric
acid.
In order to dissolve small quantities
in hydrochloricacid
for analyticalpurposes
iodide
is
added, which
on
potassium

evaporation

is not

all who

to

facilitates the
*

See

solution

p. 167 above

and

of

the

oxide

footnote.

with

evapo.

THE

ration

of

OEKITE

173

METALS.

iodine.

applicable

on

Obviously, however,
largescale,not only because
introduction

because

it leads

chloride

into the solution.

to

the

this

of too

The

method

it is too
much

is not

but
costly,
alkali-metal

of the

wsa
only way
difficulty
reduce
it
with
to
strong sulphuricacid,
sulphate by digesting
alcohol,decompose the resultingcerous
it for several days with soda solution,and
bonate
dissolvingthe carin hydrochloricacid after washing it with the greatest
pletely
Every trace of sulphuricacid had to be compossible care.
smallest
the
since
removed,
proportion of sulphate
interferes most
It was
seriouslywith the electrolytic
process.
that Bunsen
in his experiment precipitated
the
for this reason
chloride.
acid
with
barium
sulphuric
Of the crude oxides used by the authors, only those obtained
soluble in hydrochloricacid.
The inexpensive
from cerite were
thorium
material
from
the
mauufacture
of
waa
by-products
scarcelysoluble in hydrochloricacid, and only incompletelyso
after repeated evaporations. This is
in strong nitric acid,even
chieflydue to the material containing a considerable proportion
of phosphoric acid,which, consideringits low cost, is scarcely
from strongly
since all of these materials are obtained
surprising,
removal
of
The
the
sources.
phosphatic
complete
phosphoric
be ensured
before electrolysis,
is even
acid, which must
more
that of sulphuric acid.
troublesome
than
version
Moreover, the conof nitrate solution into pure chlorides,when
prepared

dissolve

with
All

the

dioxide

out

in

the strong acid,is a tedious process.


removed
these difficulties are
by the

converting the

mixture

convenient

process
in cases

which

available.

When

the

carbides, a

of insoluble

oxides

givesexcellent

in which

there

is

and

authors, by

first

phosphates into
is especially

and
results,

of energy
cheap source
heated
with
electrically
carbides ; a portion,
ever,
how-

phosphates
mainly into
becomes
phosphide,but by the addition of acid this may
be
into the corresponding cerium
converted
salt withreadily
of hydrogen phosphide. The resultingsolutions have
evolution
found
occasion
been
to contain
no
on
phosphoric acid,so that
this acid is safely and
by applying a
completely eliminated
electric
of
smelting.
process
For the productionof the carbide, of which
a further
account
used a graphitecrucible to serve
will be given later,the authors
both as melting vessel and cathode, with a central carbon anodesuspended from above, exactlyas in the arrangement employed
by H^roult in his first experiment with aluminium.
the process of carbide productionand expresAfter describing
the existence of several carbides of cerium,,
their
views
to
as
simg
the authors
point out that when the cerium carbide had been
dissolved in the smallest possiblequantityof hydrochloricacid
had
the resultingsolution
been
and
the iron, which
filtered,
carbon

they are

converted

are

174

ELECTRIC

almost

always passes

SMELTING

neutralised,and

the

120

cerous

12

of

grammes

chloride

was
solution],
finely-divided
spray of

of steam,

until

filtration. The
above

to

treated
carefully
ammonia

iron

water,

so

that it could

added

now
over

resultingmaterial was then heated


largeplatinum dish,again with constant
50

to 100

escaped

finallyobtained

grammes
in dense

in the form

behaved
stirring,

on

cool in the

to

still

by

hot, and

means

ferric

after

by
completelyseparated,
material.
A quantity
the

carbide

state

used, was

which was
then evaporated
liquid,
dried
with
constant
finally
stirring.

furnace, and

gas

chloride

reaction

to the clear filtered

The

of

the

to

described,with very slightloss of


chloride,equal to that of

of ammonium

aboat

a
[approximately

further

be

carefully

with a very dilute


into it with the aid

blown

portion gave no
first brought
was

ing,
of smelt-

contained

litre

the

test

of bromine

means

in the process
the solution was

this end

which
resultingliquid,

cent,

per

and

as

To

REFINING.

compound

into the

to be removed.

had

AND

was

red

in
stirring,

[If to 3^ ozs.].The
cloucu,and

the

a fine pure
like a fluid.

transferred

cerous

white

of

almost

air,but

dull

to a

It

into

was

heat

in

small

tions
por-

ammonium
chloride

was

powder, which,
never

allowed

globularflasks while

protected from the moisture of the air


stoppers provided with tubes containingphosphorus
was

of

there

pentozide.
The anhydrous neodidymium chloride used for the production
of that metal is prepared similarly,
except that the preliminary
in the electric furnace
is unnecessary
of
treatment
by reason
the ready solubility
acid.
of neodidymium oxide in hydrochloric
Camille
Muthmann
StUtzel * previously,and
and
Matignon t
described
the
have
the
of
more
anhydrous
recently,
properties
of the
be
neodidymium chloride. A short description
given
may
the
carried
the
of
in
out
neodidymium materials,as
purification
and
L. Weiss.
laboratories
After a
at Milnich
by R. Bohm
and
had
removed
lanthanum
been
the
of
portion
praseodidymium
in the usual
the double ammonium
out
by
crystallising
way
nitrate,the remainder

of the

lanthanum

Bunsen's

was

removed

The

as

far

as

still

material then
sulphateprocess.
praseodidymium and large quantitiesof earths
of the yttrium group.
The greater part of both these impurities
removed
method
described
were
by the chromate
by Muthmann
and Bohm.
The
rich
first
fractions
be
to
I
precipitatedwere
in praseodidymium, the next
in neodidymium, whilst the last
the
fractions contained
of the yttrium earths.
Hence
most
neodidymium was concentrated
chieflyin the middle fractions ;
acid fractionations,
55 chromic
correspondingto about 800 precipitations,

possibleby

contained

some

were

carried

out.

This

treatment

with

chromic

Berichte der detUschen ehenu OnseUschaftt1899, vol. xxxii.,p. 3413.


t Camptea Bendua, 1901, vol. cxxxiii.,p. 289.
t Berichte d. d. chem, Oeaellsch.,
1900, vol. xxxiii.,pp. 42-49^

THE

itcid

continued

was

CEBITS

300

until about

175

METALS.

[10^ozs.]of

grms.

material

there

obtained, but

were
praseodidymium
of
quantities gadoliniumi yttrium, erbium,
always appreciable
These
left after this.
next
and terbium
yttrium earths were
the
usual
and
the
potassium sulphate process,
separated by
afterwards
material
was
subjected to two other fractionation
to ensure
methods
complete purification.The oxalates were
less
from
hydrochloricacid solution,leavingthe colourprecipitated
earths
the
t
he
material
in
was
liquid; and, lastly,
yttrium
79
times
with
divided
into
fractionating
e
ight
portionsby
up
ammonia
dilute
solution, whereby colourless
yttrium
very
earths, terbium, erbium, samarium, neodidymium, and praseodidymium
were
precipitated.Those fractions which
successively

free from

almost

identical

exhibited
divided

were

13

into

spectra

parts

by

were

nitrate

and

mixed,

small

The

treatment.

portion

first and

last

exactlyalike,which afforded proof


neodidymium. The material so obtained
purity
oxide
without
of pure blue-greycolour
shade
yielded an
any
of yellow or red, such as is exhibited by those samples which
of heavy yttrium earths
of praseodistill contain
traces
or
dymium.
The spectrum agreed exactlywith that described
by
Schottlander ; * the line X 468*9 was
especially
sharp and clear,
which
was
a proof of the great purity of the material.
After
the three authors
above reExtraction
ferred
of the Metal,
to had determined
by their experiment in the electrolysis
fractions

found

were

be

to

of the

of the

"

of the

pure

chlorides

and

cerium

of
(especially

neodidymium)

for the

separationof the
cerite metals in the molten
condition,they proceeded to reduce
an
alloy of the metals of the cerium group by treating their
In doing so they
mixed
chlorides,which are readilyobtained.
somewhat
scale
than
worked
on
heretofore,and cona
larger
in longitudinal
form of furnace shown
8tructed the very practical
and
elevation
i
n
respectively, Figs. 104, 105,
section, plan,
that

and

106.

high temperature

The
axis
and

melting
measuring

the

height 7

cooled

attached
for

space
7 cm.

by

upwards

or

necessary

crucible

oval in

was

and

downwards

shape,the

the longer axis


[2|ins.],
The

furnace

was

throughout the whole


clamp to a rod, which

cathode

the

cm.

or

was

the

anode.
at will.

ensure

that the charge in the

heated

to

These
A

11

capable of
its

of

also

shorter

[4^ins.],
nally
being exter-

cm.

height, and

carried

the

latter could

specialdevice

was

was

holders

be

moved

added

of the cathode

to

was
neighbourhood
high temperature. This end was attained
sufi"ciently
small resistance-pieces,
each connected
with
the aid of two
to
in an alternating-current
a
pair of cetrbons,connected in parallel
chosen
circuit.
The alternating
for heatingbecause
current
was
there would, in this case, be no
at the ends of the
electrolysis
a

Berichte d. d, chem.

vol.
Oesdlsch,,

xxv.,

p. 669.

176
auch

carbons

used,

were

rods

incandescent

The
such

held

in iron

way

The

"

apparatus
for

mounted

was

tapping

hitherto
In

to

have

alternatingand
Each

thick,and

25

of 40

[IJ

mm.

been

oak

and

paper,

of cerium

stand.

added

requiredto

to

crucible
continuous

a
was

trial

run

filled with

currents

three

was

carbon

were

whole

metals.

An

arrangement

the

furnace, but

it.

use

made

on

switched

pencilswas

had

the

aluminium

cryolite,and

[Iin.]long ; the anode carbon


and the cathode
30 mm.
ins.],
[1^

mm.

the

supports

the

furnaces,as
alternating-current

them,

of the

heavy

never

these

test

The

has

have

termed

extraction.

on

charge

the authors

order

authors

the

their

from

for extraction

and

cathode

the

asbestos

or

clamps

of the

means

insulated

were

Furnace

"

by

fijjrures.Both

carbons
alternating-current
cord
of asbestos
by means

106.

made

were

in the

Figs.104, 105, and

were

be fixed at any required


height
hollow
down
in
pillars.
slidingup or

supports
+

thick carbons

The

could

connections
and

current

process.
carbons in

thicker

the

to

good joint

clamps,which

current

marked

connected

were

ensure

aid of

the

with

to

as

if continuous
interfere with the

occur

would

which

action

an

doubtless

would

aa

REFINING.

AND

8MBLTING

KLBOTRIC

on
mm.
a

the

taneously.
simul-

[^in.]
diameter

whilst
ins.],

the

178

ELKCTRIC

SMELTING

Unfortunately,after

about

AND

and

hour

an

REFINING.

the

had

be

to

carbons

of

cut

of

out

only be kept constant

of this
shunt-regulator.In consequence
have
which
of
led
would,
a
course,
strong sparking began
and
to the burning of the brushes
of the
a
rapid destruction
The only course
it the experiment was
commutator.
to be
left,
with

aid

half,two

burnt
and
out
the resistance used were
the
could
the circuit,and
current- volume

continued

of the

unchecked,
This

the

charge.
completely dehydrated
result

at

was

the

The

of small

still further

to

resistance

55

grms.
the 1*15

in the crucible.

of

[2 oz"] of
kilogrms.

The

desired

a
steep potential; there resulted
and the fused charge,characterised

and

arcs

reading rose

voltmeter

chloride

chlorides

the anode

formation

internal

the

by adding

barium

achieved

once

gradient between
by

effected

mixed

of fused
[2^ lbs.]

increase

to

was

was

to

the

"

singing

'*

33 volts.

increased

After
42

of the

short

anode.

time

the

the

volts

to
addition
was
by
pressure
of 10 grms. [154grains]
barium
more
chloride,and this pressure
for the remaining few
maintained
of the run.
hours
At
was

first the current-volume


to

current
as

the

and

as

decreased

to "0 amperes,

graduallylowering the anode.

85 amperes

was

raised

volume

of
by
graduallyfell,in the end to 55 amperes, in proportion
anode
(to avoid all danger of short circuit)was raised,
anode

the

remained

area
was,
constant.

in consequence,

pressure
The
alternating-current
pencilswere
of the

whole

but
The

not

reduced
altered

; but

during

of

the
the

during
G^hours period
electrolysis,
and
at 98 amperes
8 volts.
constantlymaintained
The
of the barium
of the
chloride in the electrolysis
use
is worthy of specialattention.
chlorides of the cerite metals
of varying the pressure
and
The
strength of the
possibility
addition
of
small
the
a
current
by
quantity of this salt is
remarkable.
If there should
be a marked
foaming or spitting
without
of the charge, sucli as often occurs
recognisable
any
the sprinklinginto the bath near
the anode
of just so
cause,
the point of a knife, at once
much
barium
chloride as will cover
the decompositionto proceed more
causes
quietlyin consequence
induced.
If the
of the increase in the difference of potential
so
chloride
introduced
be
barium
cautiously,a point may
very
easilybe reached at which, in a short time, the pressure varies
markedly, as may be seen
by the rapid oscillation of the needle
current

of the

to

be

few
due

This

condition

may, at will,be maintained


first mixed
chlorides and
introducing,
alternately,

ampere-meter.
a

the

was

for hours
then

which

by
grainsof barium chloride.
to the charge not wetting
chloride

of barium

be

The
the

phenomenon
anode,

if

appears
small proportion

present, whilst the fused chlorides

cerite metals, if mixed


only with alkali-metal chlorides,
The addition of
capableof wetting it justas water would.

of the
are

barium

chloride

has

metal, which

no

never

effect upon
contains

the
a

compositionof the

trace

of metallic

ated
separ-

barium.

THE

After

6|

hours

the conductant

had

risen in the

took

placeclose

circuit was

CERITE

crucible

beneath

the surface

broken, and

then

metallic

such

to

179

METALS.

the

product of electrolysis
height that a short circuit

of the

charge. The currentapparatus was cooled and taken

singleregulus weighing 170 grms. [6 ozs.]was


which
of the
speaks well for the serviceableness
have
been
This
could
end
attained,however,
only
apparatus.
A

pieces.
found, a fact
to

Fig. 107.

"

Borchers'

furnace

for cerite metals.

of the heatingeffect of
by^theapplication
for,in earlier experiments made without
of fused metal

ever

was

obtained.

the

current,
alternating

this,not

It is further

even

evident
in the

trace

that

it

is of great importance to have a high temperature


bourhood
neighof the cathode, and that the arrangements for cooling
useless for
of apparatus are
the cathode
found in
many

experimentssach

as

those

types

justdescribed.

180

ELECTRIC

SMELTING

RRFININO.

AND

good. The depositionof 170


of metal after an expenditureof 280 ampere-hours
grms. [6 ozs.]
of 35*7 per cent, whilst, in
correspondsto a current-efficiency
82*2 per
it was
the same
apparatus, when depositingaluminium
convection
in
found
the
The
this
is
of
be
cent.
to
explanation
which
always takes placewith the cerite metals,in consequence
of metal
condition
in a finely-divided
passing into the fused
in
The various metals appear
to behave
mass.
very differently
and
others
made
this respect. Experiments made
Lorenz,
by
that the phenomenon
show
and his collaborators,
by Muthmann
able
observis very marked
in the case
of lead, whilst it is scarcely
The

was
current-efficiency

with

the
positionbetween
is
more
subject it

other

types

be

cerite metals

two.

the

is heated

occupy an intermediate
Apparently, the softer the metal

The

aluminium.

to this action.

of furnace

used

electrically
(such

adaptedfor

not

probablethat
in which

Borchers.

by

that

as

It is
shown

in

certain

the cathode

Fig 107) might

this work.
REDUCTION

2.

FBOCESS.

previous edition of this work, the oxides of


can
readilybe reduced by electrically-heated
to the contrary in chemical
carbon, notwithstandingstatements
As

the

in the

stated

metals

cerite

But, as in the case of the oxides of the alkalinemetals,a metallic product is not obtainable in this way, by
carbides
and
of the strong tendency of cerium
to form

text- books.

earth
reason

nitrides.

carbide

proportionswith
the oxides,as
followingexperiment conducted
*
Stockem
L.
in
Borchers' laboratory.
by
oxide was
For the experiment a weighed quantity of cerium
kneaded
then

The

to

boiled

thick
in

paste with

tar

oxide

carbon

CegOg+30.

furnace

as

and

The

found

benzine, and

waa

was

oxide

The

obtained

so

This

mixture

just described.

carbide

with

intimate

of cerium
reduction-temperature

oxide

diluted

furnace.

again until the most

and

in all

repeated
process was
mixture
possibleof the
resulted,in proportionscorrespondingto the

crucible

again and
formula

mix

to

appears
is proved by the

had

"

See

Note,

heated

to

the

electrical resistance

of
thoroughly-fusedmixture
the followingcomposition^

by analysis:

then
in the

p, 170.

THE

It

CEBITS

181

METALS*

crystalline
yellow in colour, and its fracture was
;
it
into
with
contact
water
acid,
was
or
brought
it
liberated marsh
with
when
scratched
a
knife,
and,
freely
;
gas
emitted
with
the
is
but
not
case
so
nearly
sparks,
brisklyas
was

when

it

metallic

carbide gave

This

cerium.

when

decided

odour
that

of ammonia

is much

more
air, phenomenon
exposed
if a largerproportionof carbon
is used for the reduction
of the cerium
sphere
oxide, and if the heating is conducted in an atmoof ammonia
of nitrogen. Although the odour
might lead
the
that
to
of
a
large proportion
nitrogen was
supposition
really but little. The result,however, was
present, tliere was
the
undertaking of an
sufficiently
noteworthy to encourage
of
favourable
into the conditions
to the formation
investigation
will be given elsewhere
nitrides;the results of this investigation
described
when
clearlyshows
completed. The experiment just
that it is hopelessto expect metal to be reduced by a reaction of

moist

to

evident

the

carbide

Figs.

with

108 and

the

109.

"

oxide

of cerium.

Stockem's

funiace

for

productionof

cerium

'alloys.

known
It is well
that
of
Cerium
Alloys.
Rednotion
does
reduced
when
not
aluminium
oxide,
yield a
by carbon,
in spiteof that,the brothers Cowles
metallic
but,
;
product
pure
in so
succeeded
alloys by adding other
reducing aluminium
L. Stockem,*
metals, or their oxides, to the charge. Similarly,
"

smelting a
the

mixture

proportionthat

oxide, and

of cerium

oxide, copper

would

expected to yieldan

be

carbon

in

ing
alloycontain-

10 per cent, of cerium, obtained a metal containing94*43 per


In a second
of cerium.
5*5 per
and
cent,
of copper,
cent,
chosen
of
the
the
so
were
ingredients
proportions
experiment,
"

See Note, p. 170.

182

BLKCTBtP

8MBLTINQ

RBFINING.

AND

cally
allojcontaining20 per cent, of ceriam might theoretihalf
tihe
of
but,
expected
anticipated;
again, only
of cerium
was
obtained, the compositionof the alloy
proportion
Ge
the
89-67 and
10*3 per cent.
In each case
Doing Ca
the
been
have
unalloyed cerium was found to
greater portionof
It was
converted into carbida
not
possibleto obtain an alloy

thftt

an

be

"

of iron and

furnace

in this way.
somewhat
different

cerium
of

previouslyused
a

was

between

this

material

as

round

those

to

results in these

to

resistance

But

current.

construction

give good
crucible (Figs.108
rasgnesite
empty

An

placed as

found

the
is

with

ments.
experi109) was
carrying the

and

rods

carbon

when

non-conductor

charcoal

hard-wood

was
packed
powdered
grain and low conductance, and heated

cold,it
of

large
high temperature.
the crucible was
thus raised to a brightreidheat it
As
soon
as
began to act as a conductor, and the temperature then rapidly
heat by the action of the current
to that of a brilliant white
rose
it.
The
mixture
to be reduced
now
was
flowingthrough
placed
and
in the crucible,and the reaction occurred
in
short
a
briskly
space of time.
Extraction
The

Cerium

the

found

to be

doubtless

success.

temperature
since

But

result.

just described, be
the

The

to

if

used,

that

temperature

for

Agents.

magnesium

evidentlyinsufficient to
of heat,such as
a source
very

requiredfor

the

and

process,
of the reaction

heat

it is

boilingpoint is

Bednoing

Qoldschmidt

excess

is

of aluminium

of the

manner

possibleone)

desired

Metallio

by

experimentalsubstitution

carbon, after

the

of

to

difficult

adequate
obviously lower than

reaction.

the furnace

adjust the

yieldof the

an

The

result

of

not

(which is
bring about

to

so

was

"

for

metal,

the

optimum
using calcium

of the chloride and


reducing agent with a mixture
oxide of cerium
is equallyunsatisfactory.
But although the pure metal cannot
be thus got, it is possible
to obtain alloysof cerium
by adding oxides or chlorides of other
metals to the charge to be reduced by aluminium
(or,it may be,
and
of cerium
of the oxides
by calcium carbide). Mixtures
with
did
aluminium
the
not
expected result,
give exactly
copper
carbide

as

because

part

alloyedwith
however,

by

means

Uses

at

of

the

the cerium
least

proved

added
and
the

aluminium

found

was

reduced.

to

have

The

experiment,
copper
oxide
of reducing cerium
possibility

of aluminium.
of

of the

the

Cerite

cerite

Metals.
metals
are

"

Since

still

the methods
in

the

of preparation

quite
experimental
to
as
obviouslyimpossibleat present to say much
the industrial applications
of these metals.
The
for
openings
them
utilising
especiallyas con-'
are, however, fairly
numerous,
siderable
quantitiesof the cerite oxides may
reasonably be
into
to
the
market
come
as
expected
cheap by-products from
stage,it

is

THE

cerite

and

monazite

in

CBRITE

the

183

METALS.

manufacture

of

the

mantles

for

incandescent
The
used
of the

gas burners.
and carbides
metals

in the manufacture

would, doubtless,at

of fireworks

on

account

low

price,be

of the brilliance

sparkswhich thej produced in burning. The lightwould


probably be useful also in photography. The readiness with
-which the cerite metals
form
alloys,especiallywith copper, is
noteworthy, as are also the density,toughness,and relatively
of these alloys. The reducing power
of cerium
great hardness
be observed
also that
It should
approaches that of aluminium.
the
formation
the
of
of
of
cerite
metals
nitrides
the
a
study
may
lead to the synthesisof other nitrogencompounds.

184

PART

III." THE

METALS.

HEAVY

I.

CHAPTER

COPPER.
of

Ooourrenoe

Copper

principallyused

ores

for

in

Nature.

the

The

"

extraction

the

followingare
of

copper:

^Native

"

oxides, red copper ore or cuprite,Cu^O,


copper;
[metallici
less common
black oxide or tenorite,
and
CuO, which is much
;
copper glance,Cu^S ; copper pyritesor chalcopyrite,
Cu^S Fefi^;
variegated copper ore or embescite, dCu^S Fe^So; the salts,
blue vitriol,
CuSO^ ^Ufi ; malachite,CnJOB)fiO^ ; and blue
of copper or azuite, Ca3(OH)2(C03)2.
carbonate
the

But

besides

artificial

above

the

natural

products containingcopper

extraction

of

that

compounds,there
which
these

may

are

be used

many
for the

mattes, produced
in the smelting of lead or nickel,speise,
incidentally
slags,and
of
the
latter
be
named,
alloys;
especialimportance among
may
dross from
liquationsand certain products from the refining
metal.

Among

are

of lead.
The
treated

and

ores
so

as

copper,

which

metal.

The

of
cases

copper

cupriferousby-products are usually first


yield an impure metal, crude copper or black
then
is
treated for the preparationof marketable
followingshort sketch of the general metallurgy
the

to

will assist the

consideration

unsuccessful,to replace some

of

of the

metallurgical
:
processes by electrolysis
"

attempts, in

purely

many

chemical

or

186

ELECTRIC

SMELTING

Reducing proceu for the


OugO produced and dissolved
2.

BBFININ6.

AND

reduction
in

in
1

stage

the

furnace

Product,

"

of the

malleable

copper.
Black

containing the precious metals is purifiedby


direct or after partial
refiningby process ii.,1.
black copper ; electrolyte acidified aqueous
Anodes
solution
cathodes
of copper salts ;
electrolytic
copper.
and Cu'; atomic
(Cu'
Properties of Copper.
weight
Copper
when
exhibits
a yellowish63*4,specific
gravity 8*94),
pure,
copper
either
eUctroly9%9y

"

"

"

SB

red colour

recentlyfractured.

surfaces

on

The

granular, but

of cast

structure

rollingit becomes

by hammering or
united
for great ductility,
with a
hardness
which
has
moderate
and
of
tenacity. Copper
degree
be made
work
hardened
malleable
become
by mechanical
may
for
heat
and
Its
is
electricity
conductivity
again by heating.
very high,and the latter property has therefore led to its general
in electro- technical work.
for conductors
use
Shortly before
attainingits melting point (which is about 1,050" C.) the metal
be pulverised. In the molten
becomes
brittle that it may
so
condition
has a greenish colour, and it also imparts a
copper
The boilingpointof the metal is
green tint to oxidisingflames.
removed
from
the
not far
temperature of the oxyhydrogen flame,
and may
0.
perhaps be taken as approximating 2,000**
certain
When
has
dissolve
a great tendency to
melted, copper
which it
gases (hydrogen,carbonic oxide, and sulphurous acid),
evolves againon solidifying.Certain metals (aluminium, nickel,
is

copper
fibrous.

It

is remarkable

cobalt, zinc, cadmium,


chromium,
manganese,

tin, lead, bismuth, the


tungsten, molybdenum,

noble
and

metals,

iron) are

readilydissolved by it,as also are various metallic compounds


(cuprous oxide, sulphide, and phosphide, and the arsenides,
of lead, bismuth, "bc.).
arseniates,antimonides and antimoniates
should
of the gases and the compounds last named
The solubility
with the melting of the copper in
be remembered
in connection
and in the castingof copper and its alloys
the refinery,
generally.
and other metals is utilised in
The mutual
of copper
solubility
the preparationof alloys.
Of the chemical
propertiesof this metal the followingmay
be speciallynoted
as
bearing upon its extraction and useful
The
:
(and
applications
polishedsurface of rolled or hammered
also

"

therefore

dense)copper

may

; but, in contact
of air,the metal
is very

long time

basic
below
which
In

remain

with

unaltered

acid substances

in

the

in the

air for

presence

easilyoxidised with the formation of


salts (".^.,
verdigris). Or, again, at a low red heat, far
covered with a film or ^^9cale^^
its meltingpoint,it becomes
consists of

combining
than

of the cuprous
sulphur it exhibits

mixture

with

does any of the uther


energy
has a special
interest in connection

and cupric oxidea


far greater chemical

heavy metals,and
with

this

the extraction

property
of copper

187

COPPER.

from its ores.

loids,
Copper also unites directlywith the other metaland
carbon.
exceptinghydrogen, nitrogen,
The principal
solvents for copper are
nitric acid,concentrated
and
acid,
Bulpharic
ciqua reffia. Hydrochloric acid and dilute
other
acid only dissolve the metal
when
air or some
sulphuric
s
ubstance
solution
of
is
the
low
account
oxidising
firesent; on
be produced by the
never
pressure of this metal, hydrogen can
action of acids upon
it,and it is for this
of an oxidising
agent is required.
into
Copper enters
cuprous compounds)
element.

In the

combination
or

as

that

processes to the extraction


has found any wide
refining
It will be best to couimence
of the

the

study

the

of this

procedure connected

of

Eleotro-Deposition
be

on

COPFEB.

OF

could

process
with it.

Copper.

separated from

"

its

copper
the electric current, was
known
through
successful
researches
in 1800, no
applicationof

Cruikshank's*

of

could be made

after the invention


time

with

that

means

this observation

no

in

fact

(in

The

"

BEFINING

Early attempts

Although
solutions by

Copper.

simplicityof the

ELECTBOIiTTIC

monovalent

foregoing sketch
attempts to apply electro-chemical
of copper, only that of electrolytic
applicationin metallurgy.
practical

of

of all the

(in cupric compounds)


it is almost
always

salts

Eleotrolytic Befining
has indicated

as

acids

of the oxygen
condition.

in the divalent

account

either

divalent

that the addition

reason

was

of the
lost in

dynamo.
the
utilising

field of

metallurgy until
ever,
Following upon this,how-

in the

current

for the purpose

in

question.
to apply the current
constantlymade
and
the
t
o
treatment
especially
metallurgical
purposes,

Attempts, however,
to

were

of copper ores, even


economical
when
there was
at a time
no
work
available.
in the years
generator of electricity
Beoquerel's
1835 to 1840, on the electro-chemical
of
treatment
ores
containing

silver,
copper,

and

brieflyunder Lead,
known
became
in
soon
as Jacobi's discoveryof electrotyping
the year 1838, Smee
recognisedhow important a part electrolysis
was
destined to play in metallurgy,as may
be gathered from
his work
electro-metal lurgy.t Even
in 1867, the year in
on
which Siemens
his dynamo-electricmachine,
first described
Patera { published an account
for the precipitation
of a method
lead,will

be

referred

to

As

ot

copper

from

cement

waters, in which

he wrote

"

Xicholaon's Journal n/NaturcU PhUMOphy^


1800.
t JSmee*8Electro-metallurgy,
1841.
X Verhandlungtn
der h. k. geofogischenBeichsansfalt, 1867, No.

^^gltr'spolytechnischee
Jo7imalf 1867, vol.

clxxxiv., p. 134.

5 ; and

188

ELECTRIC

Patera's

8MBLTIKO

Frooess.

"In

"

AND

plates,a rectangularclay
walls

that

with

made

hounded

of the

by

the

clay cell,the

cell.

This

it

passedthe solution
the clay cell were

was

Within
a

stout

space

copper
each

between

brought into
of

means

wire

pair

bottom

filled with

was

that
of

sides

introduced
the other

on

one

of

the

of the
space

two

trough,
thus

was

trough, the free


trough and that of the
granulatedcopper, and through
the

to be recovered.
copper was
soldered on to
iron plates,
so
parallel

which

from

there

plates.

wire.

empty

an

guttapercha
that

of the

was

space

This

electrical connection
copper

longer sides

the
them

shorter

with

cemented,

so

was

water-tight
jointwith

formed,
walls

in contact

lined

trough

cell

were

REFINING.

The

copper
side of the

lines

four

of iron

plateswas
granulatedcopper by
tinually
consulphateliquorwas

system

with

of about

the

cell,and

run

was

off from

with
vitriol,
through
mine
a
proportionot copper equal to that of the SchmoUnitz
than
half
cb.
ft.
loses
its
waters
more
oz.
viz.,^^j^
copper
per
in traversingeven
the 1^ ft of space through which
it has to
pass in this small apparatus. By passing the liquidthrough
such cells in succession,
two
or
by leavingthe solution in one cell
for only a short time, the extraction
of copper will be complete.
a

glasstube.

"

solution

of blue

"

It appears,

**

therefore,that

this

apparatus

will

all

answer

requirements. The copper obtained in this way will be very


pure, the consumption of iron will correspondvery nearlyto the
equivalentof the copper separated,and the apparatus will be
therefore
to
supervise. The only
compact, and
very
easy
that I [t.d..
difficulty
Patera]observe is that a largequantity of
granulated copper must be employed, which, although it is not
permanently lost,is locked up in the apparatus, and, therefore,
adds considerably
to the capital
outlayin making the installation.
/ afterwards
and
the copper byfragmentsofcohe^
attemptedto replace
apparentlywith completesuccess^ for the copper coats thefragments
so
ihorougldyand so easilythat they are able at once to form a
svistitute
perfect
for iJ^egrantdcUedcopper"
The
Elkington Patents.
Elkington'sprocess possesses great
interest in connection
the first to
it was
with copper refining,
as
utilise the current
from the dynamo.
The English patent* dates
the year 1865, the American
from
f bears a considerablylater
The
date.
followingis a transcriptof the later British specification,
omittingpreliminarymatter :
This invention
has for its objectimprovements in the manufacture
of copper and in separatingother metals therefrom.
"

"

'"

"

an

For

this purpose
I smelt the
metal
therefrom, which
impure
of

means

copper
*

on

copper
I then

ore

so

far

cast into

as

to

obtain

and
plates,

I dissolve these platesand depositUie


electricity
which
with
other metals
to other plates. The

English Patent 2,838, Nov. 3, 1865 ; and 3,120,Oct. 27, 1869.


Patent 10,131,of Feb. 22, 1870.

tU.S.A.

by-

pure

the

189

COPPER.

in which

above

by

stated

ores

copper
w^ould
before

fall for the most

operate.

is not

part

This

process
for it has before

new,

bottom

to the

of the

generaloutline

in its

patented and

been

as

used

3rd, 1865, No. 2,838.)

November

improvements in the
I prefer to employ copper
of conducting this process.
which
sufficient silver materiallyto injure the
contain
in the ordinary way, and which, consequently,
if smelted
be
the silver
submitted
to a process for extracting
usually
the quantity
they are smelted. In such ores, frequently,

"My
method

(See patent dated

me.

of

combined

was

copper
vessel

present

such

silver is not

extraction,but

for the cost of

to pay

as

in

consists

invention

when
of
has, nevertheless, been necessary
copper
process
These
qualityis requiredto prevent injury to the copper.
for my use, as
their pricein the

suitable
particularly

the

the

high
ores

silver

they Qontain,
by
Ores
additional
without
cost.
me
a
containing largerquantity
any
8 ounces
and
of silver,
to the ton
upwards, and
say from
which
to a process for extractingthe
are
now
always submitted
before
also be advantageously
silver
smelted, can
they are
^worked
by my process, as can also ores containinglittle or no
but
the advantage of my
in this latter case
silver,
process over
the ordinary process is mainly in the better quality of copper
are

ivhich

does

which

I obtain.

raise

not

I smelt

all its metallic


form

of

the
which

regulus,from

essential,I carry the metal


copper ; this
ins. wide, and

in the usual

ore

(except such

contents

metal

as

stage,by
to

on

market,

I cast

the

way
be

may

is recovered

so

as

to

volatile)in

but
preference,

state

of

obtain

pimple

the

it is not
or

blister

into

plates,
say 24 ins. long,"
plate is provided at
the centre
with a stout T-shaped head of wrought copper ; it is
the
Oast-iron moulds
in
mould
in which the plateis cast.
placed
The metal is tapped out of the furnace
used.
to a sand
are
on
The
floor,and is led by channels into the moulds.
platesthus
which
is laid with a
cast are
ready to go to the dissolving-house,
1 in. thick.

floor,inclined

wooden

boards

The

impure

be

no

coated

open
with

are

floor is divided

into

end

of the

are

also saturated

receive

buildingby

three

the

of the

end

an

inch

edges, and

to

small

the

number

it

watertight. The surface


of troughs running from

ledgesof wood

fixed down

upon

foot.

stripsor

that there
into the grooves
so
surface is thoroughlysaturated

make

with

stoneware

to

their

on

inserted

and
joints,
pitch to

end

from

grooved

are

tongues of wood

end

One

may
and

of the
end

to

it; these

pitch. Each trough is of a width to


jarsside by side. The jarsare cylindriThere are pathways between
ins. wide.

high and 18
who
attend
Each
to the process.
troughs for the workmen
trough is filled from end to end with jars. There may be, say,
about
100 jars in each trough,and
12 troughs in the width of
The
that they
the building.
so
jarsshould be of fireclay
ware,
the
solution
which
Each
be
receive.
not
injured
by
they
may
caly34
the

ins.

190

SMELTING

BLBCTBIC

AND

REFINING.

plug,also a hole in
another
hole diametrically
the side 4 ins.
the
first
The
and
4
ins.
from
the
to
jarsare set up
opposite
top.
level on the inclined floor with wooden
wedges saturated with
togetherfrom the upper to the
pitch. The jars are connected
each
lower end of the room,
jarhaving a pipe passingout from
the top and entering the next
it at the hole near
jar below at
has

bottom, closed by a
from the bottom, and

hole in the

hole

the

made

the

near

with

connections

The

bottom.

wooden

with

connection

india-rubber, and
pipes may be of lead,and

the

vulcanised

intermediate

the

about

jars

are

of the

in. internal

diameter.
The

'*

solution

obtained

which

sulphateof copper
be
commerce
may

as

the copper
furnish a solution

furnace

dissolving-room
; it is admitted

tank

at

into the

of

long

or

the

is led to

sulphateof

the

much

as

copper of
tion
soluuse
a

I sometimes

from

purpose.
is stored in a

solution

The

depositfound in the culvert

boilingthe

by
by which the smoke
high chimney; this will
sufficiently
pure for the

charged with
sulphateof

is water

for economy

used, or

flue

''The

employ

it will dissolve.

upper

uppermost

end

copper
of the

jars,and

runs

jar until those at the lower end of the buildingare


connections
to stop
filled. Clipsare put upon the india-rubber
the jars are
the flow through the tubes when
and
to
so
full,
maintain
the solution at the proper level in the upper jars.
When
the process is in operationtwo
{sic)clipsare taken

from

jar

to

"

twenty-four hours, so as
jars and transfer
through
the
of one
bottom
jar to
top of the next,
off,say,

in

once

flow

all the

to

solution

the

cause

solution

the

from

to

the

so
as thoroughlyto mix
weak
at the top of the jar.
working it tends to become
This means
of readilyequalisingthe densityof the solution is
of great practical
is
importance. At the lower end of the room

in

it,as

tank

the

receive

to

solution.

When

allowed

it is thus

into the

pumped
upper
of the jarswhen
the contents
they
bottom
of
beneath
removal
the
the
the
floor
to
by
between
In the gangways
the
described.
through
tank

back

it is

reservoir.

to ran.

The

same

emptied on
inafter
plug,as herea
floor-troughs
the
in
which
truck runs
to carry the cast copper
to
plates
jars
Six metal
platesare suspended in
they are to be dissolved.
the horizontal
each jar; they are hung in couplesfrom
copper
forks
the
receive
them
T-form heads of the
to
bars,having
upon
plates. These bars rest at their ends on other bars of wood laid
the jarsso as each to extend
of three jars,
and
on
across
a
row
the

receives

bars also

same

to

support platesto

solution.
from

support

each

There

are

four

bar; they

are

over

receive

each
the

other

jartwo

depositof

receivingplatesin

are

one

laid upon

jar to the

metal

copper

jar,two

interposed between

Conducting stripsof sheet copper


to couplethe cast platesof
as
so

are

the

bars
cross-

from

the

suspended
plates.

cast

the wooden

bars

plates
receiving

191

"

COPPER.

the next

of

metal

Each

so

cross-har

is made

and

end,

one

jar,and

The

pitch.

the

at

throughout
on

prevent breakage
receiving plates may
to

jar in

of the

on

block

wooden

saturated

false bottom

but

with

of wood
fall.

plateshould

case

of,say, 100 jars.


connecting stripat

series

provided with

each

jars are

bear

to

other

the

The

ploy
preferto empowder.
of copper is obtained, the guttaperchais
As soon
as
a deposition
strippedoff and the copper left to receive a further deposit. A
I
series of,say, 100 jars being thus coupled up into a circuit,

of

wrought copper,
guttaperchacoated

be

in the first instance

the

to

connect

called

I drive

and
such
4

by

the

hours

working

their

they

melted

and

attain

way

of

may

be sent

are

be

solution.
unfit

be

machines
I use,
three

which
With

depositionof
obtained in twenty-four
When
the cast plates
for further use
they are

in the

washed

tured
manufac-

The

per minute.
series of 100 jars

jar may

magnetic
electro-

more

those

are

lower

solution

their surfaces,and they


be used an
T-heads
may

protect them

from

tank

melted
indefinite

are

solution

by coating
receivingplatesare allowed to grow
convenient
weight; they may either be
I

The

cakes,and

into

east

to

as

wrought

of times, as
with wax.
stems

until

or

machines

Manchester.

machines

the

depositfrom

The

recast.

number

in each

injury to

the

Co.,of

"

into

their remains

remove

preferto employ

bronze

2,500 revolutions

far dissolved

so

removed;
and

at

copper

without

become

to

them

5 lbs. of

or

one

the

34-inch

makers

machines

series

H. Wilde

Messrs.

by

the

of

terminals

machines.

with

copper, or the
into the market.

working

rolled in the usual

afterwards

from

platesas they come


solution

The

may

the vats,
for

be worked

very long time, evaporation being suppliedby the addition of


acidulated
water
slightlywith sulphuricacid, and ultimately
it
will become
so
charged with sulphate of iron as to make

inconvenient

to the

advanced

work

to

it will take

but

pimple or

blister

little iron into the solution.

iron) with

(exceptingthe

metals

If, however, the metal be


stage before castingthe plates,

it further.

which

silver

copper
of the

other

or

of the

cast

jars and is
until it reaches the lower side hole;
there allowed
to accumulate
when
this happens the bottom
plugs are taken out of all the jars
washed
of the series,and the contents
out into the floor trough,
tank
which dischargesthem into the
at the end of the building;
is pumped dry,
time to time the tank
here they settle,from
plateswas

the

the

lower

end

of the

There

out.
to allow

room

bottom

of

are

one

two

such

being put

tanks
out

of

at
use

emptying.

''The
known

is taken

sediment

and

before

contaminated, sinks

to the

The

the

sediment
manner

may
for the

other metals may be


desirable to do so."

be

treated

recovery

in

of the

separatedfrom

wellany ordinary and


silver it contains,and

it should

it be

considered

192

BLECTBIC

Excepting the
little

8MBLTINO

form

of the

and
unpractical,

which

essential

features

refining;and

it must

stood

onoe

how

at

be

to

of

process

is

modem

the

methods

"

electrodes,
exhibits

which

one

is

of

copper

that

Elkington well nnderadvantage the discoveries in

his

to

arranging the

of

admitted

tarn

REFINING.

deoomposingvesselB,which

method

this
lackingin simplicity,

is

all the

the

AND

electro-technologj.
of Electrolytlo Copper
The process as
Beftniiig.7"
of a
practically
applied consists,then, in the electrolysis
solmtion
with
anodes
of
crude
sulphate
copper
copper and pure
cathodes.
And
whether
the phenomena observable
in
copper
the
be
old
the
out
carrying
interpretedby
explanation,
process
or
by the new, it will be found that no great expenditure of
be necessary
the copper
to carry over
can
theoretically
power
from the positiveto the negative electrode.
According to the
older view the electric current
lyte
to decompose the electroserves
and
would
therefore
it
first
the
shown
cause
transposition
;
in equation(i.)
:

Theory

it is

"

(i.) CUSO4

HjO

Cu

H^04

O.

(-)
But

then

at

and

oxidation

the

solution

there

time

same

and
originalelectrolyte,
thus
:
equation,

seen

that the

H^04

occurring an
anode, with a reproduction

therefore

reversal

of the

CUSO4

H,0.

E.M.F.

calculatingthe

necessary to these reactions from


data indicated by the two
equations,it will

the thermo-chemical
be

be

"

(ii.) Cu
On

would

at the

of copper

of the
former

(+)

one

the

balances
modem

the

other,and

the resultant

is nil.

explanation,the

are
electrolytes
According to
the
dissociated.
In
solution
in
such
must
o
r
case
a
entirely
part
contain
equivalentOu'^ ions and SO4''ions. The solution is
nearly saturated,and the osmotic pressure is therefore more
But
favourable to the separatingout of dissolved substances.
characteristic of copper
another
refiningis that largequantities
It
of copper
are
transportedfrom the anode to the cathode.

is true that the copper of the anode possesses a solution


if it be but small ; but equilibriumis maintained
even

pressure,
without

by the back osmotic pressure


any further expenditure of energy
But
of the cations already existingin the solution.
a
even
pressure, produced outside the bath by the dynamo,
is in direct metallic connection
with the electrodes,
serves

riightexcess
which
at

once

from

to

the

set in motion

anode

providedfor
as

the

the

of
largequantities

cathode, where

copper

on

their

path

escape is,of course,


electrical chargesgiven up by the copper ions

to

an

they deposit.
Theory

and

practicealike

teach

that

only a

very small

electro-

194

SMBLTING

ELECTRIC

REFINING.

AND

"Tin at first dissolves in the bath,bat

standing,as
in the

anodes, the

the anode

salt ; but

basic

itself.

if much

partlydepositsagain,on
of this metal

greaterpart

will be left

In the moist

condition,this

as

basic

be

present

sulphate on

anode

slime

has

drying in the air it becomes


dirty pale grey
after long drying
and
in
increases rapidly
white,
weight,even
that it is almost impossible
to weigh it correctly.
at 100**C, so
besides
the
slime
contains,
sulphuric acid, tin oxide,
Finally,
which
is present almost
entirelyin the form of the o-stannic
acid,soluble in hydrochloricacid,and only in very small proportion
is insoluble in that
the P' (meta)stannic acid,which
as
colour,but

on

the bath to become


causes
presence of tin,therefore,
without
of
gaining any considerable
copper,
respect
of the
proportion of tin in exchange; and in consequence

liquid.The
in

weaker

separationof the basic salt, the liquid becomes


acid.
quite appreciably,more

but
slightly,

the presence of the tin in the solution appears to exert a


remarkably favourable influence upon the depositof copper; for,
''But

consistingof a chemicallypure neutral solution


current-density,
sulphategave, with the above-named
the same
a depositthat was
exceedinglybad, warty, and brittle,
free
from
like
wartcurrent
an
exceptionally
g
ood
produced
copper,
the
when
anode
and
tained
conprotuberances,
very malleable,
a notable
proportionof tin. This favourable result was
whilst

bath

of copper

obtained

when

even

; it

depositedcopper

was

to be found

in the electro-

for

tested

by dissolvingthe depositin
the residue in acidulated
re-dissolving
or
even
slightest
precipitate,
turbidity,

water, and not the


indicative of the presence
From

suitingsolution.
the

doubt, arose

adding tin salts to


is also
electrolysis
of tin
*^

was

and
acid,evaporating,

nitric

no

of tin

trace

no

Arsenic

arsenic

are

in the r^
of tin, could be observed
observation
of this phenomenon,

the

custom,
their

practisedby

baths.

markedly
present in the

dissolves

acid,until

the

in

The

reduced

when

electro typers, of
required for the

fairlylarge proportions

anodes.

either

solution

few

E.M.F.

acid

neutral

or

is saturated

solutions

as

therewith,and then
arsenious
bined
acid, com-

undissolved
The
in the slime.
it remains
oxide
with
other
metallic
or
oxides, passes
cuprous
entirelyinto the slime if the solution be neutral,because these
of electricity.
compounds are not conductors
If,however, the
electrolytebe acid, a secondary(purelysolvent)action takes
place,and the arsenic slowlydissolves into the bath in the form
acid ; but this solution,of course, takes place in a
of arsenious
often the action of the acid is stopped by
less degree the more
the vat and
from
the
anodes
removing the slime from
lifting
their surfaces.

The

is,therefore,to make
richer

in

add.

"

The

influence
the

bath

copper

of the arsenic
poorer

in

in the anode

respect of

deposited from

copper

copper, but
neutral
arsenical

195

COPPER.

solutions

be free from

atelyvery

arsenic,but

contain

will

this

impurity unless

that from
the

bath

acid

solutions

contain

will

proportion*

little copper.

"AfUimoM/ goes partlyinto solution whether the bath be acid


basic sulphate at the anode,
or
as
neutral,and in part remains
whilst a portion of that which
dissolves separates out again on
anode
slime behaves
like that
long standing. The antimonial
to the
containing tin, in that it gains in weight on exposure
the
makes
air.
electrolytepoorer in
Antimony, therefore,
not
The antimoniates
are
decomposed by the current,
copper.
therefore
and
remain
at first in the slime ; they are, however,
graduallyattacked by the acid of the bath with separationof

acid, and

antimonic

tend

so

the

is saturated

solution

precipitatedin
at the

cathode

so

long

an

removed
with

basic salt may


in such a
in the shape of a black

the

neutralisation
the bath.

from

antimony,

of the

least marked

and

when

Even

when

coming
salt is be-

basic

the vats, the antimony is not


deposited
the electrolyte
contains
approximately

proportionsof

the normal

towards

this effect is the

electrolyte
; but, of course,
the slime is the most
often

acid

and

copper

; at the

worst,

some

mechanicallyadhere to the cathode


muddy depositcontainingcopper and
should
solution
be nearly or
quite

case

antimony. But if the


down
with
the
the copper, and
neutral, antimony will come
deposit will be dun coloured and brittle,and will often be
bounded
characterised
by long needle-like
by
excrescences,
rectilineal planes. So, too, if the electrolyte
contain
too little
the usual proportionof acid will not prevent
copper salt,even
with the copper.
the antimony being precipitated
the action of the current, is attacked
before
even
slime
the
insoluble
into
as
sulphate,only
passes

*^Lead,under
the copper,
traces

and

going

into

solution,without

The

presence

the cathode.
bath

the
**

any
of lead in the

proportionately
poorer

IronyZinc,NiekeL,and

current

small

in

respect

refining) simple
a

and

metals

depositedat

copper
free acid, but

employed (as they are in


action
takes
place between

are

chemical

the free acids

solution of such

metallic

under the action of the

weaken
the
and, therefore,
copper,
But besides this,when
of the latter metal.

current-densities

metals

in copper.

Cobalt dissolve

readilythan

more

solution

tendency to deposit at
anode,therefore,makes

the

contains

at

present, which
the

anode

results

than

the

is

in

copper
these

greater

equivalentto

the

bath,
cathode;
in exchange a greater proportion of
therefore,loses in

salts.

when
the
always forms a ferrous compound on dissolving
but
this
is
is
to
small,
graduallyperoxidised the
current-density
the
of
influence
the
air during the circulation
ferric state under
^*Ir"m

in the vats ; and this reaction


acid. Ferric salts are formed

also

tends

at the

to

anode

neutralisation

itself

only

when

of
a

196

BLBCTRIC

SMELTING

of
high current-densitj

[120 amperes

about

metre
square
of
and
separation oxygen
forms
Sulphide of iron at the anode

free aoid at that electrode.

ferric salts.

only

replaced
by
warty
gall.J,

1,300

sq. ft.]leads

per

Even

RKFININO.

AND

to

amperes

per

if all the

be
in the solation
copper
2 grms.
litre
[^ oz. per
per
will still be formed.

iron, excepting about


excrescences

depositedat the anode may contain,after


drying, gold, platinum, silver,silver sulphide,cuprous oxide
and
sulphide,basic sulphates of bismuth, tin and antimony,
mud

The

"

antimonic

slime

or

acid,arseniate

of copper,

metallic

and

arseniates

anti-

be
moniates, lead sulphate,and slagconstituents, in which
may
and
will
also
silica
and
with
these
there
iron, lime,magnesia,
;
be

certain

The

of

amount

that

iunermost

the

surfaces

have

been

happens

much

more

portionsonly are attacked


completely dissolved ; on
frequentlythat the solvent

far into the interior of the anode


the

at

surface.
96

submitted

in pulverulentform.
copper
does not always so take place

metallic

of the anodes

gradualsolution

Brittle

while

black

when
the

thf' outer

contrary, it

action

penetrates

there

is yet much
copper
taining
plates,for example, con-

copper
of
2*5 mm.
per
copper,
to electrolytic
solution,and

[-^ in.]thick, were

cent,

after ten

even

days

in

soft throughout that they could be


so
they had become
like
without
cardboard
plates
together
breaking. Anode
direct from
cast
pyrites always exhibited a marked
copper
bulging towards the cathode after a few days in the electrolytic
The electrolyte
itself usuallybecomes
weaker
tanks.
in respect
of acid and copper, whilst taking up iron, zinc, nickel,cobalt,
the bath
rolled

tin, arsenic,antimony, and


manganese,
of metallic
shows
a higher total pro{)ortion
*'The

bismuth,

and

it then

salts.

last-named

extent,
disadvantage is,however, to some
compensated by a by-reaction;for it always happens, in the
of comparativelypure samples of crude
treatment
copper, that
sufficient
richer
without
the solution becomes
in copper,
gradually
It is
for the phenomenon.
evaporationtaking place to account
well-known
able
that
fact
is
to
exert
a
a slight
reducing
copper
influence on acid solutions of copper sulphatewith the formation
of

little cuprous
becomes
reconverted
a

salt,which
into

the action

then, under

cupricsulphate.

This

of the air,

was
peculiarity

studied by H. Boessler,* and formed


the groundwork of the
acid
This by-reaction
older sulphuric
process of treatingcopper.
solution of copper, which
leads to a slight but continuous
is

always the

more

the

circulation

the

solution

solvent

thin
*

the

as

liquid is
brought into

is reduced, and
current-density
made
much
more
so
rapid,that

of

thus

caused

upper
cathode

surface

action

of the
that

is

marked

better

is most
of

contact

with

marked

in

and

bath,
plate projectingabove
the

air.

the
the

The

hood
neighbourbe

so
great
may
the electrolyte
will

Dingier'9 polytech. Joum., vol. ccxiii.,


1881, p. 286.

197*

COPPER.

be

of eight
completely cut through at this level in the course
This
the
that
of
the
loss
fact
dajB.
weight
bj-reactionexplains
at the anode
is greater,and the gain at the cathode is somewhat
if they corresponded to
less,than
they should be respectively
the current^strength
employed,
in the
It is therefore
very importantthat the percentage of add
time
bath should
be determined
and
that
to time,
from
any efothat
it is equi^ly necessary
fidency should be fnade good. And
the proportion of copper
shall not be allowed
low.
to fall too
The
is 20 to 30 amperes
favourable current-density
most
per
"

2*8 per sq. ft.].


gradual neutralisation of the

[1*8to

sq. metre
"
The

operation

of the various

detrimental
In the

influence

above

reactions

whole

the

on

the

solution,producedby

to, has the most


the
of
electrolysis.

alluded

course

is greatly
place,the conductivityof the electrolyte
the
and
the
difference
of
between
Kiiminished,
potentialrequired
first

electrodes,under
5

otherwise

0*25

volt, solelyon account


impuritiespresent in the bath

have

of this

apart from the


from
obtained, even
if
unsatisfactory

brittle that

it

introduction

to

powder

formation

small, the

current-densityis

of

chemicallypure
liquidbe neutral ;

is the

current

creasedyuntil

oxide

diminishes

certain

at a

In acid solutions

alone.

and

it may
mortar.

The

oxide.

When

attached

good

"A

to

as

not

copper
oxide

the

in fact be

decompose
SO^, but

of the

measured;

with

the
the

as

well,and

it
the
in-

oxide

copper is deposited
becomes
decomposed
it
in neutral liquids

the cathode.

circulation

be

cause

pointpure
limiting
this cuprous

influence of the circulation


well

so

and

is
electrolyte

also

an

essential,

since,otherwise, the upper portionsof the bath will be more


less denuded
of copper, and impurities
will in consequence
deposited on the correspondingportionsof the cathode.
cannot

to

the

current-densityis

by a secondary,or chemical,action,whereas
remains

Then

in

does

sulphatecompletelyinto metallic
depositsa certain proportion of cuprous
of the

0*1

impurities,the deposit
solution,is exceedingly

of cuprous

copper
amount

from

neutralisation.

be crushed

can

trouble

of this

the

raised

liable to pass into the cathode


it brittle and useless.
to make

are

depositas alreadyexplained,and
But

be

to

trodes
elec-

(with the

conditions

normal

[2 ins.]
apart),may

cm.

addition

markedly
any
experiments,the results

of

on

the

but

potentialin normal

the

E.M.F.

or

be
The

solutions

requiredincreases

of

impurities. This
which
are
quoted in

is shown
the

by
following

table. In these, cathodes of pure


were
used, with
copper
and
the electrodes,
distance of 5 cm.
between
a current
[2 ins.]

[1*86amperes
per sq. ft.].The
sq. metre
96*6 of copper,
black copper
used contained
per cent.
0-403 of silver, 0*011 of gold, 1*23 of arsenic,1 of iron, and

of 20

amperes

0*54 of

per
anode

sulphur.

"

198
Table

Efisct

showino
FOB

**

SMELTING

ELECTRIC

The

increase

an

in

E.M.F.,

biquibed

COPFKE.

OF

in the

E.M.F.

the

ok

ElIOTRO-DBPOSITIOK

THE

of circulation

absence

necessitates

iMPUBims

of

REFINING.

AND

solution,however,
but

it exerts

not

only

mosti serious

physical and chemical


propertiesof the
finelycrystalline,
copper deposit; for this is always purer, more
malleable
in proportionas the liquidis well stirred,
and
more
when
even
perfectlypure solutions are used, and otherwise
influence

conditions observed.

normal
"

the
must

the

upon

In order
treatment

be made

to calculate

of

the

given

in which

raw

expenditureof

energy

necessary for

material,a laboratory
experiment

the difference

of

potentialbetween

the

electrodes is measured, when


they are separatedby a space
that
which
and when
will
in practice,
divide
to
them
equal
they
two

subjectedto

are

the

favourable
potentialdifference
the

that
it
in
on

on

at

requiredfor each

for the

moment

the

that
current-density

same

most

the

largescale.

the

resistance

been

If,then, for

poles of the dynamo


pairof electrodes be 0-25
external

has

be 15
volt

proved
example,,

volts,and

(neglecting

of the yat

connections),
should be possibleto couple at most
(15 -^ 0-25
) 60 paira
series ; but this number
is never
attainable in practice,
and
40
baths
would
the
be
an
so
more
arranged
probable
average
=

199

COPPER.

jHracdoeu If
above

at the

[0*625Ibu]of
the 40 baths
in

the

dynamo afforded
yoltage,oorrespondingto
now

of 240 amperes
of
deposit 283*61 grms.
would then be obtained in all
a

current

per hour, there


arranged in series a total of 1 1,344 grms.
copper

of
[25lbs.]

hour, or 272*26

kgs.[600lbs. in twenty-four hours.


copper
The
4*9
requiredto accomplishthis is (240 x 15)-^ 736
power
[German] H.P. for the dynamo, or about 6 [German]ELP. for
one

the steam

4*8 U.P. and


5*9 H.P.
engine ; [or(240 x 15) -h 746
calculated accordingto the British unit].It should
respectiTely,
be remembered
that a plant of this capacitywillrequire a
of 80 sq. metres
and that with the
area
superficial
[860sq. ft.],
normal
of
20
metre
current-density
[1*86 amperes
amperes
|"er sq.
five
will
months
be required to produce a copper
per sq. ft.]
plate 1 cm. thick," [or6^ months to deposita plate ^ in. in
"

thickness].
will's

Wohl

Anode.

at

Experiments:
^Modern

"

explanations,and
Dr.

Formation

theory is not

the

views

of

of

in accord

competent

so

-Mud
all Kiliani's

Copper

with
an

lurgist
electro-metal-

E.

of the
Wohlwill,* for many
years the manager
and
electrolytic
gold refineryof the NorddeutBche
copper, silver,
as

at Hamburg,
Affinerie

''In

will therefore

Kiliani's

regardedas

paper,
the standard

of the

processes

be

published in

attention

welcome.
specially
which
is commonly
1885,

chemical
explanationof the chemical and electrosufficient
electrolytic
refinery,
copper
the presence of considerable
quantities

not
was
paid to
metallic copper in the anode-mud.
I [Wohlwill]
finely-divided
studied
the
in
minute
have, therefore,
detail,using,
phenomena
in the first place,
anodes of pure rolled electrolytic
Even
copper.
there is always a separationof finely-divided
with these anodes
the current
is flowing,
but its
copper dust on their surface when
red because
colour is pure
it is not mixed
with any foreign
but lightly
It adheres
to the surface of polishedplates,
matter.
in part to the bottom
and always precipitates
of the containing
is readilydetached
vessel ; the remainder
by rubbing with a
camel's-hair pencilor with the aid of a [chemical]
washing-bottle.

of

It is
the

difficult,
however,

quantityof the

because, in
solutions
An

be formed

the

which

loose

to obtain

depositformed

under

approximate estimate of
by deducting the amount

made

in this way
anode-mud
of
the
quantity

estimations

the copper

lost

mud
as
may
the
lepresenting increase in
of the operationfrom
that

it appears
formed

in the
that

same

period.

"

(1)The
depends mainly on
^the smaller the current-densitythe greater
currentHJIensity
the quantity of waste
depositin a given time ;

the
IB

of

varyingconditions,

of air,it is very soluble in the acid


presence
used for the depositing
are, of preference,
cess.
pro-

weight of the cathode at the end


the loss in weight of the anode
representing
From

determination

accurate

an

"

From

privatecommunication.

200

ELECTRIC

8HBLTIKQ

REFINING.

AMD

(2) With equal current-densities


depositincreases with the acidityof

the

of the

amount

waste

the

electrolyte
;
and
of current-density
deposit,measured
by the
acidity,the quantity of the waste
is
difference
of
the
in
anode,
relatively
weight
greater
tionately
proporsmaller the longerthe interrupted
action of the current

(3^Given

has

otherwise

similar

conditions

continued.
Since

particles
slightest
separationof finely-divided
dissolved
is
observed
when
by
pure copper
when
in
chemical
for
immersed
solution"
a
example,
simple
as,
solution of ferric sulphate it is to be assumed that the formation
due to electro-chemical
action.
of the copper-mud is entirely
metal when
The different behaviour
of the same
exposed to
mation
could be explainedby the forthe solvent action of the current
the
with
of a small proportionof cuprous
sulphatealong
of cupricsulphateat the surface of
greatlypreponderatingmass
the cuprous
immersed
acid solution,
in
anode
a sulphuric
a copper
salt decomposinginto cupric sulphate and
metallic copper
in
*'

of

the

not

metal

be

is to

"

"

immediate,

almost

or

immediate,

the copper-mud is
to this explanation,
decompositionof the anode, but of the cuprous
the

The

solution.

assistance

from

self-same

action

electric current

an

the anode.

with

contact

that

product,not of
passinginto

ions

without

occurs

dissolves in

when

copper
of copper
sulphate and depositsagain
therefore,here repeated in a very narrow
space

solution

has been

(This action,which

cording
Ac-

any
hot

cooling,is,

on

at

the

anode.

to of late years,

repeatedlyreferred

knowledge, first described by


The effectof usingalowercurrent-denBity,and
therefore
Rossler.*)
the
sub-division
of
of
same
quantity electricity,
causinga greater
best

the

to

was,

of the

writer's

ions to
is,that the proportion of monovalent
of
is
also
the
waste
as
increased,
quantity
copper
is formed

picturethat
"In

writer's

the

of the process of ionisation.


also be further
opinion there must

effects

the

that is

copper

least,as

mud

of the

action

current, but
lying immediately beneath

and,

is

from

depositedcopper-mud which is in contact with


as
yet unattacked, behaving as an insoluble or, at
less attackable
If this be so
or
more
negativemetal.
uninfluenced
must
remain
not
by the solvent
only

from
resulting

the

ions

produced
correspondsexactlywith the mental

this observation

; and

them

divalent

therefore,from

action

would

of the

anode.

will be to

muddy
increase

thus

petiod of

time
"

on

the
this way
reduced
extent

deposit,and
the

it from

influence

be exerted

In

some

and

the

in

number
must

be

protect the part

must

with

contact
of

the

the

of the

the

current.

anode

electrolyte,
The

solvent

adjacentunprotected parts

available

unattackable

surface

separationof the
must
current-density
consequence
of monovalent
ions produced in a given
diminished.
It is thus
proportionately
owing

to

the

the

Dinghr's polytech.JatinUf 1881,

vol.

ccxlii.,
p.

286.

202

SMELTING

ELICTRIC

anode

BEFININO.

able to dissolve in the chloride

are

that

so

AND

there

is

no

dischargeof

solution

ions

in any
anode

the

at

proportion,
and no

Further^
separationof copper as in the case of the sul phate bath
the quantity of copper dissolving
is independentof
at the anode
the current^ensity,
and exactly correspondsin all cases
to the
If the concentration
of the
equivalentof monovalent
copper.
chloride
in the electrolyte
is low there will be a separationof
white cuprous
The same
chloride at the anode.
phenomenon is
observed
chloride or hydrochloricacid be added
if sodium
to the
added
with
ever
whatchloride at once
reacts
sulphatebath, since the
sulphateis formed at the anode and produces the
cuprous
.

insoluble cuprous
formation

no

In this case,

chloride.

last,there

in the

as

is

of metallic mud.

separationof the red anode deposit is a characteristic


small proEven
indication of the purityof the copper.
a very
portion
of impurity can
be recognisedby the blackening of the
deposit and of the anode itself. Hence, all copper produced
black when
used as
otherwise
will become
than
electrolytically
will
also electrolytic
in the depositionof
an
anode, as
copper
which
sufficient care
has not been
taken
to avoid the co-precipitation
mony.
of arsenic and antiof foreignsubstances,and especially
'*

The

It
conduct
a

The

the cathode

anode-mud

anode

depositof

of the

insoluble

of

laws

and

obtain

for the

control

that

the anode

to

of black

proper

side of the vat.

copper

admixed

constituents

contained
the

govern

therefore

with

it.

in the mud
the

deposit on

becomes

the

differs from

only
imperfectlypurifiedfine copper

dust
metallic-copper

same

to

transferring
electrolytic
process by occasionally

platefrom

test
"

is,therefore,easy

of the

greater when

black

in the
The

quantity
proportion
the

depends upon
pure
the

copper

anodes,

current-density
always
With
lower
currentdecomposition is reduced.
used
in the
scale
for
densities,such,
on
a
large
example, as are
Norddeutsche
at Hamburg
viz.,40 to 50 amperes
Affincrie
per
^the quantity of copper in
4-6
ft.l
metre
to
[3'7
sq.
amp. per sq.
the anode-mud
is very considerable.^
'*The
irregularcorrosion of the surface and the breaking^
of
sizes is much
of various
more
fragments and particles
away
used

for the

"

"

marked

with

copper,
attendant
insoluble

black

since

consequences
or

are

than
of the

increased

by

those

with

copper-mud
the

of
and

addition

pure
its

of the

of the black copper.


metallic copper in the anodeof finely-divided

presence
furnishes
the

copper

anodes

constituents
difficultly-soluble

"The
mud

copper

protectiveaction

the

sulphateand

explanationof

decrease

the

gradual increase

of free acid observed

in the

of

baths

that Kiliani must


have regarded what
was
actuallycopper
oxide.
in anode-mud
This oxide can
to the
only occur
blac*K copper, and has escaped
that
it already exists
in the
extent
decompositionby acid.
as

It appears

best

being cuprous

203

COPPEB.

need

electrolytic
refining. The copper in this form is readily
as
sulphate in the presence of sulphuricacid
copper
of
and
air; hence, in those refineries which employ a current
of
air to agitatethe bath
and
centration,
conso
overcome
irregularities
there
is a notable
consumption of free acid and
is no doubt
that the few cuprous
formation
of sulphate. There
in

dissolved

ions

which

exist

the

dilute

acid

in

the

on

solution,and

cold

chief

the

chemical

which

cathode

is

copper,
of the changes in the

action

of

commonly

electrolyte,
with
compared
respect
the
The
the
anode-mud.
in
secondary
finely-divided
copper
reactions above referred to do not suffice to explain the marked
refineries in
increase
that is commonly observed
in electrolytic
the anode
the amount
when
of copper sulphatein the bath, even
such
material
considerable
contains
of
a
impurities
proportion
teud
as
by their solution to deposit copper on the cathode,
and 80 to lessen the proportionof copper sulphate in solution.
lack of causes
for such an
no
Although there was
ment
impoverishof the NorddeuUche
of the solution in the works
Affinerie^
that
it regularlyhappened throughout several
years of work
r^arded
only exert

the

as

small

cause

influence

in this

about

of the
2 per cent, or more
instead
the form of sulphate
of

in

the continual

doubt

contributes

sulphate
produced

as

recovered

was

copper

Without

metalliccopper.

compressed air to mix the solutions


of a large proportion of copper
The
quantity of this salt ultimately

of

use

baths.

the

would

anode

formation

the

to

in

as

not, however, be less if mechanical

stirrers

or

cause
employed to mix the solution,begases
oxygen
that portionof the finely-divided
which
ordinarily
copper
into the bath as sulphate would
in the end have to be
enters
in the form of sulphate,by the subsequent treatment
recovered
free from

were

of the anode-mud
''The
be

should
is

outside, the bath.


of

Chlorine

that

chlorine

Behavioiir
remarked

constituent
never-failing

in

the

Electrolyte.

in combination

of the anode-mud

"

It

with

copper
produced in the

industrial

After the
means.
refiningof copper by electrolytic
have
which
been
is
it
just
explanations
given
scarcelynecessary
well as cupricions
of cuprous
to point out that the formation
as
the anode
is a phenomenon that has to be reckoned
with.
at
chloride
in
and
immediate
of
The
separation
production
cuprous
with

contact

of

the anode
ions

cuprous

is a necessary
of the formation
consequence
chlorides
wherever
is
water
containing

used for the preparationof the electrolyte.It may readilybe


observed
that during the prolonged electrolysis
of solutions
of
copper
water

sulphatein river water,


to
graduallydiminishes

free from

chlorine

Hence,

originallypresent

is used

to

proportionof chlorine in the


nil,provided that water
good the losses by evaporation.
the
chlorine
of
precipitation

almost

make

extensive

very
follows

the

this formation

of cuprous

ions.

The

204

SMELTING

KLKCTBIC

AND

REFINING.

of a relatively
largeproportionof chlorine in the water
presence
used
is im mediately recognisedby the white
deposit on the

Anode; but

quantityis small the colour of the cuprous


by the
always formed is liable to be masked
in
the presence
of air
impuritiesin the copper, especiallyas
the sub-chloride
tends to be converted
into
a
dirty
rapidly
green
coloured
It need
that,like
scarcelybe remarked
oxy chloride.
in the
-divided metallic
the sub- chloride
mud,
finely
copper,
influence
u
nder
the
of
combined
decomposed gradually
sulphuric
acid and air,contributes
of copper
to the increase
sulphate in
chloride

when

that

the

is

the solution.
'*

The

in

cathode,

elimination

of

the

degree, plays

smaller

chlorine

from

the

its part
for the

water,

the

in

copper

depositedfrom chloride solutions always contains chlorine, and


this happens also,especially
when
at low current-densities,
even
river water
small
containing a comparatively
proportion of
chlorine
variable
is used.
The
quantity of chlorides in
very
the

of the

waters

Elbe

afforded

has

the

writer

many

tunities
oppor-

and cathodes
observing this phenomenon. Anodes
be
baths
that
all
the
the
of anodein
so
rows
arranged
may
between
and
the
backs
of the
platesare placed
cathode-plates,
cathodes
therefore facingthe walls of the tanks ;
outermost
are
the current-density
these surfaces will then be less than it
on
of

is

elsewhere, and

present in the

found

it will be

used,

water

much

that, when
the

even

chlorine

sides of the

reverse

is
end

with
white
chloride,
cathode-plateswill be covered
cuprous
which
air.
Much
of
becomes
to
on
rapidly
green
ex])Osure
this depositclingsso persistently
that it can
to the copper
only
be entirelyremoved
the
as
anodes,
by hanging
plates
or, in
other words, by partialre-solution.
In the years 1892 and 1893
the amount

of chlorine

abnormal

extent,

and

grms.,
The

and

diiiiculties thus

in

order

to

to

necessary
that

so

amounting

January

on

89*5

to

and
'*

be

both

in the

obtain
reverse

surfaces

25

to

subjectedto an
smaller quantity of
in

of sodium

characteristic

chloride

per

litre.

and
proportionately,

increased

deposit of

the connections
of the

to an

69*5

red

good

increased

Mansfeld

September 17, 1892, to


grms., correspondingrespectively

on

grms.
introduced

at

54*33

114*5

it became
copper
and
of the anodes
cathodes
face the

latter should

uniform

Elbe

anode-plates,

current-density.

chlorine

in the

It has

way.
writer for many
addition
in
years,
to hang lead stripsin the baths

to the
as

water

been

may

customary

be

nised
recogwith the

ordinarycathode-plates,

they

are

brought

into

use

stripsweekly in order that the deposited


be
strippedoff and examined, and a control be so
may
copper
the
kept over
propertiesof the metallic product of electrolysia.
It is found
that the depositedcopper, which
is always brittle at
the
first
at
first,commonly breaking
attempt to bend it even
and

to

remove

these

205

COPPER.

with

great

until after

the

weeks

few

ductilitywith
plateproduced

bending twenty

will withstand

the

in

improves

care,

lapse of time,
the

from

bath

same

forwards

and

backwards

times

breaking.

without
"This

in the brittleness

decrease

period is prolonged

of the

is not

the

depositas

with

consistent

the

working

view

that

the

in the copper of antimony


of the brittleness is the presence
these impuritiesare
since
of
that
nature,
or
impurities
th"
absent from the newly-preparedsolutions and increase with
cause

other

that both the brittleness of


The
observation
age of the bath.
the proportionof chlorine in the bath steadily
the depositand
ness
decrease as the time of action is extended, points to the brittleof chlorineof the copper depositbeing due to the presence
with the aid of
of chlorine is readilyshown
in it. The presence
nitric
acid and
dissolved
in
be
the
if
a silver solution,
copper
the solution
acid.

On

evaporated to dryness with an


hanging a pieceof brittle copper

is not

the

dissolves

presence

before

in the

of chlorine

sulphuric-

anode

an

as

in the

that

which

anode-mud

and

products is easilyrecognised.

waste

"It
cause

so, and

chlorine

free from

bath,the copper

of

excess

is clear that this cause


the writer believes
which

brittleness of copper,

of the
has

not

been

hitherto

a.

noticed,

typistand electroplater,
worthy
the
into
examine
should
who
proportion of chlorino
carefully
that they employ.
in the water
contained
the other hand, it will be understood, after a study of
"On
that it is not advisable to
certain other "cts and considerations,
plating
that is entirelyfree from chlorine either for electrowater
use
of the electro

of the attention

is

and
"

the

of

Ooourrence

course

of

of the work

Crystallme

Growths

has
the

on

on

occasions

many

"

Affmeriethe manufacture

of the Norddeutache

electrolytic
copper
difficult by

rendered

of copper.
In
Cathodes.

like,or in the industrial extraction

periodicalformation

been
of

delayed and

crystalsof the

cm.
[4ins.]
long,on all
which
for
were
crystals,
be
proved to
aggregates
of varied grouping.* Although both the crystals
of octahedra
from which
and the ground mass
sisted
they appeared to spring conconsiderations
of
practical
electrolytic
copper,
pure
mechanically,and
requiredthat the growths should be removed
in wages.
ally,
Occasionthis led to the expenditureof no small sum
the epidemic had spread to 600 baths, night work
when
in order that
became necessary for several weeks consecutively,
contracts
might be completed in the requiredtime.
that the compositionof the Elbe water
observed
It was
soon

most

diverse

sizes,often

as

much

as

10

These
parts of the depositedcopper.
the most
part of columnar
appearance,

"

Descriptionsof these crystalmasses, which are


have been publishedby Professor
mineralogist,
Hamburg, now of Konigsberg.

the

of great interest to
Miigge,formerly of

!206

SMELTING

ELECTRIC

AND

REFINING.

important part in connection with this phenomenon.


that the crystalline
almost
pletely
comgrowths vanished
when
(usuallyin July and August) the proportionof

played an
It

found

was

chlorine

reached

in the water

its

and

maximum,

all the

anodes

deposit; whilst, on the


when
other
hand, the trouble was
regularly at its worst
the
months
the
chlorine
in
of
the
early
year)
(generally
centage
perIt appeared, therefore,that the
its lowest.
at
was
substance
unknown
causing these growths in the latter case
reached to the cathodes,whilst,in the former, it was
intercepted

appeared

covered

be

to

with

white

between
the electrodes.
space
of
views above expressedas to the formation
copper anodeand its prevention by the agency
of chlorides present in

either
The
mud

the

at

anode

the

in

or

be the cuprous
bath, led to the assumption that it must
ions which, having escaped dischargeat the anode
owing to the
of chlorine ions in the electrolyte,
absence
produced a separation
the

The buildingup
at the cathode.
finely-divided
copper
of
relativelylargegrowths
copper depositon these particles
The writer has been guided
could then be readilyunderstood.
this
in
hypothesis
conducting experiments aiming at the
by
growths. In the first place,at a
preventionof these crystalline
of very

of

there

when

time

was

of sodium

chloride

or

but

magnesium

quantity. The
that at best only a

sufficient
found

effected.
with
act

action

diminution

the

in

added

was
was

addition of ferric

The

the

little chlorine

Elbe
the

to

unmistakable,
of the

water,

baths

but

it

evil could

sulphate,which

is

thus

in
was

be

incompatible

of cuprous
ions in the solution,appeared to
immediately,but the quantity of oxidisable material in the
existence

quantity of the salt sufficient for any


length of time could not be employed without disadvantagesof
kind.
scale experiments it was
another
of small
By means
that
suitable
the
found
of
diaphragms between the
interposition
electrodes afforded a solution of the problem ; and the growths
unfavourable
under
the most
were
ditions
conentirelyabsent, even
baths

was

great that

so

Elbe

of the
wooden

water, when

the

anodes

enclosed in

were

casing.
and

attainingthis
no
growth in
baths in which
the electrolytic
regularlyinterrupted
process was
day by day, in order that the quantityof depositmight be controlled for experimental purposes
by weighing,whilst it often
"*

end

resulted

continued
at

convenient

more

without
The

time.

half
to

from

hour

an

prevent

restricts
"

that

of

far that

was

whole

it is

baths

for weeks

of work
dailyinterruptions

growths
crystalline
so

there

in all the other

intermission
introduction

provisionfor their removal

of

means
satisfactory

observation

throughoutthe

the

them

an

no

plant is
upon

not

the

found

by
completelysatisfactory
explanationhad

entirely

cathodes,

longer necessary

mechanical

for

to

but

it

make

means.

yet

to

be

found.

207

COPPER.

both

of the

protectiveeffects of an interruptionof work and


phenomena that have been described above, but it can
of cuprous
ions at the
scarcelybe doubted that the formation
anode is the actual underlyingcausa
The formation
of those hair-like growths on copper deposits
of trouble
which
to the electrotyper
a
are
source
is,no doubt,
allied
be
therefore
concluded
and
it
that
an
phenomenon ;
may
in the water, and
it is generallydue to a deficiencyof chlorine
be
addition
of
little
sodium
chloride to
obviated
the
a
by
may
of the

*'

the bath."
Forster's
in

the

and
of

course

voltmeter,

have

question of

the

served

SeidePs

experiments
made
the

solutions.

From

of

the

on

certain

existence

confirm

to

Ezperimeiits.

Forster and

"

reactions

in

Seidel,*

the

copper

bearing on the
sulphate,and these have
ions in sulphate
cuprous

observations

cuprous
of
presence

experiments it would appear that cuprous


sulphate may be formed at the cathode, because,under certain
circumstances,the cupricions may not be completelydischarged
into the
there, and so a portion of the copper is returned
solution
ions.
The authors
in the form
of cuprous
explainthe
conditions
of this phenomenon as follows :
their

"

current-densities

1. At

of less than

001

the action of the current


[0*09amp. per sq. ft.]
solutions
concentrated
of copper
sulphateat

ampere
per sq. dm.
the
cathode
at
in

ordinarytemperatures

solelyin the

results

production of cuprous
the current^lensity
is increased
more
cupricions

ions.
are

But

as

completely

fewer cuprous
ions are
discharged,and, in proportion,
produced,
at high current-densities the latter phenomenon
although even
is not completelyabsent.
2. The
tendency of the cupricions in a sulphate solution to
into
ions increases very markedly with the temperapass
ture,
cuprous
that

so

per

at

100" C,

[2-8amp.
sq. dm.
the current

current-densities

at

even

when
per sq. ft.],
forms
ions
cuprous

the

of 0*3 ampere
solution
is concentrated,

almost

exclusivelyat

the cathode.
3. The
may

of cuprous
ions in copper sulplifate
solutions
of the reaction of metallic
place in consequence

formation

also take

copper with
case

of

cupricions present in the solution,exactlyas


thus f
cupricchloride solutions,
"

Cu

This

reaction

saturated

in the

with

continues
cuprous

until

Cu

the

sulphate.

2Cu.

sulphate solution is
cupric
It is difficult to decide off-

Zeit9ekrift/urEUktrochemie, 1897, voL iii.,


p. 479.
observed
t This fact was
by Jacobi
many
years aso
Lekre von der Elektr.^ii.,
was
p. 610), but the "aco76ry
"m later work.
Cf. also liote on p. 200.

Wiedemann,
((j/l
without

inflaenoe

208

ELECTRIC

hand

far the

bow

SMELTING

of

REFINING.

of cuprous
sulphate solutions

formation

of copper
electrolysis
process

AND

sulphate during the


dependent on this
it is a purely electrolytic

solution,or, indeed,whether

is

phenomenon; but the author considers


simplestand most probableexplanation.
4. Under

similar

otherwise

concentration

of

the

latter

conditions,an

the

cupric
sulphate,is accompanied by

increase

solution

ions, in a
increase
an

to

the

in

the

of

copper
number
of

the

in

be

ions.

cuprous
5. If

solution

is neutral, the cuprous


sulphate formed
to the equation:
undergoes hydrolysis(according
the

2Cu
as

soon

In
free

6. If the
and

HjO

there

than

when

the

form

certain

oxide

this, cuprous

in

SO4)

exceeded
of

the

But

it is neutral.
ratio

also,for

when

ions

has

exceeded

into

cupricions,and

is

limiting

frequently

sparkling crystals^

value,the

metallic

copper
+

Hence, referringback

dealingwith

reversible
+

limit

here

to

cupric
again

back

pass

depositedthus

"

Cu

is

is

of cuprous
former

Cu.

will be

paragraph 3, it

to
a

there

of concentration

certain

2Cu

here

4- 2H

sulphuricacid is formed in the solution.


acid no
solution is sufficiently
hydrolysisensues,
of cuprous
is a much
ions in the
larger number

solution

are

Cu^O

has

of

consequence
the cathode

deposited on
whilst

SO4

its concentration

as

value.

reaction

that

seen

we

"

+
.

Cu

7. From
the

the
is

current

at the

formed

productof
of small

^3.

Cu

when
foregoingit is evident,therefore,that even
producing only cuprous ions, metallic copper ia

cathode.

This

copper
secondary reaction,and

isolated

depositsof

2Cu.

rather
crystals,
electrolytic
copper

than

be considered
the
as
may
in the form
is precipitated
that

obtained

of the
in the

uniform

even,

usual

way

from

acid solutions.
8.
and

Ouprous
there

ions

become

arrivingat
converted

doing other work


ionisingthe anode copper.
may

be

observations

The

Seidel
will's
Von

first

are,

in

at

receive

cupricions,so

the

anode

Hiibl's

published

industrial

des k.

u,

1886,

that the current

explanations given by
points,in agreement

Experiments.
in

charges,
positive

in addition

all essential

experiencein

*MiUh.

and

the anode

into

may

to

that

Forster
with

of

and
Wohl-

work.
"

Von
be

Hiibrs*
referred

work, although
to

after

that

k, militdrgeogr.
Instit.,
1886, vol. vi.,p. 51.

of

210

SMELTING

ELICTRIC

obtained

those

of

20* C.

about

at

of

BBFININO.

copper

35*

at

the

production of electrolytic
copper
obtainable.
properties
made

be

must

attendant

in

Alcohol

the

Oettel's

to

the formation

on

mitigated by

are

sulphate

solution.

in the

caused
sulphate,

the

are, under

follows

by

these

that

of cuprous

suitable

most

the

best

Solutions.

for

mechanical

ence
Finally,refer-

"

experiments,in

an

the evils

which

dissociation
electrolytic
addition

of alcohol.

circumstances,fewer

the

with

this temperature

and

C,

the

as

of cuprous
meter
ions in the copper voltaaddition
of alcohol
the copper
to
attribute
and
Forster
this action

Oettel

diminution

to

Copper

40^

to

must, therefore,be considered

of

perties
pro-

always distinctlyinferior to
has
which
been
mechanicaUy worked.
to it,however, as already shown, when
are

They approach nearer


the electrolyte
is maintained

XJae

mechanical

Nevertheless, the

electrolytic
copper
pure

AND

conditions

free

the
that

copper
there

cupricions,it naturally

less favourable

are

of

Given

to

the

formation

ions.
of

Deyelopment

the

Electrolytio

dustry.
In-

Beflning

Copper

the
England, was
pioneer of the
refiningindustry,and the works of Messrs.
electrolytic
copper
Mason
"feCo., at Pembrey, in South
Wales, seem,
Elkington,
for some
time
after the 1865
was
granted (see above,
patent
have
been
the
which
the process was
to
only place at
p. 188),
in practical
followed
use.
by other
They were, however, soon

[Elkington,in

"

which
" Co.,
those of Messrs. Vivian
works, among
may be named
Messrs.
T. Bolton
at Swansea;
Messrs.
k Son, at Oakamoor;
Williams
the
and
at
W.
A.
at
Foster,
Swansea;
Hill's, Chester,
Co., at Hunslet, as well as the
English Electro-Metallurgical
Elliott's Metal
Co., of Selby Oak, near
Birmingham, who also

acquiredthe Pembrey
In
a

the
small

enormous

the
and

; but it

Boston

and

Co.,

Great

at

Laurel
The

which

Balbach

took

later that

ten

has

years
resulted
in the

(Guggenheim

Works), at Perth
Consolidated
Copper and

Montana

Falls,Montana,
Hill,New
York, and others.]
and

electro-chemical

gained

foothold

nineteenth

works, and
the

made

about

up
the

colossal

Copper Co., at Perth Amboy, New Jersey;


Anaconda
Mining Co.,at Anaconda; the Baltimore Smeltiog
Rolling Co., at Baltimore; the American
Smelting and

Befining Co.

the

ville Works

shortlyafterwards
until

not

was

progress was
of the Baritan

works

Phoenix

1880, and

scale in

the work

Elkington,Mason h Co.
were
refiningon

of Messrs.

works

States,the

United

from

Norddeut8che

commenced

work

in

the

of the

Silver

Mining

Chemical

Co.,

in

Germany

first

seventh

decade

important
developed rapidly. At the
Affinerieand the Mansfeld
Copper
with experimentalplants,and they were

century
this

time

some

the

Nichols

refining of copper
the beginning of the
in

Amboy

most

of

copper
outset

Mines
soon

211

COPPER.

followed

at Oker; the Altenauer


Hiittentoerk,
by the Communion
in the Upper Hartz
Mountains; the Siadtherger
KuipJerhiUte^
HiUte^in Niedermarsberg ; and C. Schreiber,at Burbach, Siegen;
and, later,by Borchers
Bros.,in Goslar, in the Hartz, and the
Elmore
the
at
Schladern, on
MeUtU-Aktiengetellschaft,
Sieg.
The last-named
a
nd
articles,
produced
especially
copper
company

hollow

such

wares,

firm of Siemens
in the

"

of the

development
Germany, and

first in

there, in
will be

other

industryof

of many
space and

Plant.

of

great service

The

"

works

newest

of the

there

original

rent-density
relativelylow curthe placing

necessitates
copper-electrolysis

of electrodes

rows

in the

specialcharacteristics

Arrangement
in

also done

electrolytic
copper refining,
ence
experinecessary

Even

countries.

of the
many
this
of
firm.
designs
used

The

copper.

then, after gaining the

fonud

General

the crude

tubes, direct from


Halske, of Berlin, has
as

bath, in order
apparatus.

each

in

to economise

It was
ready
only
natural
that, duriug the early years of the development of the
mistakes
be many
in the choice
of
industry, there should
and
in regard to the relation
dynamos, in the connections,
between

to

ensure

the

and

pressure

unnecessary
of these matters.

it

is

usual

volume

the

of the

It

days to enter into


is scarcelynecessary

shunt-wound

It

current.

further

these

in

however,

the

to

access

to

is,

particulars
that

state

machines

employ
producing
of
strength sufficient for a large number
in
the
baths
series
the
small
coupled
voltageat
;
comparatively
of the dynamo
terminals
being chosen according to the number
now

of the baths

Up
viz.

this

to

there
"

used, and

point all

the

system

parallelsystem
but

little doubt
theoretical
of copper

in the

that,

for

but

Series
in

any

System.
one

bath

parallel,whilst in
bath are
arranged

bath,
the

In

as

are,

the

latter

in series.

SYSTEM.
most

refining.
of

all the

the

electrodes

at distances
alternately,

apart, the first and

Electrodes
are

in

the

Baths.

suspended, anodes

of from

20

the last in each

suspended, parallelto one


to the longer sides of the tanks.
arrangements for suspending them
are

in agreement;
in the

are

widely used, and there is


and
in spite of
practicalreasons
bound
with
the future
closely
up

is the

it is
objections,

Arrangement

all

in

of the electrodes.

electrodes

the

PARALLEL

THE

system

and

use

the

electrodes

all similar

system, all the electrodes

The

in

arranging

implies,coupled

name

arrangement

systems

of

ways

to the

Parallel System

The

former
the

to be

two

are

to

of moderate

currents

to

50

mm.

In

"

and

this

cathodes

[| in. to

ins.]

They
being cathodes.
another and at right angles
All consist of plates with
tank

and

for

connecting

them

up

212

to

the

SMELTING

ELECTRIC

the

electric mains.

process

of

Ill, 112, 113,

The

preparing
and

114

AND

best-known

them

must

illustrate

Fig. 111.

Fig

Fig

REFINING.

now

certain

Fig

described.

be

of

forms

114.

112.

Fig

Fig

113.

Typical anodes

Fig
and

and

types of electrode

cathodes.

Figs.

anode,

115.

116.

117.

and

213

COPPER.

115

Figs.
anodes

and

116, the

shown
of

Casting
is

bought
directlyor
becoming

in

for the

well

works

Instances

"

of

purpose

correspondingto the
113 respectively.

and

more

refiningit

of crude

copper

are

now

copper

either
electrolytically,
furnace

process, are
of the electrolytic

conditions

The

rare.

black

in which

previouslyrefiningit by
and

more

treatment
8o

Figs.Ill

Anode-plates.

after

of cathode

forms

Fig. 114 and

so

well

known

and

are

adapted to those of even


quitesmall copper works, that
purchase crude copper as such will in no very

which

distant

be

most

unusual.

direct

from

the

date

that,under
obtained

Hence, it
existingcircumstances,the anode

reverberatoryfurnace

if this is so, and


the metal
of anode-plates,
it is clear

And
form

re-meltingand

of treatment

The

anode-platesof
deutsc/ie Affinerie,
which
were

may
that

in the

Siemens

and

be

direct

run

furnace

extra

into

the

costs

of

obviated.

are

and

Halske,

converter.

or

all the

represent the oldest


(Figs.Ill and

made

so

be considered
may
material is usually

Nord-

of the

and

simplesttype,

114) that they may be hung


directlyupon the conductors
In precarrying the current.
paring
these
ladled

the

is

copper
of
out

the
tapped
and
reverberatory furnace,
then, with the help of ladles,
is poured into moulds
which,
for

or

the

Siemens

anodes, consist

bed-plateswith

and

Halske

of strong iron
frames
iron

projectingupwards from
shaped according to the
and

thickness

of

the

them
form

anodes.

Figs. 118 and

119."

Mould

used

by

One

Morrow
for castinganodes.
portion of this frame is
the
attached
iron
to
firmly
plate(Fig.117),or is in one
piecewith it,whilst another part
is removable, and
into the fixed portion
is simply dowelled
Moulds
such
used in
of
as
are
during the period
casting.
bars or
running copper
ingots suffice for the comparatively
of the Not-ddetUscIie Affinerie.
small anodes
*
Morrow
prefersto use lugs of sheet copper cast into the
crude copper plates,
instead of the side supports or hooks which
are
employed to carry the anodes in the case of the electrodes

the same
be cast of almost
above described,and which
must
The
used for this
mould
thickness as the anodes themselves.

Figs.118 and 119.


in Fig. 112
shape shown
designed by Thofehrn, who was

purpose is shown
Anodes
the works

in

of the

"

United

Stetes Patent

631,471,Aug.

are

at

chieflyused
one

22, 1899.

time

in

tech-

214

ELECTRIC

nical assistant

with

SMELTING

the firm

AND

REFINING.

of Siemens

Halske.

"

Thofehm,

using
large baths as
but at the same
time
not
possible,
wishing to produce anodebe too difficult to handle, employs anodes
plates that would
of
the width
of which
is not appreciablygreater than the width
Halske.
He
then
those used
"
hangs at least
by Siemens
side
of hooks, from square bars
two
or
three,
by side,by means
baths.
the very
wide
The
plates are therefore
placed across
with
the
hooks
instead
of with projectfor
ing
provided
lugs or eyes
believingin

at the

arms

works

the

specialadvantages

sides.

different

of

as

is used

of anode

type

Guggenheim Smelting Company


the electrodes
Jersey, U.S.A.),* where
that the number
the
with
result
closelytogether,

are

therefore,the output

These

New

per
provided with

(Fig.113) are

side,whilst

one

on

12

[^

mm.

in.]in

other

to the

type
75

about

depth
side

is

of about

one
on
projectingarm
whilst the free end
positiveconducting-rod,
the other side of the plate rests in a small

cast

block
the

which

as

The

distance

[1^ to 2

mm.

baths.

will be described

Anode-Cafiting
anodes
and

as
ins.],

plant also

This

which

the electrodes

between

with

the

Two

wooden

has

wall

supports

of

rest

carriers

possibleto

20

mm.

on

the

make

instead
[fin.],
the distance

commonly
simplifiedsystem

insulating
that

on

is

it

is

of

in other

of connections

hereafter.
The

into
casting of copper
necessarily
comparativelycostly
soon
were
anode-casting machines

Machines.

"

help of ladles is
hence

inconvenient;

devised.

of the

wooden

similar

about

the
upon
iron pin on.

rests

(without any iron pin) directlyon


the opposite side.
In
this way
40 to 50

[1in.}.The

support for the electrode


comparatively small cathode

serves

vessel.

pin about
[3 ins.]long,

mm.

anode

the

of

electrodes

iron

an

mm.

25

and,
plates,

support only

of side

side there

and

diameter,

in the anode

inserted

the

on

the older

placedmore
of

increased.

tank, are

in the

(Perth Amboy,

of the

of these

may

be described

here.

of Hixon

That

Dyblie,tshown in Figs.120 and 121, consists of a number


to a bottom
placed together,and attached
plate,
The
bottom
exactly like the parts of a filter-press.
plate rests
of which
the whole
of the moulds
a truck, by means
on
(which
should be capableof containingthe entire charge of a converter)
and
of

frames

run

are

to the

up

On

converter.

the

under

plate are two rails resting on rollers,and


rack engaging with a pinion actuated
by means
With

the

aid

of this device

underneath
successively
so

that

the

copper

from

the several

funnel
the

of the

side

between
of

moulds

may

passing through

converter

may

be

bottom

them

is

hand-wheel.
be
cover

run

brought
plate,

into

each

in turn.
A

very

complete castingappai*atus,designed by Walker, J is in


*

Ulke, Mineral Induslries,1899, vol. viii.,p. 186.


t United States Patent
639,270, May U, 1895.
J Keller, Mineral Industries,1898, vol. vii.,p. 252.

215

COPPER.

in several

The metal
largeAmerican
copper works.
into a tilting
ladle placed before the tapbole.
The
filled ladle is so arranged that the side nearest
the
furnace
be raised by means
of a lifting
can
device,and the metal
then flows from the spout on the oppositeside. Thence
it passes
through a small runner
or deflector,
adjustableby hand, into the
use

is

from

run

moulds

which

and

use

with

123.

carried

are

wheel.
for

of the

the furnace

These
moulds
On

the

on

casting ladle
metal
platesare

the

to
radially

table
turn-

made
that they may be adapted
are
arms
so
of any requiredshape,as shown
in Figs.1 22
side of the turn-table diametrically
opposite

Fig.
Hixon

attached

arms

and

is

an

121.

machine.
Dyblie'sanode-casting

elevator

lifted into

the

by

means

vat-room

of which
or

on

the
to

heavy

whatever

provided for conveying them there. By the


time
platescast on the furnace side have been brought
round
to the elevator
by the rotation of the wheel, they are
turned
cold to allow of their being [automatically]
sufficiently
which
them
of the moulds
inclined
out
to
an
on
plane
conveys
inclined
to the elevator.
[The bosh in which this
plane and the
lower part of the elevator are placedis filled with water.] They
also sprinkled with
before they are
water
are
tipped out of

apparatus

may
that the

the

moulds.

be

216

ELECTRIC

SMELTING

AND

REFINING.

218

SMELTING

ELECTRIC

Cathode
thin sheet

-Plates.

cathode

The

"

copper which,
this purpose

sheet

lead

or

on

REFINING.

-platesare

always
formed

refineries,

in most

lytically.For
on

AND

are

thin

is
copper
plates,the surface of which
a

layer of

copper
coatingof graphiteor

made

of

electro-

deposited
has

been

by greasingslightly.The
it was
is then strippedfrom the plateon which
size required for the cathode.
cut to the shape and
be
holes by which
is provided either with
it may

prepared by a
depositedsheet
formed

and

Lastly,it
suspended from the hooks, or with bends to support it on the
conducting bars. At the Buffalo works the matrix
plate is
iodine
dilute
with
solution
of
in
a
painted
naphtha [toprevent
the adhesion
that the purityof the
of the depositedcopper],
so
solution

is not

affected

it is when

as

tallow

employed

is

for

the purpose.

Depositing

Fig.
almost
tanks
with
use

124.

"

Vats.

Section

"

of

Wooden

all
with

exposure

lined

with

lead

copper-rciiDingvat, shoi^nnganode

exclusivelyused
are

vats

for

the

are

now

(Siemens).

Cement
electrolytic
process.
varnished.
But
are
they
porous
the acid-resisting
varnishes
recommended
formerlyfor
wooden
it has been
found
vats
that,after prolonged
to the action
of the constituents
of the electrolyte.
too

for

use

unless

219

COPPKK.

thej introduce into the solution


the copper that
prejudicially
upon
other

The

of

arrangements

be

given

of

In

plant erected by

chemical

the

installations.
works

of

substances

which

act

being deposited.
baths, and the
electrolytic
be best illustrated by a description
the first place,an account
may
is

the

subsidiaryappliancesused, will
of actual

soluble

of Siemens

the firm

Messrs.

Borchers

Halske

Brothers,

at

in

Goslar,

importantrespectsby Messrs. E. and H.


Borchers.
Thanks
these gentlemen, it is possiblehere to
to
of the details of the plant.
publish illustrations of some
anodes were
of the originalshape commonly used in plant
The
designed by Siemens "feHalske, as may be seen at a in Fig. 124.
has already been given of the castingof these anodes.
An account
The
cathodes always consist of thin copper plate(Fig.125).
improved

and

baths

The
with

with

On
oil

"

Cross-section

other
which

as

place,the

withdrawal

suitable
serves

conductors.
lead
of the

is bent

of copper-

this is laid the

or

wooden

depositing-cells
are

lining,which

and

water,
used
,
in

or

leaden

Fig. 125.
vats.

in several

substance
Before

to

of the

is saturated

which

prevent it from

the

the
x

rims

the

over

frame, r,

to insulate

H,
(pitch-pine),

(Siemens) showing cathode

vat

wooden

siphon pipe,

round

vats

two

copper
electrodes
are

(Figs.124

solution, is introduced

and

into

absorbing

bars,

and

suspended
126),for the

the vat;

this is

220

ELECTRIC

followed
and

the

by

supports

SMELTING

wooden
leaden

AND

REFINING.

the bottom
rests
on
table,", which
latter
the
is
turned
tray, $;
up at its

edges, in order that it may collect the depositof mud which


graduallyseparatesfrom the anode.
The
anodes hang directly
from the sides of the vat, but must
be insulated from the
conductors
i
by the india-rubber plates,
1
The
cathodes
h
ooks
(Fig. 24).
are
suspended by sheet-copper
from strips
of wood
above. One of the copper strips,
bent below
-

~=dtiii!^

Fig. 126.

"

Longitudinalseclion

of copper-vat (Siemens).

longer than the other,so that it may be


in Figs.124 and
the wood, as shown
the
with
contact
conductor,
125, and may ultimatelymake
the negativepole of
with
be in electrical communication
and
the dynamo.
of liquid that is so
the circulation
In order to maintain
into

is made

hook,

folded several

times

around

the

to

tubes,so

that

Each

of these

tube,

with

conveying

success

the whole
rakes

arrangement

process,

resembles

communication, by

means

garden
of

rake.

rubber

pipe,running along the sides of the vats, and


The supply of liquidto each
solution.
electrolyte

main

the

is in

of

the

whole

is
bath
every
provided with a tube, V (Figs.124 and 126),to the lower side
of narrow
of which
are
attached, at right angles,a number

essential

UNIVERSITY
OF

^m^^mma^mmm^^^

.Sr-gJSIKfe-

mS

"li^'^

222

SMELTING

ELECTRIC

only for

short

AND

time, because

it

REFINING.

led

the

productionof
of stirring
liquid,
found
air was
to be illusory. Yet
were
soon
clearlythe best
for
the
certain
to
a
and, up
stirring,
agent
point,for the purification,
of the liquors,
if it only could be satisfactorily
applied,and
the idea of using it must
undoubtedly be considered one of the
discoveries
in connection
most
with the refiningof
important
The
merit
of solving the problem belongs to Messrs.
copper.

turbid

K.

and

so

H.

Bros. ; and
method

bath

131."

On
that

to

above-mentioned
should

be

firm

observed, is

of Borchers
not

patented.

carryingit into efiect will Ije first described.

Siemens-Borchers'

fitted with

132.
seen

of

soon

advantages of this method

Borchers, of the
this invention,it

The

Fig.

that the

Borchers'

copper-

vats

section).
(longitudinal

is shown

Figs. 131 and


comparing these with the previous figuresit will be
there has been practically
no
change in the arrangement

of the electrodes.

pipe,b, which

passes

apparatus

But

there

downwards

has

from

added

been
the

beneath

in

upper
the

wide

surface

leaden
of the

of the space
the very centre
mud-depositing
this
within
and
is
out to a
a
tube,
glass
pipe
g, drawn
tray, 8 ;
tube
The
is
fine jet at its lower extremity.
passedthrough
glass

liquidto

stopper in the
and

lowered

in

is

leaden

cap,

d, by which
that

so
arranged
position. A current

it may
of air is

the

tube, 6, is

easilybe

raised

mounted,
suror

continuouslyforced

223

COPPER.

through
with
as

the

it

the

glass tube
that

result

rises

the
a

it mixes
into the vat, where
overflow
electrolyte.Meanwhile, solution from
bath

is

constantlyentering at

small

pipe,b,
bubbles

gravity of the
specific
portion of the liquidto
with
the

bottom

the

the

liquidin

air,dividing itself into

surface, lowers
tube, 6, and causes

of the

contents

the

the

to

of

into the column

the

lowest
of the

bulk

of the

level

of the

tube, 6.

The

It^

Fig. 132.
of

aeration

Siemens-Borchers'

"

electrolyteis

the

at the

uniformly,whilst
air affords
the

the

most

liquid.

the notice

of the

thus

and
practical

eflected
the

time

same

very

method

economical

of

quietly and
applying the

means

ing
of circulat-

itself to
therefore commend
process would
the
latter
if we
refiner on
ground alone,even

The

the advantages to
disregard
of the

copper-vats (cross-section).

air,which, however,

be derived

must

not

from

the

chemical

action

be under-rated.*

Engineering and Mining Journal^ 1896, vol. bcii.,


desirable,in practice,to assist the circulation of the
in the course
of a day, by causing a
to three hours
for two
electrolyte
plished
general circulation from vat to vat, in addition to the air-mixing accomby Borchers' device." Translator.]
[According

to

p. 603, it is found

the

224

ELECTRIC

SMELTING

glance at Figs.131
portion of
the
solution
distributing
inconvenient

AND

BEFININO.

and

132, suffices

the

older

show

to

that

^the "'rake"

apparatus
"

very
for

^has been

dispensed with, and that


of the liquid have
also
conveyance
attachments
of
the
These
tion
installatwo
disappeared.
original
had rendered cleanliness in working the process impossible,
owing to the constant and unavoidable
splashingof the solution ;
while
time
at the same
to the
they prevented ready access
the

side

channels

electrodes,and
whole

the

for

installation

fact,the

in

were,

"

account

on

chief

of the

of trouble

sources

in

the

supervisionthat

constant

they demanded.
Details

plant,as
baths

the

of

present used, both

at

In the
Installation."
and dischargingof the
the filling

SiemenB-Borohers'

effected

by

singlepipe,R (Fig.131, and Plate II.,


for all at the
Figs.133, 134, 135),the former being done once
and
the
latter
of
a
beginning
refiningoperation,
being necessary
only when the impure liquorshave to be run off at the end, or
as
required. This is in strikingcontrast to the older system,
are

necessitated

which

through

the

connected
attached
of the
there

to it

by

process
be
may

Plate

series

the

circulation

constant

whole

with

of

Every

vats.

main

electrolyte

individual

is

vat

a
pipe, R, by means
siphon, N,
tube, S (Fig.132). During the working
tube,S, is closed by a screw
clamp, so that

of

rubber

this

electrical communication

no

the

of

between

the baths.

previousplate,is concerned
mainly with
the method
the solution,and
with
of circulating
the general
struction
plant,the details of bath conarrangement of the electrolytic
been
shown
and
scale
in
131
on
a
Figs.
having
larger
132.
In the new
installation
a
compressed-airchamber, D,
effects the conveyance
of the bath-liquor.In startingwork
the
allowed
i
n
into the
to run
placed originally A, is
electrolyte,
forced
is
the
whence
it
into
D,
vessel,
vat,
distributing
pressure
flow
the
the
the
and
that
vats
it
to
V, so
through
pipes,R,
may
The
siphons,N.
liquidmay be dischargedfrom any given vat
the
during
by drawing it into the pressure kier,D,
electrolysis
through the siphons,N, and the mains, R, so that it may be
treated either for the recovery
of its salts or by cementation
or
which
in
regeneration. Any solution
consequence
escape
may
of leakagesin the vessels or conveying pipes,or through irregularities
in the working of the vats, is conducted
through the
beneath
the flooring),
into the tank, B, whence
drains,G (placed
it may

The
a

II.,like

the

for re-distribution.
pressure chamber
for the washing of the anode slimes have also found

be conducted

vats, C,

placein

this

Siemens

warmed,

"
the

room

Halske

the

under

the

that

being

antimoriyand
of

present arrangement.

recommend

conditions

of
precipitation
Pmiflcation

to

Old

then

the
more

bismuth

Iiiquors

from

solutions

should

be

for

the

favourable

compounds.
Bismuth

and

Anti-

5^

[To face p. "A.

-^^".

__^wt^'

'^*^';:'"''^'^"?**^^^P!J^^^p^

226

ELBGTRIC

''

this table it is evident

From

new

sunk

the actual

that

of

cost

refining

20 per cent, through the introduction


by
the capital
and
since
the interest,both on
process ;
buildingsand site,and on the silver in the anode

reduced

has been
of the

REFINING.

AND

SMELTING

in

about

copper, will also be reduced, the actual comparison is even


than
in favour of the application
of high current-density
from

appear
"In

introduce

to

the

works, either
have

the

improved

into

process

present baths, after the


in them, may
be used

existing

alterations

necessary

produce a higher
by increasingthe power of the engine and
be employed with a smaller
same
power
may

made

been

table.

the above

order

more

would

of copper
dynamos ; or the

output

to

diminished
outturn, but
electrolysing
plant and a somewhat
of
with a higher efficiency
three-quarters
; in the latter,about
the
so

rendered

available

the former
The

purposes.
will prove more
advantageous."
of Siemens
" Halske, in a communication

ZeiUchrift fUr
of

EUktrochemiey

the invention

of Borchers
and

was

tube

into

inner

tube

shown

was

sunk

by

of

means

refineryin

Borchers

solution
Bros,

from

themselves

to tank

this

introduced

in

into
an

as

the
air-

for circulating

electrolytic
the

in

started

of

double

means
an

or

first

copper

the

copper
in the earlypart of 1891 ; but
effected by the overflow of the

case

and

firm

same

Bros.* works
in this

was

tank

The

number

blown

was

beginning of 1886
they were
laying down

Heckmann.

the circulation

used

the

at

The

engine working

Halske

air

1884

in

'Geyser Pump.'

steam

Siemens

refinerywhich
of C.

as

to

use

of the

lation
of air circu-

raisingof water.
actual

von

members

Siemens

von

well-shafb,and

the solution
copper
works

in

known

injectorpump.

Werner

for the

ihe

circulation

the

this kind

**

to

Werner

for
the

to

that

state

Dr.

used

then

was

plant installed
engineers,and
was

by

Borchers

by

They

discovered

was

1885,

Bros.

claimed

have

of air to
application

of the

ascribed

solution,above

firm

for other

set

alternative

firm

Siemens

free,and
Generally,however,

will be

baths

the

occupiedby
originally

area

not

the

by

means

system

their

of air.

Borchers

of air circulation

into

it did

not
plant afterwards; but, as applied by them,
works.
At a later
appreciablydiffer from that in Heckmann's
date the arrangement
was
considerablyimproved by W. von
and
baths
Siemens,
wa"^, after his death, appliedto electrolytic
of very different descriptions."
Borchers
be the
that while
writes
obviously there cannot
doubt
the accuracy
of the above statement, it must
on
slightest
be overlooked
that the plant actuallyinstalled by Siemens
not
ik Halske
in the works
of Borchers
Bros, was
not
provided

with

air circulation, but

themselves

recognised

system, and

that

they

originaldesignersof

did

the

the contrary, the latter firm


advantages of, and applied, the

that, on
the
so

without

plant.

any

suggestionfrom

the

227

COPPER.

The

method

of work

described

above

and

the

undoubtedlypossess

reasonably be

may
installation
access,

exclusion

advantages which
well-plannedelectrolytic

from

control
far

in

all

apparatus

all the

a
expected
of arrangement,
namely, simplicity

"

and

of the

construction

parts, cleanliness

convenience

in

of

operation,and

work
of a disturbing
possibleof all intermediate
sufficed
have
limit
the
to
account
might
of copper refiningto that alreadygiven, and to recommend
the
for universal application,
but certain
system of Siemens-Borchers
as

as

It

character.

other

works

above

must

which

differ in

also be

described.

[Beforeproceeding to
however,

be

it may

the

many

ways

from

those

described

of

these

processes,

consideration
that

worth

in

American

noting
practice
much
than that employed in
is used
a
higher current-deusity
than
lower
10 amperes
Europe; it is rarelymuch
per sq. ft.,
that amount.
In conseand, in some
quence
cases, is nearly double
of this the turnover
is greater, and the cost of refining
the
fixed charges are
is correspondingly
as
reduced, inasmuch
distributed
over
a much
higher tonnage of refined material,and
locked
the interest on
in the vats is
capital
up in the copper
also

diminished.

and

this

whole

at a lower
cost,
process is worked
for
the
for
higher charge
compensate
wages.
Tsee
Works
the average
at the Anaconda
wages

The

helps to

Thus, although

that
232) is about $3 per diem, the cost of refining(including
whilst
is
the
silver
only $14 ("2, 18s.)per ton,
mud)
treating
Perth
at
Amboy (New Jersey)it is stated (exclusiveof office
expenses) to be $9 ("1, 17s.)per ton, as against 59 marks
("2, 19s.)per ton in the table given on p. 225. The charge for
labour at Perth
Amboy is less than half that at the Anaconda
that in (Germany. Hence
but
is
still nearlydouble
it
Works,
the gain in applying the highestcurrent-density
that can
be
the
the
of
without
endangering
deposited
safely used,
quality
copper, is emphasised as stronglyas by the figuresquoted in the
table (loc,
Above
cit). Translator.]
p.
of

"

and
[Schneider
similar

XJnited

States

to

by

Szontagh
that

of

System.

Borchers,

Schneider

and

"

has

system

been

of air circulation

patented
The

in

the

method

of
Szontagh.*
pipecommunicating with the
the same
is practically
; but,

introducingthe air into a vertical


electrolytetank above and below
the centre
of a
instead of taking off the liquid from beneath
draws
in
horizontal
it
it
a
perforations
through
pipe
tray,
running along the whole length of the vat at one of the bottom
Angles,whilst the solution overflowingfrom the uprightair-pipe
horizontal
pipe,which is placed along
passes through a second
From
this pipe it is
the top of the vat on the oppositeside.
delivered into the tank through perforations
pierced between
diameter
of
a
nd
in
as
each pair
electrodes,
they are
increasing
"[U.S. A

Patent

663,093, June

30, 1896.]

228

ELECTRIC

farther

SMELTING

from

removed

the

vertical

greater uniformityof flow.

refineryof
"

Messrs.

AND

The

REFINING.

pipe, in

is in

system

Guggenheim

at

order

Perth

use

Amboy,

to

secure

in

th^ large

New

Jersey.

Translator.]

of the
According to the account
be distinguished
Thofehm
process publishedby Hering,* it may
either
from all others by the use of very largebaths,for which
be
wood
lined with lead or concrete
ployed.
empainted with tar may
2 metres, a length of
The baths have a width
of about
I *5 metres
3 metres, and a depth of about
[6^ ft. x 10 ft. x 5 ft.].
that adopted in the
The
form
of the anodes
is the same
as
of
Moebius
for
treating silver,!and the method
apparatus
viz.,by hanging
suspending them in the bath is also the same
baths each
In Thofehm's
several small platesfrom a metal bar.
anode
rod carries three plates0*6 metre
long by 0*6 metre wide
002
2
thick
ft.
ft.
metre
x
x
by
| in.]. The cathode consists
[2
six are
of copper
of which
hung on every rail,each one
plates,
being 06 metre long by 0*2 metre wide by 0 0002 metre thick
tion
[2 ft. X 8 ins. X 0*008 in.]. A diagrammatic sketch of the posiused
in conveying the current
of the conductors
to the
supporting rods for the electrodes is given in Fig. 136. It will
The

Thofehm

Prooess.

"

"

Fig.
"

136.

"

The

electrical connections

recognisedat once
appliedin plant laid
be

an

old

arrangement

down

for black
sq.

aqueous

copper
metre

apparatus.
which

by Siemens " Habke


published. As an
process was
anodes with a current-density
of

of Thofehrn's

account

per

as

of Thofehm's

[2*8 amperes

solution

of 15

sulphuricacid

per

per
cent,

ft.]he

sq.
of copper
50 amperes

had

been

before

any

electrolyte

30 amperes
recommends
an

sulphate and

5 per

[4'6'
per
of
one
amperes
per sq. ft.],
per cent,
copper sulphateand
5*5 per cent, of sulphuricacid; whilst for bessemerised
copper
and
of 60 amperes
current
a
[5*6amperes
per
per sq. metre

cent,

of

or

with

sq. metre

of 20

he prefersa bath containing 25 per cent, of the copper


sq. ft.]
salt and 6 per cent, of the acid.
The circulation of the solution
bath
bath
from
to
is effected with
the aid of siphons,which,^

however, afford

securityfor the uniform circulation of the


An interesting
electrolyte
through the largebaths themselves.
account
was
given by the Engineering and Mining JotMmal, in
no

*Herinff, Berg- und HiUUnmdnniwhe


Industrielle,
1892, p. 24,
t See Chapter on Silver,

Revue

Ztitung, 1893, vol. Hi., p. 53^

229

COPPEB.

of

1896,

in
plant laid down
by Thofebm
and
Oompany,
Mining
designed to

Anaconda

the

works

refine 150

of the
of

tons

per diem.

copper
The

contains an
engine-hotue
ordinarydouble-cylinder
engine
H.P., a Westinghoase compound engine of 400 H.P., and
Each
of the
two
triple-expansion
engines,each of 900 H.P.
latter enginesis direct-coupled
There are
to two dynamos.
two
thus
The
3,000 H.P. provided,but this includes the reserve.
first-named engine is of the Oorliss type, and drives the dynamos
For the work
of the old plant by belt transmission.
lysis
of electrothere
are
provided three Westiughouse dynamos, all
of 220-kilowatt
of
two
belt-driven,
capacity each, and one
four
270
Westinghouse dynamos, each of
kilowatts; and
270-kilowatt capacity,
two
coupled to each of the triple-expansion
engines. These dynamos afford,therefore,1,790 kilowatts,
One
of these
wliich corresponds to 2,400 E.H.P.
dynamos
295
its
with
kilowatts
(220
corresponding steam
E.H.P.)
to any
one
engine forms the reserve; and can be connected
of the other dynamos
of one
of the six circuits in the event
requiring repair. There are, in addition, two dynamos for
of them
one
lightingand power-transmission,
being held in
An air pump
reserve.
absorbing 30 H.P. is used to drive the
acid pomps.
the whole
As
to deposit
plant is constructed
the
that
of
it
170 tons
a
exi)enditureof
day,
copper
appears

of 800

"

"

work

the

is at

done
The

of

rate

17-5

of all mechanical

inclusive

H.P.-hours

work

which,

machines.
by electrically-driven
divided
itself
is
into
refinery

as

per ton
far as

of

blocks,separatedby

two

free space of about


100 ft.,
the
in order to minimise
The buildingsare constructed
covered with
of wood
^

iron ; each building has


and contains
600
about

lengthby
3 ins.

vats,

4 ft. 7 ins.

ins.].In

3 ft. 3

with

is lined

planks,and

compartments separatedfrom

space.

Each

of these

rows

of 10

fire risks.

corrugated
sq. yards

2*5

in

metres

1 metre
in depth [8 ft.
the construction
of these

so

10 vats, is first put


up as to form

divided

another

one

6,500

measuring

and

frame, sufiiciently
large for

wooden

this
together,
10

in breadth

1*5 metres

of about

floor space
tanks, each

copper,

is
possible,

by

sufficient air

is mounted

vats

its

on

own

foundations,
separatedfrom the next rows and from the working
floor. All jointsin the wood
well caulked
with
are
insulating
material.

The

insulated

The baths

are

vats

are

and carry the conductors,


the
of
the
side
walls.
lining,
top
the
known
as the
accordingto
system

lined with

the lead

from

connected

lead

on

Siemens system. The

electrodes are suspended by copper hooks


from flat transverse
iron bars which
the longitudinal
rest on
conductors. The
actual number, size,and
dispositionof the

electrodesare

not

Fig.136a) it

would

stated,but
appear

from
that

the
to

illustrations

every

vat

given (cf.

there

are

16

230

ELECTRIC

rods, and

cathode

8M9LTING

anode

tanks

200

tanks, or

REFINING.

rods, each supporting two or


compartments, each containing 10

15

Two
Btrip-electrodes.
of 10

AND

in all

coupled in

are

each of these circuits is arranged in


mechanical appliancesand
necessary

one

more
rows

circuit ; and
the

one

thus, with

hall,and

generalequipment, forms a^
of
all
the other systems. All
independent
quite
system
baths
in
the
system are coupled in series,and it has
any one
that there are
alreadybeen stated,in the preceding pai-agraph,
of
reservoir
is provided for each row
six of these systems. A
the circulation
from which
of the liquidis ensured, the
tanks
and thence to
solution flowingthrough the 10 vats in succession
the help of
it is again pumped with
a collectingtank, whence
the
kiers
r
eservoir.
to
distributing
pressure
that

three

systems

first

of the

electrodes

was

the

In

removal

is

pulleys.

full load

The

whole

the

of copper,
the three

of

installed,the
effected

by

of overhead

tank

tons

time.

In

to about

amount
may
is introduced

of which

and

introduction

means

at

one

electric

cranes
recently laid down,
work.
The
this
for
rawprovided
[overheadtravellers]
and
in
the vat-room
and fine-copper
through
platesare conveyed
of an electric tramway
of 500 mm.
the works
by means
[20ins.]
The
rails
the
floor
of each
in
to
are
brought
working
gauge.
beneath
for
the depositingtanks
hall,and other rails are run
of conveying the anode-mud
the purpose
to the silver refinery

systems

more

are

attached

to the

works.

Work,

The

first
anode-platesare weighed when
brought into the refinery,and are then suspended by copper
hooks
the flat transverse
from
iron bars already referred
to,
lifted
in
which
turn
of the pulleys or traveller
are
by means
and
cathodes
The
are
dropped into positionon the tanks.
for
anodes.
the
similarlyprepared
Finally
suspension between
Method

of

the solution
the

is

"

into the

run

electric circuit.

The

tank, which
work

is then

of

connected

up in
cleaning up, and

emptying,
It is
requiresa little less than an hour.
to point out
that the process of emptying a
tank is similar to that of charging it,but in inverse order.
The
anode
material
is black copper
containing 98 per cent,
of copper, with small quantities
of arsenic,antimony, selenium,
re-charginga vat
scarcelynecessary

tellurium,iron,and
0-GOl

lead,and

about

gold [110 ozs.


per cent,
In order to control the work
of

from

set

every

of five tanks

0-35 per cent, of silver,and


Ag and ^ oz. Au per ton].
of depositing,
leads are taken off*

to

measuring apparatus

the reading once


automaticallyregisters
each

series

of "ye

commutator,
series

of ^ve

oppositeends
are

tanks

in such
vats

of
all insulated

one

is connected

way

that the

joined up

are

diameter
from

one

of

to

the

another.

an

up

hour.
to

To

kind

of

dynamo

oppositepoles of the
nuiial

which

effect this

same

platesat the
These
commutator.
plates
A
with
two
yoke-piece
copper

Mi

r
I
i\

)'

4.^.\
Jigitrzed
by

232

ELBGTBIC

8MBLTINO

AND

REFINING.

around
the commutator
brushes, diametricallyopposite,is revolved
the
brushes
connected
and
to
once
an
are
an
hour;
voltmeter, so that each series of five
automatically-registering
is

vats

the

up to the latter instrument, and


the terminals
of each of these

connected
individually

slope of potentialbetween
is therefore
registeredseriallyonce

series

is thus

manager

that
irregularities

Conditiofu

of

able
may
Work.

to

detect

remainder

of the

to

hour.
The
every
locate preciselyany

be
"

taking place.
The
refineryof

Mining Company yieldsfrom


The

and

the

100 to 120 tons

Anaconda

Copper

of copper per diem.


80 to 100
to about

amounting
produced by this Company is refined in Baltimore, so that
the dailyoutturn
The refinery
200 tons in all.
about
averages
above
described is now
so
arranged that, in case of need, the
whole
of the daily production of the
Anaconda
Company
could
be treated
there,with the addition only of the necessary
dynamos.
In regard to the cost of the work
of refining
in Anaconda, it
about
reckoned
that
the
12s.
be
($3)for each
may
wages
average
had
man
furmerly cost from 228. to 24s.
daily. The fuel used
boilers
have been arranged to run
but
the
ton
new
($5.50)per
;
6d.
with a coal costing 8s. to 8s.
($2)per ton. Sulphuric acid
tons

copper

"

"

"10 per ton.


assumed
It may
be generally
that,in
dustrial
in
the inall
about
twice as high as
are
Anaconda,
expenses
The
States of America.
total
of the "astem
centres
about

costs

of

cost

refiningis placed at $14 (nearly"3)

per

ton

of refined

metal.
There

are

120

men

employed

in

the

works, including the

The
foregoingillustration (Fig.
assayers, and clerks.
of
labour in a modern
show
the
to
plant.
136a) serves
economy
The older existingbuildingswere
not strong enough to carry all

foremen,

the

but the new


labour-saving
appliances,
plant was put
down
Both
according to plans prepared by Thofehrn.
plants
of
about
turn
50
out the same
tons
quantity
namely,
copper
diem
but in the old plant 50 men
are
employed as against
per
this
25 in the new
and
must
certainlyefiect a great
portion,
modem

"

"

economy
The

in wages.

of the electrolyte
is only effected with a view
purification
the
the
of
anode
keeping
proportion
impuritiespassing into

to

solution

within

certain

limits ; but

the works

indication

chemicals

in addition to air.

givesno
saying that it is simple,and
The

the writer

as to the method
calls for the use

of the

account

of

employed beyond
only of inexpensive

monthly productionof gold is 46 kilogrammes, 0*950 fine;


silver,10,886 kilogrammes,0*999 fine.
The washed
anode-mud
is boiled with acid by means
of steam
after the piecesof copper have been removed
from it"and is then
tiltered and washed.
Compounds of arsenic and antimony are
and

of

234

ELECTRIC

copper when
been
detached
It is said
those

BM^TINO

they have
the

prepared by

wires

the

BBPINIKO.

depositedan

been

the cathode

from

that

AND

are

thick

inch

cylindersmay
15

over

direct.

stronger than

cent

per

have

and

be rolled

old

electrolytic
refiningprocess followed
of such an electric refining
of
for
the
drawing
wireor
required
rolling
mill is $16 (J"3,
68.)per ton.
distinct advantage in the use
One
of these jetsis obviouslyto
be found
in the certaintythat the electrolyte
at the surface of
the cathode
is constantlyand thoroughlyrenewed, so that a very
much
be employed than would
greater current-density
may
otherwise
be possible. No
details whatever
ing
are
given concernthe process, and it is therefore impossibleto criticise it.
It

by fusion ; and that the expense


the metal
to produce the bars

be noted that the same


may
paper states that white metal anodes
with
been employed in this
75 to 80 per cent, of copper
have
but
hint is given as to the manner
in
no
process with success,
which

difficulties that

inventors

been

have

Baritan
The
be made
to an

installation

baffled

have

obviated.

of

previous

Plant.
Finally,reference may
Addichs"^
of the electrolytic
by
"

account
given
newly-erectedworks

of

attempts

Tbamslatob.]

"

Works

Copper

the

the

belonging to

Haritan

Copper Works, on
Amboy, New
Jersey [U.S.A.].The works are designedto produce from 5,000
of electrolytic
to 6,000 tons
to
copper
per month, in addition
from
The
7,000 to 8,000 tons refined by the furnace process.
ft.
contained
200
is
in
a
by
electrolytic
buildingmeasuring
plant
includes
electrodes
600 ft.,
which
and
the
1,600 depositingvats in
are
arranged on the parallelsystem, whilst the baths are placed
in series.
used only for the electrolytic
180 of these vats are
productionof the originalcathode-plates.These are prepared by
depositingcopper upon rolled copper platesabout 4 mm.
[0*15in.]
thick.
In order
of the deposit the
facilitate the removal
to
platesare smeared lightlywith tallow,and are then clamped in
wooden
frames, so that the edges may remain free from deposit.
In about 36 hours the depositwill be sufficiently
thick to allow
of it being strippedfrom both sides of the plate; the sheets are
then sheared otf straight
bored by suitable tools
at the edges and
to take the suspension hooks.
The cathode-plates
so
deposited
then carefully
mallets
are
straightenedby strikingwith wooden
of
and
cells
the
in
or
are
blocks,
electrolysis
by means
suspended
the

hooks

copper
with

the

thick

from

copper
conducting bars

bath

in the

for

for further

the well-known
Each

Raritan

vat

The

treatment.

pattern, with
22 anodes

is about
"

which

conveying
days, by which

seven

contains

density used

rods,

Mineral

150

Perth

river,at

serve

the

time

anodes

mnke

to

current.

are

they

are

made

side supports.
and 23 cathodes,
and

amperes

per

sq. metre

Indrntty, 1900, vol. ix,, p. 261.

contact

They remain
sufficiently
accordingto
the current-

[15 amp.

per

235

COPPER.

ft.].The

sq.

and

main

conductors

consist

of copper

amperes,
The depositing
vats
into two
therefore

for the

of 4,000
current
a
carry
cross-section.
4
ins.
in
1^ x

can

bars

each series divided


arranged 400 in series,
which
the
of
electrolyte,
circulating
purpose
are

200

passes through
facilitate the circulation

tanks

in

tanks

double-terrace fashion, sloping,/^-like,


away
central

side from

feed-pipe.
regulatethe proportionof

In order to

each group
of 400
with it. All these
side of the

one

placed in

are

each

on

order to

In

succession.

liquid the

the

of

lead anodes.

becomes

smaller

main
It

vats

well

in copper as
anodes]proceeds,and these
the

be

be

placedin

the

small

tanks
But

at

annexe

with
electrolysis

electrolyteusually
deposition[withcopper
with
in

as

used

well-ventilated

separate and

small

for

the

of

copper.
of gas, the tanks

brisk evolution
a

that
work

of

excess

used

are

known

richer

to reduce

placed in

are

building,and
is

copper in the electrolytes


tanks
connected
in series

Iihs 8 small

tanks

lead

doing

anodes

serve

there

so

must

for tlie purpose

must

room.

In the main

is maintained
at
depositingplant the electrolyte
id"
and
this
of
is
a temperature
C,
accomplishedby pre-heating
the liquidwith steam
reservoir
of
in the distributing
by means
coil
lead
the
of
vessels
for
a
are
provided
separation
pipe. Special
of the tallow

that

from

part

of the solution

which

is used

for the

these
electrolytic
production
cathode-plates.
vessels contains
which
does not reach to the bottom.
a partition
The solution
flows through the space beneath
this partition,
of

leavingthe
remain

in

tallow

in

circulation

Each

the

the

first

The

compartment.

several

for

montlis

before

becomes
purification

The method
of
necessary.
referred
will
hereafter.
be
to
impure electrolytes
Conneotions

of

forms of anode
the

Eleotrodes.

reference

was

advantages of
baths
are
placed

baths, the

Every two

In

"

made

to

which

of

solutions
process

working

up

of
the

treating of the various


system of connectingup

must

be

at

once

apparent.

closelythat the
cathodes of the one
bath and the anodes of the other are suspended
ftt"m a common
conducting bar. [Compare Fig. 149.] Apart
from the fact that in this way
conductor
is dispensed with
one
for
the
bar
middle
two
be
of considerably
baths,
every
may
smaller section than the leads conveying the main
to and
current
from

the

cathode
of the

baths,

of the

side

by side, so

for

the current
it conveys
direct
In
first bath to the anode of the next.

from

the

the works

the
Smelting
RefiningCompany,
side conductors
are
IJ ins. thick,the middle strip is only \ in.
a
nd
This system of
is
than the others.
thick,
slightlynarrower
connection was
adopted in connection with the so-called Marchese

Guggenheim

and

where

system at Casarza."^
"

Compare

p. 247.

236

ELBCTRIC

SMELTING

SERIES
The

Stalmann
made

been

SYSTEM
Prooess.
foundation

the

electrodes,which

has

and

with

in

some

plates.

AND

cases

Schnabel'^

REFINING.

REFINING.

OF
The

"

of

voltaic battery has


oi-iginal
another
system of arranging

into

come

the stated

describes

in

use

varioas

of these

one

methods

he

has

it in

seen

Without

U.S.A.

difficult to believe
should
have found

in the

use

testimony

that

this

StalniRDii's

shown

apparatus
being taken

to

and

inconvenient

in

work
practical

be

electrode

states

Montana,

at

been

have

very

arrangement
; but

Fig. 138.

Fig. 137.

been

it would

most

favour

any

Works

Anaconda

this

(in which,

used),and

are
however, specialseparate cathode-plates

that

modifications,

economising cathode

objectof

as

it has

Fig. 139.

connections.

it will be necessary
the
to describe
possible,
method
this
the
at
account
shortly
point,
the patent specifications
of Stalmann,t whose

the

from

it is.

process
Stalmann

couples the electrodes of each individual bath in


and then cathodes and anodes
series,suspending an anode first,
in
until
united
at last a cathode-plate
ends
alternately,
pairs,
the

whole

series.

The

connected

immediately
joined up in series

are

The

"

to

139.

In

the

with

details of the electrode

Figs.137

in

first anode
with

and

main

other

the
leads

baths

connections

arranging the

last

cathode

of the

are

circuit,or

similarlyarranged.

in the
first

bath

pair of

are

shown

electrodes,

C. Schnabel, Handbuch
der MetaUhiiUeiikunde,vol. i.,p. 270 (18W).
t U.S.A. Patents
467,350 and 467,484, Jan. 19, 1892.

23r

COPPER.

the

either

k^ is fastened directlyto the anode, a


cathode-plate,
with a cathodeeach
anode-plate,
(Fig. 137),or
a, is connected
of a wire or by the short copper bars,v, lying
plate,k^ bj means
the rim of the vat (Fig. 138), or, finally,
the anode, a, is
on
united
shown
in Fig. 139, with
to the cathode,ky in the manner
material
of
a
i,
plate,
insulating
separatingthem, so that only one
side of each

in contact

plate comes

Fig. 140.

"

Stalmann's

with

the solution.

last*

(cross-section).

vat

copper

The

The

pairsof electrodes are suspended


adopted in the older systems. If
attached
the electrodes
to supporting arms
not
are
by screws
the
shown
in
with procast
as
anode-plates,
Fig. 138,
a, are
jecting
lugs,X (Fig.140),by which they are supported on the rim
The
of the bath.
vats (H and
electrolyte
H^) are double, one
being placedwithin the other, whilst the interveningspace is
filled up with paraffinwax,
tar, or
material
similar
other
; they are

named

made
is

of
wooden

walls

to

of the

after the fashion

wood,

provided

of

is the latest.

method

in the baths

and

with
internally

studs, F,
prevent

electrodes.

any
The

its

on

fllEE-

vessel

inner

the

series
side

displacement Fig.141.

"

Scheme

connections

connections

in

of electrical
Stalmann's

vat.

of
will
the

the
be

electrodes

and

understood

on

first anode. A; the

double

electrodes.

conductors
reference
last

It

what
patent specification
possesses

over

the other

Fig. 141,

to

cathode, and

is not

easy

to

advantages
systems

in

use.

ak

in

the

understand

Stalmann's

which

is

intermediate
from

this

arrangement

238

KLBCTRIC

SMELTING

REFINING.

AND

Frooesses.
Hayden*
Hsydeiiy Smithy and Bandolf
t
his
cathode
all
the
simplifies
plates
apparatus by omitting
except the one connected to the negativewire of the generator.
He joinsup the first anode-plateto the positive
conductor
from
The

"

the

and

dynamoy

platesinsulated
a
plate of
copper

suspends behind
from

it,and

it

from

series of crude

one

another, and

copper

connects
finally

The
to the negative lead.
pure copper
pure
is therefore depositedon those sides of the intermediate

platesthat

turned

are

towards

the

first

the metal

anode, whilst

face
time dissolved
is at the same
from the other sides,which
towards
the last negativeplate. But, unfortunately,
the crude
copper
uniform

which
plates,

always of

are

in structure

; or,

cast copper, are


never
quite
if the electroaes could be obtained

even

the

due
homogeneous, certain irregularities
perfectly

to

of the

like,would

insoluble

unavoidable
the

metal

residue

; there
at

placesthan
in

f_.
^

of

course

h"

T T

the

surface

must, therefore,be

some

formed, which,

to

+--"

111
r"t^^

the

and

Cavities

extend

this

metal
pure
time
to some

thickness)on

the

other

that the pure


is

.L.J...J...1.J dissolved

to

the

surfeu^e ;
then be

must
copper
fact that does

not

connections

in

further

of electrical

Fig. 142.-Soheme

shows

Hayden's vat.

the

emphasis. Fig.

electrical

connections

the

anode-

which

Hayden bath,
cathode-plate.The intermediate

k the

and

as

serve

z,

of

thus

are

deposited (by

time,

need

the

be

rapid solution

more

others.

at

clinging

cathodes

their

on

in

left-hand

and

anodes

U2
in

ia

plates,
their

on

right-handsurfaces.

[The Hayden
be said to have

introduced in 1886,may
process, which was
been anticipated
in principle
by Hugon

perhaps
in

1884

and

The Hayden system was


at one
time
by Farmerf in 1885.
in
and
in
most
cases
America,
largely
employed
although
very
it is still used in the largeworks of the
it has been relinquished,
Electrical Refining Oo.
Baltimore
It is said, however, that
here
of
is produced in
even
a
large quantity
scrap copper
and
this is of necessitya serious disadvantage.
working it;
in series processes
is often found
in stripping the
Difficulty
from
the
residue
of
the
depositedcopper
previous anode
material ; the labour involved in this process adds considerably
and
it has even
been found
to the cost of refining,
occasionally
economical

more

charge of anode
few

By

this

the

paper

"

sheet

arrangement
instead

of

the

to the

cathode

whole

obviate

To

of paper
rivets through,and

sticking a
a

remelt

to

metal.

back

of each

blackleadingthe

the
upon

with

this,Stalmann

would

copper
the surface

the

next

proposed

anode, fastening

surface
be

has

of the paper.

deposited

of the

anode

upon

oopper.

Translator.]
"
Engineering and Mining Journal (New York), 1892, vol. liv.,p. 126.
t [U.S.A. Patent 322,170,July 14, 1885.]

239

COPPER.

through a right angle,so that a is


Fig. 142 be turned
and if
placed at the top and k at the bottom of the illustration,
between
be
stretched
the
tsanvas
imagined
diaphragms
electrodes,
will be obtained.
fair mental
-A
picture of the Smith
system***
The
diaphragms is to retain the depositof
objectof the canvas
If

below

cathode
If
that

same

A; is at

the

this

and

top

of any

much

more

is

appears

the

The

ions

copper

impurities,therefore,
diaphragm which was

for the

circulation

latter forms

accidental
difficult.

of the

of construction

disturbance

is effected

solution

disturbance

the

of the

the vertical

With

such

however,
often

as

need

no

The

oppositedirection,so
the principleof the

clear.
sufficiently
and

of the

direction.

these

cause

is

in the

underneath,

upwards,

Smith.

horizontal

In both

turned

figurebe

beneath, there

employed by
a

fall u])on the surface


the depositedmetal impure.

render

travel

case

remain
in

otherwise

arrangement t is

Randolf
in

and

the

now

would

which

anode-mud,

is

operation is

the

rendered

trodes,
suspension of the elec-

readilyfound, and

of these

Neither
easilyremedied.
to afford any grounds on

discoveryof

which

very

methods, therefore,

adoption could

its

be

recommended.

[The Multiple
usual

and
of

processes

Halske, Thofehm,
one

tank

latter
It

of

SystemB

such
refining,

copper
and others,in which

as

all the

anodes

now
parallelcircuits,
hung
Multiplesystem, to distinguishthem
are

^The

in any

classed
from

as

the

similar

be

the

remembered
the

that

electrodes

in

these

way

must

and

give the

as
parallel,

to

be

so

refer

terms

single tank,

relate to the connections

which
installation,

of the

grouped in

maximum

The

amount

should

not

of copper
be less than

not

and

with

the
in

in the
of series

the current

interest

in the
the

unfortunate,as

upon

the

baths, as

well

above-mentioned
it tends

deposited under
95

to

do

combination

economy
the

capitallocked up in the copper contained


selection of
in the plant itself. The
as
is,therefore,somewhat

only

different tanks

conditions available,taking into account

system

"

of Siemens-

the anode and cathode


processes, in which
connected
electrical series.
in
The
vat
are
the Series system.
as
arrangement is accordinglyknown

must

names

Beflning.

those

the

dispositionof
any

Series

in

are

belonging to
Hayden and
pairs within

the

the

per cent, of that


the Series processes

to

fusion.
con-

Multiple
which

is

a
theoretically
possible,whilst in
higher
is required for each tank, and there is a greater loss by
E.M.F.
short circuiting
through the mud upon the bottom of the bath
that the electrical
and through the walls of the tank itself,
so
reduced
from
85
90
The
i
s
to
to
cent.
efficiency
capital
per
representedby the copper electrodes is also greater in the case
*

Engineeringand

t U.8.A.

Patent

Mining Journal, 1892, vol, 11v., p. 126"


514,275, Feb. 6, 1894.

240

BLECTRIC

8MELTINO

AND

REFINING.

of the

Series system than


in the Multiple; but, on
the other
hand, the total capitalexpenditure is high^ in the latter case.
Kroupa states that, weighing the costs of the two processes one
against the other, the balance in favour of the Multiple system
8s. 4d. per ton of copper, a difference which
is quitesufficient to account
for the substitution
of this system
for the series in so many
of the works
in which the latter had
works

at about

out

tried.

been

Translator.]

"

The

of the

arrangement

Company

the

on

the view

Multiple system,

Mining

above

described,supports
system has not, in practical
use, shown
the Multiple system.
as

that the Series

over
superiority

TREATMENT
the

From

IMPURE

OF

the

descriptionof

is clear that there

above, it

which

anodes

of the Anaconda

works

new

these

that

of

electrolysis,
given

substances

present in the

copper, and
and it will be
electrolyte;

the

in

render

may

phenomena

are

many
solution
with

into

pass
graduallyaccumulate

ELECTROLYTES.

the

continuance

which
stood
under-

of

possible
imelectrolysis
good qualitiesof the
in largequantities
in

of the

danger to the
their presence
by
depositedcopper
bath.
such
But
the
solutions,although unfit for further use as
contain
metals
too large a proportionof valuable
electrolytes,
allow
their
of
with
to
the
being run away
(including
copper)
account

on

caused

of the works.

waters

waste

of the copper
of metallic iron,
by means
precipitation
referred
need
not be treated of here.
to,
althoughvery frequently
There is no lack of ferrous sulphate(ironvitriol)
as a by-product
and
in
of metallurgical
most
works,
cases, indeed, it is scarcely
The

saleable.
which

There

aim

at

is

be said in "vour

to

more

of the

the

recovery
of copper sulphate.
which
of works
In the case

of those
from

copper

processes
the solutions in

the form

constantlypassingthe
recommended
solution
BJxd

air

should

the

matter

with

fresh

any

one

There

tank

two

are

treatingthese
system,
from

and
liquid,

the

is aimed

to

attempt

in

at the

several

replacethe
from

solution

use

is made
in the other

at, in order that the

to the baths

the

principaland

solutions

the

from

time

tanks
whole

as

entirelydifferent
recover

the

the

removal

are

thus

In the

copper
of the

purifiedelectrolyte
may
first opportunity.

required.

systems

in different works.
to

time,
which

separate, it is
of the liquidin

to time

time

to

In works

and
promoting circulation,

liquid in

keep
obviouslyan easy

be withdrawn

sulphatesolution.

pure copper
the agent for

as

closed system of circulation,

liquidthrough the baths, it is to be


portion (generally20 per cent.)of the

in circulation

to

same

by
replaced

employ
able

that

use

of
one

sulphate
impurities

be returned

242

ELECTRIC

the

liquor,after crysUlliungout
should
be again conoentrated

REFINING.

AUD

8MBLTIKG

bulk

of the

copper sulphate,
by evaporationin lead pans, such
of sulphuricacid.
used for the ooncentration
as
are
During this
evaporationprocess the solution exposes a large surface at a
high temperature to the action of the air,and the
comparatively
When
iron salts are therefore readUj oxidised and precipitated.
the solution has attained a strengthof 55* B6., it is run
through
of
the remainder
cooling apparatus into settlingtanks, where
the copper sulphatecrystallises
out, and thence into precipitating
with the
and
which
in
arsenic
are
tanks,
precipitated
antimony
has been
aid of thiosulphate,
after the solution
again diluted.
the
The
of
thiosulphateproduces free sulphur,
decomposition
which

for the

mony,
with the arsenic and antipart combines
retain
It
is
of
dioxide.
to
sulphur
importance

most

and also
the last-named

again, because

used

the

acid,
acid,and
the

in the

substance
in
of

arsenic
with

the

sinks,for

anode-mud
For

the

latter is to

contain

is converted

anodes

of ferric salts.

formation

if the

which
electrolytes

the

in this condition

bottom

solution

most

be

sulphuroua

into

arsenione

part^ insoluble,to

to prevent the
; it also tends
this reason
the solution should be

thiosulphateis added to it.


of
again,owing to the settling
the sulphide of antimony and arsenic,sulphuricacid is added,
and
the solution,now
stronglycharged with sulphurousacid,is
returned
of the refinery.
to the tanks
cooled
After

much

as

as

possiblebefore

the liquidhas become

of

Treatment

In

Impure

the

clear

Solutions

in the

Chicago

Copper

Chicago Copper Refinery the practiceis to


the mother
concentrate
liquor by evaporation,whereupcm a
mixture
of copper sulphateand arsenious acid crystalcrystalline
This mixture
treated
Uses out.
is then
with
just sufficient
Belinery.

"

the

the acid ; and the


resultingcopper sulphateis then put into use, whilst the solution
the original
from which
crystalshad separatedis treated for the
water

to

re-

dissolve the

former

productionof sulphuricacid.
According to the statement

of

Ulke,

not

above

referred

to, those

and
electrolyte,
of the solution
use
again after the impuritieshave
been
have
not
eliminated,
given very good results in practice.
The objectin most
of these processes is,mainly,the conversion
of the arsenic,antimony, and iron into insoluble compounds, in
the first case
of metastannic
acid,in the second bj
by means
with
and
in
the
third by oxidation
treatment
oxide,
cuprous
In the case
Uown
into the solutions.
through the agency of air
of anode
rich in arsenic,a useful precautionary
copper
very
before
is
0*1
to alloy
measure
per cent, of tin with the copper
casting; the tin is found to retard the formation of arseniates,
and also even
to unite with the arsenic,forming arsenite of tin.
In exceptionalcases, where
cheap water-power is obtainable

processes
the direct

which

aim

at

the

salt,but

of the
purification

243

COPPER.

and

where

there

recommends

cells,in which

is but

sale for copper sulphate,Ulke *


of the solution in specialelectrolytic

small

the treatment
the impurities(chieflj
arsenic

and

antimony) are

"deposited copper cathodes,opposed to lead anodes, by means


which
of a current
is not strong enough to deposit iron from
throws
down
the copper, arsenic,and
the solution,but which
Where
is
available,as at Great Falls,
antimony.
water-power
is not excessive,and currents
Montana, the cost of the current
300
metre
of, say,
[28 amps, per sq. ft.]may be
amperes
per sq.
on

used

with

advantage even

with

copper
copper
and
antimony, and

rich

composition by

normal

The
in

of

ordinaryprocess
thus

solution

depositing

freed from

sulphuricacid, is made
addition

the

used

is then

and

is

in the

anodes.

again
repeated until, at last,the

and

of water

solution

contains

the

to

up

phate,
sulcopper
the process
much
iron

and
electrolysis,

for

arsenic

so

it appears
to be desirable either to separate the iron salts
of copper sulphate.
to work
up the solution for the recovery

that
or

of the
process necessitates the precipitation
This
is
lead-lined
in
covered
impurities.
accomplished

The

above

which
12 (tliree
groups
280
for
refiningtanks.
provided
every
2 mm.
thick,900 mm.
high,and 200 mm.

cells,of

The

lead

are
anode-plates
supportingbars.

copper
the
cleansed

from

the

This

months.

mud

is treated

The

from

the

cathodes

60

to

of copper,

in which

ins.].

part adhere

in

The

ceils

per cent

worked

in

finery.
re-

with

unserviceable,

into

up

the

are

two
every
of copper

once

very
be otherwise

to

to

on

thickly covered

are

impurities,or show themselves


they are melted together and
sorts

40

welded

are

metals
precipitated

contains

36

[008 x

about

are

[metallurgically]
by Bessemerising or

When

other

wide

lytic
electro-

each) are

cathodes

size and

same

cells

four

The

in part fall to the bottom.


accumulated
metallic mud

cathode, and

to

and

of the

of

principal

cake

of arsenic

copper or
mony
antior

because

presence
be of direct advantage
even
may
fusion of certain alloys. The solution,

thus

up

is

or
unobjectionable,

it promotes the
purifiedand made

into the

run

have

in the

become

is the solution

rough
treated

use

either

after

in

the

state and

then

hj working with

darker

the

again used
to

such

an

in colour.

that

extent

Only

of the copper

now

iron salts

until

in this

the
case

sulphate.

cupellationprocess is in
in neighbouring works, the slime,
or
largerfragments of anode in the wet
the

drying it,may
the rich

composition,is

ANODE-SLIMES.

OF

same

screeningout

and

solution

or

in which

cases

normal

for the recovery

TREATMENT
In those

the

decomposing tanks,

accumulated

""thode8

to

German

be

treated

lead which

direct

is there

Elektroehemie,18M,
*Zeitiehrift/"r

on

under

the

hearth

treatment.

vol. iv.,p. 312.

244

ELECTBIC

According
in the

to T.

8M"LTING

RBFIRiyO.

AKD

Ulke,* the dried slimes


of the

refineries

in the lead

washed

are

Lead

Other
Company.
into
other hand,
works, on
briquettes
with lime,and then work
lead
reduction.
But
rich
into
by
up
works
in the newer
American
it is preferredto dissolve out
the copper, together with
arsenic, antimony, and the bulk of
the other impuritiesby means
of sulphuricacid in the presence

Pennsylvania

the

make

slimes

the

of air.t
of Anode-mud

Treatment
Electric

Heflning

Electric

in

Company.

of the

In the works

"

Refining Company,

WorkB

the

the

slimes

Baltimore

of the

Baltimore
in

treated

are

lead-

hours
with
dilute
tank
for from
wooden
two
to three
sulphuricacid (1 part of acid to 4 parts of water) and air,the
lined

being blown into the mixture in a continuous stream


by
of a Korting'ssteam -jet injector. In this short period,
means
the whole
of the arsenic,togetherwith the bulk
of
practically
then
The
the other impurities,
liquid is
passes into solution.

latter

allowed

to

settle,after which
now
mud, which

the

clear

solution

is drawn

ofiT.

residual

only contains lead sulphate,


and antimony, is
quantity of bismuth
and
fused
the
hearth
of
a
washed, dried,
on
refineryfurnace,
where
it forms
small
a
slag containing
quantity of brownish
about
20 ]"er cent, of lead and
10 per cent, of antimony. This
is broken
slag is drawn off,and, after solidification,
up in order
and
the greater part of the enclosed
to recover
silver granules,
The
lead
is then treated with
takes
lead scrap in the refinery.
the
silver
and
gold still remaining in the slag,and after
up
until
60 per cent, of silver,leaves a slag
it
carries
enriching

The

tellurium, and

so

that

poor

small

it may

of lead

recovery

from

the

smelted

products.
molten

is thrown

upon
is so rich

that

be

the

metal

element, the refineryof


removed,

obtained

in tellurium

this

the silver is cast

as

been

the

drawn
with-

above-described,nitre

slag thus

The

if there

were

duced
prosale for

any

would

works

one

for

furnace

first slag has

metal.

that

After

blast

the

of the

surface

[6-6lbs.]
daily.
been

in

After

yield 3

grammes
kilo-

this treatment, the slag having


into platesand treated electro-

for the
lytically

separationof the gold. The copper contained


in the sulphuric acid solution
after the
drawn
off the mud
been
has
is
steam-injectionprocess
applied, precipitatedby
of scrap iron,cast into bars,and
means
placed on the market
as

crude
ProoesB

Baritan

copper.
used

the clear solution


cleaned
bottom

at

the

Copper Works,
the

up,
of the
"

has

been

slimes

tank

and

Engineering and

t Of. Wohlwill'8

Baritan

to

are

which
run

out

of the

withdrawn

received

in

At

the

made,

after

Works.

Copper
allusion

has
tank

been

"

which

is to be

through a plug in the


movable
collecting-vessel^

Mining Jotimal, 1896, vol. lii.,p. 512.


Btatements, pp. 199 to 207 above.

245

COPPER.

they are carried to the so-called silver building. Here


of 8 meshes
to the linear
they are
passed through a screen
retains the largerfragments
inch (3 meshes
to the cm.) which
in which

first

of

the

copper

then

are

from

both
the

sieve

is

washed,

are

with

60

washed

are

and

meshes
and

slimes

the
to

inch.

the

returned

to

the

the

anode-plates. The slimes


into settlingtanks,
run
placed
presentlyrun into receptacles

cast

to

second

the solution

which

latter

sieves

used

melting furnace
passing through
from

The

passed through

residues

The

anode.

are

screen

phuric
building. The slimes are next treated with sulwhile
acid and
heated
of
a
compressed air
by means
coil and
steam
agitatedby paddles,until the copper is almost
into sulphate. The
tion
completelyconverted
copper sulphate soluthe impure electrolyte
is conveyed to the plant in which
is
The
freed
from
worked
into
slimes, now
sulphate.
copper
up
steam-heated
into
are
run
drying
pans, and after drying
copper,
treated
from
40
of silver)
50
contain
to
cent,
are
(when they
per
with lead in cupellingfurnaces.
After cupellation
is complete,
the silver is treated by the sulphuricacid process for the separation
the resultingsulphate
in it ; and
of the gold contained
solution is precipitated,
dried,and fused accordingto the wellThe
residual gold in the sulphate liquorsis
methods.
known
and
fused
to give gold in the usual
dissolved, reprecipitated,
the

outside

way.
of

Summary
in

observed

the

Industrial

important
Eleotrolytio
Copper
more

Containing preciousmetals,otherwise

Beflning

"

consisting

as

Conditions
1.
far

Anodes,
as

"

possible

of refined copper.
2. Cathode-plates,
Consistingof thin

platesof copper electroor


on
depositedon
greased copper plates.
lytically
3. Electrolyte.Solution containing not less than 12 and
not
16
of
than
cent,
more
CuSO^ + SH^O [crystallised
per
copper
sulphate]and from 5 to 10 per cent, of free sulphuricacid. It
is of great importance that the constantly-decreasing
proportion
the ever-increasing
of acid and
proportionof copper do not vary
beyond these limits respectively
throughout the whole period of
The cause
of these alterations is to be found in the
electrolysis.
often passes
action of air and sulphuricacid on the copper which
in considerable
into the slimes
quantities(2 per cent, of the
anode
copper),through dischargeof the cuprous ions thus:
"

lead

"

"

Cu

+
+

Cu

+
=

Cu

Cu.

T
A

small

when
of

proportionof

low

chloride

current-densities

in the

are

cathode-growths,probablyby

the cathode.

is
electrolyte

used, as

it checks

hindering this

of

the

advantage
formation

decomposition

at

246
4.

"

[104*F.]

increase

^An

Temperaiure,

copper.
5. CurrefU^eonditions,

them,

of the

account

on

anodes.

low

strength of the

the
be

fore
there-

and
current-densities,
and

of copper contained
in
their surface of cuproua

discharge on

also

may

40* C

to

up

"

3) from

Copper

current-densities

the

CurrentKlensity 40 to 150 amperes


proportion
amperes
per sq. ft.].The

"

quantityof anode-slimes

(seecondition

ions

temperature

improve

to

[37 to 14*4
per sq. metre
of cuprous
ions is greater with
also the

REFINING.

of

tends

the average

on

AND

SMELTING

ELECTBIC

immediate
formed

neighbourhood of
the

at

cathode

when

the
low

to the

incomplete dischargeof
Ou, and g^iyerise to crystallinegrowths through the action
described above (compare condition
3).
Potential
to 0*3 volt^
Differenceat Terminals
of Bath.^O'l
and
the
the
of
anodes and
to
according
purity
currentdensity
used.
electrolytes
6. FrodtuUe

are

used, owing

obtained.

(a) Cathode

"

(97

copper

99

to

the

of

cent,

per

anode

copper.

)
(d) Copper sulphate
(e)Impure arsenical copper J
Treatment

of

Sulphides

the

from

Ores.

and

pure electrolytes.
Reference
will be

from

and

anode-slime

"

in the

made

chapter on nickel and the preciousmetals to the


of alloysof these metals
with
small
treatment
proportionsof
of other coppertreatment
Although the electrolytic
copper.
has
far led
not
waste
ore
so
or
bearingmetallurgical
productsor
to any great and permanent
success, the experiments undertaken
less worthy of study than
those connected
to this end
not
are
with
the more
fortunate
process of copper refining. The study
of the treatment
of sulphide products and ores
therefore
must
the
of
not
be neglected,nor
the solution
must
problem be
regarded as impossibleon account of a previouswant of success.

Undoubtedly
beset

as

in band

the

it is with
allowed

objectsaimed
available

in

material

that

obstacles,was
themlselves

to

that
be

those

this

in
who

led

of all the

arrangements
as
refining,
types for the

took

were
metallurgists

accustomed

that

matter

following the
they attempted
known

were

of

treatment

the anodes
different
in

direction,
the

into

altogetherdifferent

required
the compositionof
left after electrolysis,
were
an

Both

waff

with

met

away
in electrolytic
refining.Thus

at

the utilisation

first failure

the

and

method

to

anode

an

of

the residue

from

those

treatment

to

of

be

ling.
handthat
which

metallic

anodes.
It

has

been

shown

electrolytic
copper
the

that

in

the

for
preparation of anodes
is commonly used in which

refininga metal
to only a fraction
impuritiesamount

of 1 per

cent,

of the

247

COPPER.

total metal

present ;

consist
chemical

and

be remembered

it most

do

metals, which

largelyof

that

not

take

part in the

reactions of the process, and which


not
are
bnt
the copper,
with
with
only alloyed

combined
dissolved

in

these imparities

chemically
or
simply

has commenced,
the
electrolysis
from
is gradually and
less uniformly removed
or
more
copper
the surface of the anode, whilst a slightinsoluble
residue
is at
first left in its place. This residue,consistingfor the most
part
of the precious metals, copper, cuprous
oxide, lead compounds,
and the like,is very small as compared with the weight of the
it.

Then,

in which

copper

it

was

after

that

dissolved,so

form, and, becoming detached

plate,collects (on
anodenslime

the bottom

at

its

which
hindrance

cling to

to the

progress

part conductors.
But
these are

conditions

but

with

is true

that

the

in

the

mattes, because

surface

purity
quantitiesof imtime, offer scarcelyany
for the most
; they are

work

in the whole
alterable

an

sulphidesof

an

small

of anodes

treatment

coherent
non-

metal

favourable
exceptionally

so

rarelymet

they are
practice. It

dealt with

of

the

the anode

Hence

the

short

of the

from

soon

very

of the bath.
it for

separates in

high specificgravity)as

comparatively clean, and

remains

that

of

account

it

which

course

has to be

material

prepared

from

anodes

are

the

kind

of metallurgical

ores

or

formed

that the metal,


in such a manner
decomposed by the current
and, so
leaving the sulphur behind, passes into the electrolyte,
far as it is capableof precipitation
ing,
obtainunder
the conditions
cathode.
The reactions
the
it is deposited upon
by which
this is brought about may
be left for future consideration.
It is
and
the
well known
that in ores
is
not
mattes
only
copper
has shown
soluble metal to be dealt with, and all previouswork
how
that as few foreign
work
important it is for continuous
are

substances

possibleshould

as

into the
copper
the
most
clearly,therefore,
cogent

There

pass

with

the

are
electrolyte.
of treatment
which
is
arguments againstadopting the method
It
of
in
be
the
here
case
marked
repossible
re6ning.
may
copper
that it is sometimes
desirable to make
test- experiments
the
unfavourable
in
face
of
on
a
even
large scale,
prospects.
But in this instance,costlyinstallations have often been almost
disagreeable
recklesslyefected,with the objectof investigating
less expense.
truths that might have
been discovered
at a much
A continuous
experiment with one, or at least with quite a few,

baths

of the

large scale
sufficed

dimensions

same

and

to show

as

requiringonly
all the

would

about

have
to

difficulties connected

been

3 H.P.
with

used
would
this

on

have
method

of work.
The

Marohese
Miniere di Rame

obtained
sacrifice,

The
Societd, anonima
ProoesB.
di EleUromekdlurgia in Genoa
"

proofof the

Italiana

has, at

di

great

of this method
impracticability

of

248

8MBLTI1IO

XLECTRIC

treatingcopper
H.P.

at

mattes,

their works

test

the

account

which

process

for

this

follows

to

plant,of

to

put

Marchese.*

work

the

given by Badiat

order

in

ascribed

was

erected

they

Casarza

at

REFINING.

AND

the

and

125

some

practical
According to

to

installation

at

:
placewere as
metal (matte),of which the anodes
smeltingof the coarse
were
made, was accomplished in the usual way ; and, at first,a
matte
containing30 per cent, of copper, 30 per cent, of sulphur,
considered
and 40 per cent, of iron was
good. The
sufficiently
shown
in Figs.143 to
used in casting the anodes
moulds
are
"

The

"ig, 144.

Ih
Fig.
Mould

146, which
800

800

for

need
X

casting anodes
further

no

30

mm.

145.

[31^

of matte

Casarza.

at

description.The
x

31^

1^

anodes

ins.].Each

measured
mould

was

provided with a clamp,which served to hold in its placea copper


used
This stripwas
stripthat was to be inserted in the anode.
electrical
the
connection
with
subsequentlyfor making
necessary
here be pointed out
It may
the dynamo during electrolysis.
later
of
wire net
a copper
that,accordingto a
proposal Stolp*8,|
be cast into the block of matte, in order,on
which
to the anode-plate,
stability
give more

should

the

to

is very easily
uniform
dis-

ruptured,and,
*

on

the other

hand,

to

ensure

more

one

hand,

German
Patent 22,429, May 2, 1882.
[EnglishPatent 1,884, 1882.]
vol.
Nos. 40, 42, 44.
t La Lumiire
1884,
xiv.,
Electri^ne^
t Evgineering and Mining Journal, New
York, 1886,

350
The

SMELTING

ELECTRIC

lead sheet

in the

sufficiently
explainthis
The

down

screwed

was

soldered therewith

Eleotrolyte

AND

customary

consisted

instead of being
Figs.150 and 151

of

an

acid solution

of copper

SJ

Fig. 150.
of attachingthe

Fig. 152."

the wood

fashion.

of construction.

method

-%
Method

with

REFINING.

Fig. 151.
lead

to the vats
linings

Section of vats, showing method

of

(Casarza).

circulatingthe

(Casarza).
electrolyte

Fig. 15.3."

Plan

the
showing method of circulating
(Cai
(Casarza).
electrolyte

of vats,
"

"

and

251

COPPER.

iron
and

and was
obtained
sulphates,
by roastinga portionof the ore
acidulated with
extractingthe roasted material by water

sulphuricacid.
which

were

pipes and

The

solution

Fig. 154.

Fig. 155.

"

"

step form, was


of wooden
flowed

the baths,
through
with the
about
brought

circulation

uniform

arranged in

aid of leaden
the vats.

The

channels

through a

Plan of the Casarza

on

the

bottoms

installation.

CroBs-section of the Casarza

depositing-room.

stood at the

^hole

of

gutter to the vat which

highest level (Fig.152),and, passing through


into the next, as shown
length of this vat^ overflowed

the
in

The
of the installation is
Figs.152 and 153.
arrangement
illustratedin the accompanying three drawings,of which
Fig.

154 is the
a

ground plan.Fig. 155

generalview
With

anodes

of the interior of
of such

complex

the
one

and Fig. 156


cross-section,
of the

s.
depositing-room

character,it is obvious

that the

252

ELECTRIC

reactions

which

SMELTING

REFINING.

AND

be of a very
must
placeduring electrolysie
the
of
decomposition
sulphidesof whi"ji
the anodes
are
composed must precede the migration of copper,
iron,or other material capable of forming ions. And this was
supposed to have happened partlythrough direct oxidation and
partlythrough the action of ferric salts,tnus, e.g. :
varied

take

character.

"

Cu^

2Fe,(S04)j

the

Remembering
of
many

blister and

2CUSO4

which

reactions

4FeS04

take

place in

refined

as
a
copper, and
accumulate
the
in
impuritiesgradually

Fig.

puritiesthat

of the Casarza

156. "Interior

here

are

present

in

S.

lysis
electro-

the

result

of which

im*
electrolyte,

depositing-room.

far

greater quantity from

to decide that
the outset, it cannot
require long consideration
be wasted
considerable
a
proportionof electrical energy must
through changes, which take place both in the solution and

upon
It

the anode

itself.

is unnecessary
force

electromotive

It will suffice to

here
that

to

enter

should

point out

that

be

upon

calculation

requiredfor

after

this

of

the

process.

preliminaryexperiments,

that could
1 volt per bath had been fixed upon
the maonmum
as
and on
based his whole
be necessary,
this assumption Marchese
estimate

of the

cost

of

the

undertaking.

But

as

the

account

25a

COPPBR.

(to be given shortly)of the experiencegained by the AktienffeselUchaft


fur BergbaUy Blei- und ZvnkhvUenhetrieb at Stolberg
(Rheinland) will show, the expenditure of power increased very
even
considerably

after

short

Chemialfyfm

time

of action.

/Residue

Solution

plates.

eoniaininq

Sulphur.

h^cipitMle
of

Copper

Cu

S.

mTOKSSKifihU

"

"

Raa MattriaL Marketable Prcducts.

Fig. 157.
In
that

General

scheme

of the Marohese

process.

Marchese'**'

of a nine-daytrial
published an account
in that year with the experimentalplant,but hethe increased expendiof this fact,ascribing
mention
ture

made

was

makes

by

1885

"

Bye-product*.

no

bad contacts
that had been overlooked
of energy
to some
the operator. At that time Marchese
still estimated
net
a
TraitemeiU

clea Mattes
dtctrolytiqut

Cuivrexutes

au

G^nes,
Stolberg^

1885.

254

8MBLTING

ELBCTRIC

AND

REFINING.

75 per cent
capitaloutlay on plant in a factory
upon
of
The
scheme
for the systematictreatment
of this character.

profitof

Fig. 157.
In addition to the above-mentioned
faultsof this system, the
o
f
the
matte
anode-platesis a serious difficulty.
great fragility
ing
Then
there occurred a separationof insoluble and non-conductcavities
small
the
and
surface
of
material
the
on
sulphide,
of the
graduallydeveloped into deep pits during the prc^ess
caused
these
both
circumstances
irregular
electrolysis.And
the Marchese

hy

ores

solution

the

of

of

increase

anode,

and

other

actions

In

place of

the

in

the

in

plates,inferior

the

crumbling
material through

is shown

system

the

formation

of

electromotive

crust

the

prejudicialto

resistance, premature
of insoluble

matter,

of the

process.

working

which

force

had

of the

stoppage
These
written

the

by

three

even

or

the

absolute

work.

remarks

last

plantsit

the

the

for

calculated

been

satisfactoryoperation of
became
to
employ double,
frequently
necessary
that
four times
or
voltage,in order to avoid
sufficient

as

anode

the

of

extraction

have

been

in

1893,*

author,

reproduced from
the

on

paper

electrolytic

direct

metallurgicalproducts. At the same


he gave an
of his own
time
account
experiments with ore and
He added that these negative
in the years 1883 to 1887.
matte
obtained
after a series of experiments lastingover
results were
conducted
with the aid of a 1 H.P.
few
and
engine,
a
weeks,
and
yet they established everything that the later plant of
of

treatment

H.P.

125

The

had

Casarza

at

Stolberg

determined

and

ores

shown.

Installation.

The

"

Stolberg Company
experiments

with

with

also

large
a
plant. Laboratoryexperimentshaving given promisingresults,

plant was
dynamo,

relativelyquickly upon

first run

months

for several

5-volt

150-ampere

mine
deterwords,
either the conditions for,or the impracticability
of,working
and
This
scale.
was
Marchese;
on
a
inspectedby
large
plant
the
doubts
erection
had
been set at rest by Marchese,
then, after
of

or, in

have

as

sufficient

plant of

in 24 hours

was

been

vats, each

anodes

different

to 20 cwts.

It consisted

upon.

of 56

of copper
baths,such

already described,consistingof lead-lined wooden


ft. 2 ins. long by 3 ft. 3 ins. wide
by 3 ft 3 ins.

at

contained
a

distance

15 anodes
of 2 ins.

Stolberg were

and

16 cathodes,

arranged

apart

prepaidfrom

mattes

of three

7
grades of concentration,containing respectively

8 per cent,
*

sufficient to

current

capacityto deposit10

determined

deep.t Each bath


in parallel,
and at
The

with

other

15 to 20 per cent, and

about

to

50 per cent, of copper.

und ffmenmdnnUehe
Zeitung,1893, voL lii.,
pp. 251, 269.
and the followingaccount
of the results of the Stolbergexperiments
taken from an
aooount
are
published,with the sanction of the

Berg-

+ This

StolhergerOeselUehqft,in

the

ZeitMhtyt/Hr Slektrochemie,1894, p.

50.

255

COPPER,

these, the

directlyfor the production of


concentrated
the anodes, the first was
by roastingand fusing
the
third
with siliceous materials,and
was
employed for the
The compositionof two separate
preparation of the solutions.
used
the
for the anodes, is given in the
of
matte, as
samples
variable,a third
following table, and as the composition was
of
column
is appended, showing the average
of a large number
analyses made at a later periodthan the others :
Of

second

used

was

"

SHOWING

TABLE

The

anodes

ins.

COMPOSITION
STOLBERG.

80

were

2 fb. 7^ ins.

the

melted

tank

from

matte

which

moulds.

ins. J.

1^

flow

to

it

The

high,80

cm.

removed

was

moulds

mould

and

wide

cm.

before

into which

it

screw

copper

make
of the

were

into

furnace
the

slowly,as
easilyfractured.
thick

mm.

[| in.

the

bath,

was

bent

the
A

over

might
wooden

in iron

cast

that

so

laid in the

into
The

the

anode,

free end

fastened

and

the

anode-plates
long copper

^ in.]was

of

by

anodes

the

under

their

weightyfor each weighed about


supported upon two stripsof wood placed
own

[O'Sin.]wide

cm.

be attached

to

cross

riveted

to

stripswhich

slats

stripswith

placed above the vat.


ihe negative conductor

each, in
were

The
were

by

80

four

order

laid upon
connections
like those

by
stripsof
cm.

that

they

transverse

of copper
adopted for

the anodes.
The

consisted
of a
clamp
positiveconductor, which
and
rod of about 3 cm.
-2
served
to
so
diameter,
[1 ins.]
electrical connections
To avoid
with the matte.
rupture
to

2\ cwts., they were


in the bath.
beneath them
cathodes consisted of copper plates80 cm.
The
with
1 mm.
[2ft. 71 ins. x 2 ft. 7^ ins. x 0*04 in.],
copper

by allowing
large iron

ground

otherwise

[2 fbb

ladles and

iron
in

thick

cm.

made

pouring,so that it might be cast


penetrated to about the centre.

strip,outside

the

by

sunk

were

sulphidesmight cool very


developed cracks, and were
strip2

They

AT

USED

wide, 4

cm.

of the

out

ANODES

OP

was
electrolyte

made

by extractingthe

richest mattes

256

SMELTING

BLGCTRIC

50

(those carrying about


acid,and

when

ready

for

contained

use

phuric
dilute sul-

copper) with

of

cent,

per

REFINING.

AND

about

27

15 grms. of iron per litre [about4^


and
grms. of copper
copper and about 2^ ozs. of iron per gallon].In order to
the constant
circulation
of the solution during the
the
electrolysis,

of

terrace

form,

bottom

of

Two

and

vats

pipe of 2 ins. internal

Siemens

at 700

and

800

The

volts.

in

revolutions,gave

bath

each

in
current-density

35
x
amperes
about 30 amperes

of 430

current

profitsto
15

005

was

followingresults.
160

kg.
kg.
kg.

140
0-5

per

matte

of

cent,

taining
con-

lead,and

all these metals

recover

he

able

was

only

the

In the ton

he reckoned

of matte

of copper
of lead

at

Fr.

I 3

Fr.

195

at

Fr.

0*25

Fr.

35

of silver

at

Fr.

180

Fr.

90

Fr.

330

Value

But

14

anode

insoluble

because

"

by

and the other two


from the
by direct electrolysis,
residue by a subsequent treatment) he arrived

(the copper
at the

per

estimated

were

Starting with

of copper,

cent,

electromotive

the

process

and expectingto
silver,

of

per cent

the

by

followingway:

20

to

earned

be

the

in

size

twenty-fourhours, were
dynamos, running

and
[2*8amperes
per sq. ft.],
per sq.
force requiredwas
at first 1 volt per bath.
The

in
the

These

metre

Marchese

course

led from

of that next below.


of
dynamos of the CF^^-type,

Halske

"

deposit5 cwts. of copper


produce the necessary current.

to

tate
facili-

other

the

diameter

of

ozs.

vessel to the rim

one

sufficient to
used

above

arranged one

were

28

to

to

of 1 ton

of matte

purchase the
contents

copper

matte

at

taken

were

:
"

Fr. 112*5

per ton,
account, and

into

a clear gain of Fr. 207*5


upon obtainingat once
The interest
per ton of matte, or Fr. 1,383*33per ton of oopper.
locked
of
the
the
in
capital
shape
upon
up
copper in the baths
thus estimated
of 1 25 kg. each in
20 anodes
: there
was
were

he thus

reckoned

weiglitof anode
this represented(inround
numbers,
Fr. 100 per ton) Fr. 14,500. But
the anodes
graduallygave
their copper
he therefore
took
and
auring the electrolysis,

every bath,and as there were


material was
145 tons ; and
at

up
the half of this
Fr.

as

the

baths,the

the average

value

operation,and

so

total

of the
arrived

material
at

the

in the
of
sum

8,000.

Then
But

sum

throughout

baths

58

580

kg. of

since three

of the usual

copper
months
were

marketable

depositeddailyin
required to produce

were

thickness,there

remained

the 58 baths.
copper
in the

plates
baths

26,100 kg. of copper (becausehere also the half of


"iPX
the total copper is taken as an average); and the value of this is
580

Fr.
was

32,000.
so

small

The

percentage of the copper

that it

this calculation

was

is that

an

in the solution

itself

regarded as negligible.The result of


annual
productionof 210 tons necessi-

258

ELECTRIC

under

the

8MBLTIN6

of

oxidisinginfluence

counter-electromotive

that

force
It

then

current.
was
electrolysing
of a reducing agent would
Sulphurous acid was selected

the anodes

with

AND

REFINING.

the

current, and
and

opposed
hoped that
this

eliminate
for the

that it

the

the introduction
of

source

and

purpose,
combine

yielded

so

weakened

trouble.
led into

was

with the oxygen


might
acid.
small
A
sulphuric
experiment
therefore made with a bath containingfour lead anodes of
was
0'37 sq. metre
lead
[4 sq. fb.lsurface area and four copper-coated
cathodes of like dimensions.
The electrolyte
contained
litre
per
contact

separatedthere,and

39

so

form

of iron in the ferrous


14*4 grms.
of copper,
state,
and 9*6 grms. of free
of iron in the form of ferric salts,

grms.
3*9 grms.

sulphuricacid.'*'' The sulphurousacid was obtained by burning


The
sulphur,and, mixed with air,was injectedinto the bath.
E.M.F. requiredwas
the
introduction
not diminished
through
of the reducingagent, but the yield of copper
was
increased,
and the metal was
99*984
of
cent,
per
purer, containing
copper.
A largequantity of sulphuricacid was, of course, formed, and
this extracted
that

much

so

trouble

was

baths.

It should

the

of

use

soluble

caused

then

was

At

apparatus.
but the gases

first the

replacedby
But

ores.

various

be

experimental
furnaces
raatte-calcining
acid
sulphurous
required;

dilute,and

too

used

in the

calciningof

(among others,the
Halske) interfered with

depolarising
agent, was
and

process,

which

set

were

other

in

on

zinc

offer of
the

have

of insoluble
be

cution
prose-

anodes,

regrettedthat

other

have
installations,

not

be

involved

departure from

could

foot
with

would

great

it is to

experiments
through; experiments,however,

Stolbergand

therefore,

were,

circumstances

original Marchese

at

the lines of the


from

in this direction,which
of the whole
plant. The use

the removal
of the

providethe
to

process by
of the work

and

from

patent t was granted for


A
depolarising
agent in 1885.

the muffles

from

Siemens

new

as

that

gases

to

found

were

those

the copper
mattes
salts
in the
of
crystallisation

arranged on

led into the baths

were

by

be added

here

sulphurous acid

largerbath

material
the

the
the

carried

both
depolarisers,
not

as

yet led

to

results.
satisfactory
Before
reference

closingthis
must

the method.
form

be

The

of

of the so-called

account

made
idea

in

passingto the

of

treatingcopper

Marchese

process,
practicaloriginatorof

mattes, either in the


in the granulatedcondition, as anodes
in an

platesor
of sulphuricacid was
electrolyte
clearlyexpressedby Andr6 in
the specification
of his German
patent, No. 6,048,of November
went
1877.
as
beyond Marchese^ inasmuch
1,
Andr6, however,
nickel
he proposed an
electrolytic
separationof copper from
*

oz.

[This

is

equivalentto

of ferric iron, and

t German

Patent

about 6i ozs. of copper, 2| ozs. of ferrous iron,


of sulphuric
acid per gallonof liquid.]

1^ ozs.

32,866, March

13, 1885.

259

COPPER.

during

the

process

will be made
Prooess.

Body's

that

remarked

of the

treatment

Farther

matte.

"

chapteron
working the

In

part of the

current

reference

to this

Nickel,

in the

Marchese
was

used

process, it was
up in converting

ing
sulphate present in the liquorsinto the correspondferric compound, and that this salt again attacked the anode
that more
attention
It was, therefore,only natural
material.
iron
should be given to the action produced by
salts,with the
The
first step in
convenient
it in some
objectof utilising
way.
with electrolytic
this direction, at least in connection
processes,
in a patent granted to Body;**^ but in purely
is to be found
works
the utilisation of iron salts as a carrier of
metallurgical
of
had,
long been known.
Although Body's
course,
oxygen

the

ferrous

apparatus and

alone,but

process

were

with

concerned

not

are

intended

for the

copper extraction
extraction
of metals
electrolytic

Fig. 158.

Fig. 159.
Body's apparatus.

from

in

ores

ibrerunner
and

be

general,they

of the

may
well-known

here

processes

described
of Siemens

as

being
"

the

Halske

Hoepfner.

The

of Portland
(Figs. 158 and 159), is made
without
is paintedwithin and
with an impermeable
cement,
The
material.
partitionwalls,S, which are also of Portland
of the bath ; and in the
cement, do not reach quiteto the bottom
thus
beneath
left
them
material
are
space
placed platesof some
that is perviousto water.
The raised floor is covered
(likefelt)
with a carbon
plate,C, in connection with the positivepole of

vessel,A
and

an

electricalgenerator ; and

of the vessel

are

also

the inner

lined

The
practically
unnecessary.
suspended in the

cathodes,
are

U.S.A.

surfaces

of the outer

walls

with

Patent

carbon, D, which, however, is


metal
plates,K, which form the
space

outside the

338,150,Jan. 5, 188G.

S.
partitions,

260

ELECTRIC

solution

solution,and

similar

REFINING.

AND

of ferric salts with sodium


chloride is used as
been
which
has
previouslymoistened
ore,

The
inner

SMELTING

space,

J,

and

is still saturated

with

is here

constant

kept

stirrer,R.

of the

electrolysis
by means
through the opening,O,
marked

in

it,is

with

placed in

motion

The

the

the

during

solution

floor,follows

in the raised

lyte.
electro-

enters

of

course

the

arrow
S, and,
figureover
partitions,
finally,after traversing the cathode
compartment, escapes
through the aperture,O, in these outer chambers.
While
the solution is thus slowly circulating
the foUowing
reactions take place:
contained
1. The metals
in the ore are
brought into solution
which
of the ferric salts in the electrolyte,
are
at the expense

the

the

in

"

reduced

thus

to the ferrous

2. The

dissolved

3. The

chlorine

state.

is depositedat the cathode.


the
is set free at the anode
peroxidises
chlorine
have
and
been
of
ferrous salts that
produced,
any excess
able to act directly
that may
is
in
this
escape absorption
way
the
ore.
upon
The
and

Siemens-Halske
Halske
then
went
between

reactions
take

metal

which

the

Process.

Matte-Beflning

step beyond

"

Siemens

caused

this,and

the

the copper
compounds to
vessel.
They stored
electrolytic

ferric salts and

placeentirelyoutside

the

in
apeakfthe anode energy in a part of the electrolyte
The process
order that they might utilise it outside the baths.
thus
the
German
taken
in
described
first
out by the
was
patent
upy

80

to

firm.*

powdered copper
pyrites is roasted at a moderate
in a Gerstenhofer
furnace,in such a way
temperature, preferably
that the iron is almost
completelyoxidised,whilst the copper is
the
roasted
contained
in
material, partly as copper sulphate
and
sulphide.
partly as copper oxide, but mainly as cuprous
with
The
treated
after
is
material,
calcination,
finely-divided
the solution flowingfrom the electrolysing
tanks.
This leaching
is best performed in a series of vats, through which
the liquid
flows successively
that it passes last- through
in such a manner
the vat that was
the ore.
The
latest charged with
solution,
which
enriched
is thus
with
sulphate,and no
newly
copper
The

contains

longer

any

cells,where
electrolytic
is then
copper

to

the

deprived of its copper,


be used afresh to extract

and

salt,

it is first

that it may
so
peroxidised,
another chargeof ore.

from

and

owing

ferric

to

the

the

same

solution

absorptionof

in the ore, it has

become

too

is

The
may

be

process
used

foreignmetals
impure

returned

now

is therefore

the
tinuous,
con-

repeatedlyuntil,
previouslycontained

for the

process

of electro-

deposition.
*

German

1886.]

Patent

42,243,Sept. 14, 1886.

[EnglishPatent

14,033,Not. 1,

261

COPPER.

solution,for

This

use

in

should
cells,
separateelectrolytic

be

introduced continuously
nearlyat the bottom of the cells which
and
to the top of these,
the cathode-plates
surround
; then rising
the
action on
depositinga part of its copper by electrolytic
cathode

it flows

its way,

on

into the anode

the top rim of the membrane


it passes to make

over

compartment, through which

of this cell (Fig.160). During


its final escape from the bottom
of the electrolyte
the passage
through the anode cell,the
into a basic
ferrous sulphatethat it contains is first converted
ferric
which in turn is changed into the normal
ferric sulphate,

sulphateby the absorptionof sulphuricacid produced through


the electrolysis
of the copper
sulphate; the higher specific
it to
the
salt
latter
of
causes
gravity
sink to the

of the

bottom

this

liquidescapingfrom

vessel.

The

\^

compartment,

less copper than was


into the
present in it when introduced
cathode cell;and it also contains neutral
ferricsulphatein solution. This solution
contains
therefore,

Ml
a'

of

convertingcupric
and cuprous
sulphidesand copper oxide
into copper
sulphate. In thus acting
first-named
the
compound
copper
upon
into
the ferric sulphate is reconverted
ferrous sulphate,whilst the liberated
to oxidise the sulphideof
oxygen serves
The
product from the roasting
copper.
has

the power

now

of the

low
contains
explained,
ore

at

temperature,as

above

of its copper in
most
the form of sub-sulphide
; but the iron
is present as peroxide,
a substance which

"-^

and is
sulphate,
"
160.
Siemens
Fi
acid. The
affected by sulphuric
scarcely
Salske electrolytic
cell
for treating
cally
sulphide,however, is energeticuprous
copper ore.
dissolved
by the ferric solution.
The chemical processes, which take placeduring the electrolysis,
in the following
and the leachingprocess are
clearlyshown
is not attacked

by

ferric

"

equations:
"

I.

arHaSO^+ 2CUSO4 + 4FeS04


=
Cu^ + 2Fe2(S04)8
CuO
+ HjS04 =
(h)
3CuO
+ Fe2(S04)s
(c)
CuO
+ 2FeS04 + HaO =
{d)
=

11. (a) a;H5S04 +

2Fej(S04)8+ XH5SO4
2CUSO4 + 4FeS04 + S + xUfiO^
CUSO4 + HjO
3CUSO4 +FesO,
CUSO4 + (Fe,Os+ SOj) + Hj
2Cu

(a) shows that if


the
the ore
hold all its copper in the form of cuprous sulphide,
after passingthrough the leachingvats, will contain
electrolyte,
ferrous sulphate,
the same
quantityof copper sulphate,
"exactly
A

comparison of

the

equationsI.

and

II.

262

ELECTRIC

and

SMELTING

salphuricacid

free

AND

it did

as

REFINING.

; and that it
priorto electrolysis
be
used
again for
may

and
is,therefore,completelyregenerated,

electrolytic
decomposition. But
the ore
partlyas copper oxide, it is
and
(d) that in this case the
(6),(c),

the

copper, but
before
was
It is not

used

present

electrolysis.
to point out
necessary

almost

this case,

the

of

the

solutions

electrolytic
process
of the

givesrise to

no

Fig. 161.

"

Whilst, with
the above
case

method

vats, which
in

terrace

in

materials

may
copper

it
be
is
In

sulphide.
a complete

cuprous

dissolved,and

regardto

in

the

copper and iron could


that in the described
and

the

that the

position

electro-chemical

series

force.

of vats in the Siemens-Halske

matte

anodes, an

process.

of
and

to

KM.F.

whilst
adopted. And^ "gaiii"
the

current-volume

is therefore

processes,
there is no loss whatever

In order

form

counter-electromotive

process is
about one-third

reduction

of

polarisation
occurs,

Arrangement

matte

raw

than

in

of 1 '5 volts is necessary


0*7 volt will suflBce when
requiredcurrent-density,

give the

to

no

electrode

two

the

It is to be remarked

be maintained.

not

that

also be

iron would

richer

sulphuricacid

material, because

entirelyin the

however,

uniformityof

roasted

be present in
eqnationsII.

will be

solution

in respect of iron and

poorer

lieu

in

if the copper
evident
from

in the

is used

lost,by

the

for

former
other

alternative

of this nature.

produce the rapid circulation

of

liquidthrough the

is necessary
for satisfactory
work, the cells are placed
form (Fig.161),and
all the cathode
compartments,
connected

togetherby siphons,/^,Z^,A3,in one


cells,
A^, A^, Ao, are similarlyconnected
group, while the anode
in another series by the siphons,A;^,
k^,"3. In order to maintain
the level of liauid in the vessels independent of the quantity of
solution added, the ends of the siphons in the lower vats
are

Kj, Kj, Ko,

are

26a

COPPER.

upwards for the space, a, which


height, jS,between two consecutive

is

tamed
in

Modified

Process.

Siemens-Halske

equal to

the difference

yessels.
"

From

subsidiary

Fig. 162.

Fig.

163.

Fig. 164.
Siemens

patent
the

use

"German

1889.]

taken

out

" Halske's

by

of this process

the

same

cell (1889).
electrolytic

firm,it

led to difficulties.

Patent 48,959,Jan. 3, 1889.

be

must

The

[English

concluded

that

cells
electrolytic

Patent

3,533,Feb. 27,

264

ELECTRIC

SMELTING

AND

REFINING.

previouslybeen divided into two (positiveand negative)


in the second
compartments by a membrane
; but it is shown
these
that
membranes
liable to become
are
patent specification
membranes
have either too high
The
torn
during electrolysis.
else they are not sufficiently
electrical resistance,
an
or
durable,
for they stretch and allow the solutions to escape.
cell in which
this
Figs.162, 163, and 164 show an electrolyte
had

evil is remedied.
suitable

flat

of
of wood
or
vessel,G, made
with
is
with
lead, provided

coated

material,and

other
a

forated
per-

false
The

bottom, L, on which the anode, A, is extended.


either of platesof retort carbon in direct
may consist,
connection
with
one
another, or of perforatedlead

anode

electrical

platescovered with small fragments of retort carbon, or, finally,


of deeply corrugatedlead platescontainingperforations
to allow
of the passage
anode
of the electrolyte.The horizontal
is provided
insulated

with

the necessary
with a layerof

covered

electrical

connections,and

is

material that may


to
serve
some
filtering
of
the
solution
anodes.
the
the
The
surrounding
prevent
escape
be of felt or any other suitable organic or inorganic
filter may
material.
The cathodes
consist of the surfaces of the cylinders,

K,

which

quite covered

are

maintained

in slow

cylinders may

made

be

other

by
of

the

and are constantly


electrolyte,
waterproofbelt,S. These
by
the

revolution

wooden

material, and

coated

core

surrounded

with

with

wax,

conducting
in any
connected
suitable way
electrically
with the journalsof the cylindersand the conductors, k.
The regeneratedsolution,consisting
phate
of copper- and ferrous-sulinto the
stream
solutions,is conveyed in a continuous
which
is
of
the
The
rotation
liquid
alreadycovering
cylinders.
cement,

or

material, which

is

the

latter effects the continual

the

partitionseparatingit from

tube, U,
filter at

conducts
the

this,a

rate

same

constant

the

salt is reconverted

as

of the solution

anode

down

compartment.

from

to

The

the space beneath


away
into
the regeneratedliquor is run

the
the

C ; and, there is,in consequence


of
transference
of liquidthrough the filter

through

but

the cathode

from

mixture

the solution

compartment

upper

slow

to

the anode

Here

compartment.

the

ferrous

sulphate by the liberated oxygen,


salt,having a higher specific
gravity,sinks to the
bottom
and is at once
carried
through U, so that by
away
the
inflow
of
properly regulating
liquid,the strength of the
and
the quantity of copper
current,
and
iron in the solution,
the result of the process should
be that the electrolyte
in the
and

into ferric

the ferric

upper compartment loses son^e two-thirds of the coprer contained


in it,while in the anode portion the whole of the ferrous salt is

peroxidisedto the ferric state.


conveyed from the anode cell
the ore
acting upon
powder,
system

again.

The
to

solution

is

the extraction

it circulates

uninterruptedly
tank, and

through

the

after
whole

266

SMELTING

ELECTRIC

that

account

The

only

imperfect apparatus
very
both
of the membrane
durability

of

want

anode and cathode


difficultiesin the

extractingthe
that
increase

REFINING.

AND

employed.
separatingthe

compartments, and
with

ore

resulted

of the carbon

turbid

the

clearingof

solution

the anode

and
liquors,

these

troubles,caused

from

was

ancKie

rods,

obtained

on

all the

ments
derange-

unforeseen

an

in the E.M.F.

required(from 0*75 to 1*8 volts per bath),


and finally
led to the suspensionof the experiments.
The
from
a
published account
given by
process
appears
Siemens
" Halske*
been put into operationat works in
to have
into
Spain and in the Tyrol,but it cannot be said to have come
the
remarkable
since it is
more
practicaluse there. This is
from
the treatise above
mentioned
to be inferred
t that ample
experiencecould have been gained in an experimentalplant at
Berlin.
This
Martinikenfeld,near
however, to have
appears,
been neglected,
had
it
been
the
not
for,
so,
great cost of the
in the
in Spain and
Southern
plant laid down
Tyrol, and
the
would
with
have
at
latter
certainlyexperimented
place,
been saved, and the unpleasant record of an unsuccessful
ments,
experisuch

it may

as

to have

be assumed

now

been, would

have

been averted.
The

result

Borchers'

of all Dr.

sulphide copper

ores,

whether

laboratoryexperiments with

raw

the

compounds resultingfrom

copper
is that

in

his

it is

opinion
only by a considerable

changed

or

and
The

extract

of such

ores,

the copper

pletely
com-

alteration of the leadingarrangements,


either be
electrical part of the work
must
be omitted
pleted
altogether. This work will soon be com-

that

so

calcination

possibleto

the

with

roasted, and

or

the

account

an

of the results

Process.

Hoepfher

Hoep"er

process, { which
theoretical interest.

published.

similar

overtaken

fate has

has,however, many

pointsof

the

able
consider-

published shortlyafter his


granted,Hoepfher described his discoveryas

In the first account


first patents
follows:
"

"

were

of his process,

"

"I

diaphragms into
permit

anode

to

series.

In

the

anode

incapableof

are

cathodes

cathode

and

through circulation
cathode, through

cathode

of sheet

Jahrbuch

der

from
any

separated by

are

of

number

carbon

are

solution, and
electrolytic
copper.

solution

reliable

compartments, and which


anode
from
to anode, and

compartments

Siemen^Bche

in

cells

placed

anodes,
the

of cuprous

Eltktrochemie^1895, vol. ii.,p,

t Gruflonwerk-Magdeburg. Daa
mis

which

tanks,
electrolytic

use

in

which

others

are

chloride

in

155.

Kup/ergewirmungwerfaLhreH

Krzen,

t German
March

Patent

53,782, March

1, 1888.

[English Patent

26, 1888.]

%Zeit8chriftfuraiigeiaandte
Ghemie, 1891,

p. 160.

4,626,

267

COPPER.

brine

in calcium

chloride solution,or the like,flows past a


in turn ; and a similar solution
of anodes
into
comes
w
ith
convenient
cathodes.
of
number
successively
any

or

number
contact

Metallic

is depositedupon
the
copper
2 '36 grms. [36*42grains]
per ampere
per
the rate at which
double
the same
current
from

the solution

"At
chlorine

cupricsalt,such

no
anode,
cuprous
be liberated;and

the

exactly
depositthe metal
copper sulphate.

as

present, free

were

of 1*8 volts would

for electrolysis.But
the chlorine
necessary
combines
with
the adjacent cuprous
at once

process
and
converts

it into

cupricchloride.

of

rate

can

KM.E.

an

at

hour, that is at

chloride

would

be

then

of

if

the

latter

In

in

this way
an
in a direction

thia

chloride,
E.M.F.,

able
favournearly 1 volt,is produced
in the electrolyte
the
that
is
so
electrolysis
;
with
difference
of
of potential
a
practicallyaccomplished
only

amounting

0'8

to

to

the action

volt

between

becomes

cells

the

electrodes.

and

weaker

through them
passes
last of the series
the

The

weaker

in the

solution

in

respect

until
successively,
from
free
nearly

cathode

of

it

as

copper
finallyit flows

from

Leaving the
copper.
above-described
process

electrolytic
vats, it is collected for the
The anode solutions retain their
through the ore.
but
no
longer as cuprous chloride;for it has become
copper,
converted
into cupricchloride,and the solution containingthe
latter salt flows continuouslyfrom the vat.*^
The cupricchloride solution thus coming from the anodes
is

of circulation

*'

used

in the
the

from

system

finelycrushed

of about

"ats

should

10 cb.

be suitable

solutions,and
The

of circulation

solution

[350 cub.

be

that

the

used

of the material

with

heated

upon

they

providedwith a good stirring


ap|"aratu8.
accordingto the equation:
copper ores
"

CuClj
So

ft.]capacityare

for the treatment

should
acts

of these

ores

m.

the copper and silver


metals.
Large leaching

to extract

CuS

CujCla.

cupricchloride,by combining with

copper,

becomes

It is well known
that silver
chloride.
cuprous
and
even
by
sulphide, Ag^S, is readily attacked by cupric,
reduced

to

chloride,so
cuprous,
the ore, it is converted

equation,and the
chloride liquor:

that
into

when

this

substance

chloride,as

silver chloride that

shown

is present in
in the

following

dissolves

is formed

in the

"

Ag^S

2CuCla

CujCl,

2AgCl

S.

regenerated cuprous chloride solution is treated, as


l^low,for the separationof silver,arsenic,bismuth,
the depositedcopper
would
render
and other substances,which
impure, and is then caused to flow to the anodes and cathodes.
the former, cupricchloride is produced,whilst at the latter
At
the separationof copper takes place.
''The

described

Cheniie,1890,
XeitMhrift/iir
angeiaandte

p. 622.

ii68

REFINING.

AND

8MBLTINO

ELECTRIC

of the solution is most


cally
readilyand practipurification
oxide
lime
chemical
or
being
cupric
by
means,
the arsenic,antimony, or bismuth, which
employed to remove
that the
known
be especially
to copper,
to
-are
so
prejudicial
silver
metal ultimately
be
The
is
separated,
depositedmay
pure.
either electrolytically
or
Any
chemically,before the copper.
small proportionof iron that may
dissolved from
become
have
the copper ores
with lime ; if this
is separated
by the treatment
the
not
effected,
reparation were
proportion of iron would
gnidually increase,and hence the solubilityof the cuprous
The

*"

effected

chloride

would

value.

reduced

be

oxide

about

to

is such

a
Cuprous
before
precipitated

oxide of zinc is
of alkali
The

**

or

alkaline

earths

quantityof

number

of

that of copper on the addition


of cuprous chloride.

to solutions

depositedin 24 hours in a sufficient


interpolarpotentialdifference of
439
kgs.[96-6lbs.]per H.R (= 690

copper
with
an

baths,
volt,is equivalentto

0-8

one-quarter of its former


the
powerful base, that even

Since each
hours),allowing for a loss of 10 per cent.
works
in
ture
horse-powerdeveloped
large
only requiresan expendiof 22 kgs. [48'5 lbs.]
of coal per diem in the boilers,it may
be estimated
each pound of
that in a well-managed installation,
coal burnt should produce 2 lbs. of depositedcopper.
Allowing
for the crushingof the ore and the work
1 lb. of coal
of stirring,
should
the original
suffice to produce 1 lb. of copper from
ore.
in
The extraction of copper ought, therefore,
even
to be possible
ampere

countries

which

in

coal

the

resources

are

of the

most

limited

character.
The

"

above-described

is
process, which
in Germany and abroad

shortlyto be applied

placesboth
will,as I [Hoepfner]
hope, quitedisplacethe ordinaryprocess of copper-smelting.
a daily
calculation,
According to ray [Hoepfner's]
production
of 1,000 kgs. [1 ton]of copper from a 5 per cent, pyriteswould
and
require a capitaloutlay of about 123,000 marks ["6,1 50J,
the daily working cost of such an
inclusive of
installation,
interest and amortisation
charges,would be about 190 marks
10s,]. The daily working cost of all other processes
in many
"

E"9,
litherto

used

than

more

''The
process

may

be stated

as

sulphate process

b}'

**2.
extract
"

up
and

otherwise

similar

conditions, be

as

follows

the

cheapness of

the

present

"

of the current in the cuprous solution,


be possiblewith a
would
as
per hour
the cost of the electrical installation is reduced

greater depositing
power

affordingtwice
one

under

this amount.

contributingto

causes

1. The

**

would,

double

much
so

that

copper

half.
The

of the chloride solution, which


is able to
hiffher efficiency
the ore all the valuable metals that it contains.
take
of this solution (which may
considerable dissolving
power

from

3. The
much
150 grms.
of copper
in consequence
as
per litre [1} lbs. per gallon]),
of which
the leckching
siae
be
of
small
comparatively
plantmay
demands
the expenditure of out littlemechanical
power.

as

26^

COPPER.

the described
venture
to consider
''Although I [Hoepfner]
process as already [1891]proved to be sound, there is a possibiiitjthat it may be even
yet improved, so that the cost of
productionmay be stiJl further reduced."
Unfortunately,the hopes which
Hoepfner then expressed
been
have
not yet
fulfilled,
although,in a paper read in 1898
at the annual
meeting of the Verhcmd deutschen Elektrotechniker
the greatest confidence in
he shoved
at Frankfort-on-the-Maine,
the final result of his work.
The process was
put to a practical
works
in many
test
at
Schwarzenberg in the
experimental
e,g.^
Saxon
Weidenau
near
Erzgebirge,at Giessen, in
Siegen,and
A
has
finallynear
specialcompany
Papenburg on the Ems.
been
formed
at Papenburg for the working of this and
other
the company
isby Hoepfner, and to all appearances
processes
still carrying out
works
built
that
in
at
experiments
place.
of works
Owners
if they refuse
must
certainlynot be blamed
of their work, and of results which
to
publish early accounts
"

demanded

have

of time

both
great sacrifice,

It ia
money.
results ;
only possibleto judge of such work by its commercial
has
made
been
bat of Hoepfner's,
public,although,
nothing
yet
a

and

accordingto his statement, the last-named works must have been


The
in operationfor over
four years.
difficulties in attacking
with
ferric
chloride
are
sulphide ores
cupric or
great,
very
notwithstanding that the reaction takes place far more
rapidly
when
ferric sulphateis used.
than
Experience has been gained in old-established works which,
conducted
the leaching of
for many
successfully
years, have
this
but
confirms
difficulties
the
which
ores
experience
;
copper
have
te
given trouble with the Hoepfner process.
Copper ores arebe had which, having been attacked
natural
by
processes,,
the

contain
and
with
the

of their copper in the form of carbonates,


yield this portion to dilute hydrochloricacid

greater part

which

the utmost

chlorides
has

copper
with them,

readiness;but

remaining
dissolved

been

the

in

and

in this

case

the reaction

residue,after
the

copper

the

bulk

between
of the

sulphidein contact

requiresmonths or years for its completion. Indeed,


with these residues.
it is only completed in the heaps formed
There
three
for
the
are
means
hastening
decompositionwithout
previouslyroastingthe ore :
"

1.

2.

Crushing to a very fine powder;


Heating during the periodof leaching;

3. Constant

movement

of the slimes

while

and

being leached.

These, however, are


considerable

requirements,of which the


proportionof the advantage

first swallow"

be derived
up a
from its use, whilst the fulfilment of the last two
increases the
difiicultiesof the process, and adds to the cost of constructing
the apparatus.
Then, too, the further difficultyby no meana
"

to

270

SMELTING

ELECTRIC

AND

REFINING.

account.

clearingthe solutions
Hoepfner, in the last-named

favourable

account

inconsiderable

which

from

of

"

of the

originallypresent
per centb of
but
he
makes
the

of

cost

the

reference
It

nearly

as

gives

paper,
Rio

Tinto

raw

iron

dissolved

was

whatever

the

in

further,

must,

taken

into

very

pyrites,

3*37 per cent, of copper


in four hours, while only

out

accompanying

no

process.
conditions

these

under

dissolved

was

of

of the

nine-tenths

over

extraction

be

must

to

paper

be

iron

much

with

observed
as

it;
the
that

passed

copper

into solution.

Hoepfner, at the end of his paper, says that proof is thus


of pure
given that the electro-metallurgical
recovery
copper
direct from
its ores
by the cuprous chloride process is based
sound scientific principles,
but also more
not only on
larly
particutechnical
on
merits;" but the author
(Dr. Borchers)
considers that this expressionof opinion is optimistic,
and that
sufficient
of
the
there is not
of the
proof
yet
practicability
process technically.
The original
account
Experiments.
[The Sohwarzenberg
given by Jensch of his experiencewith Hoepfner's process at
Schwarzenberg may not be available to many readers ; and as it
short abstract
sets forth very clearlythe details of the work
a
The
here.
used
be
contained
from
9*5 to 12*25
oi'e
given
may
"

"

and

of copper,
finelythat on

per cent,
so

pass

through

34*5 to 32*6 of

pass

100 sieve.

The

revolvingwooden

drums, holding from

into which

was

the

ore

chloride
rise of

the anodes
trouble

ores

and

owing
and

temperature
the

to

it

crushed

was

latter

leached

was

to

in

large

1,500 gallonseach,

the reaction

consistingof

chloride.

The

between

the

cupric

drums

gave

leakage,which increased with the


the growing percentage of cuprous

It

the
to treat even
necessary
the leachingsolution ; but
samples,although half of the copper was removed
four times

or

the poorer
the first extraction,ten
half.

remaining
cupricchloride was

It

or

The

necessary,
slimes

was

with

twelve
found

was

reaction,magnetic pyritesand
this substance.

ore

200

hasten

calcium

with

solution.

three

the

to

solution,the

the

with
in

admitted

and

";hloride in
richer

steam

from

considerable

iron;

85 per cent, of any sample would


an
average
sieve with 200 holes to the linear inch,and 96

would

per cent,

from

were

also

to dissolve
necessary
that a large excess
of

the temperature of the


pyritesare both attacked by

because,at
iron

after the leaching


filter-pressed
in order to extract
much
as
as
possibleof the solution from
The anodes were
them.
of paraffined
carbon, the cathodes of thin'
of copper-coated
sheet copper, the use
carbon
cathodes having
The
earlier difficulties with
the parchproved unsuccessful.
ment
here
with.
These
met
diaphragms were
diaphragms were
as
previouslydescribed by Coehn
swelling up and becoming
tender
after
few
the carbons
a
days' use, so that when
very
were

271

COPPER*

disintegrated,as

did

tbey

fragments

at

slightestprovocation,*the

the

collected

of the anode

the bottom

at

of the bath

and,

pressingagainstthe parchment, produced rupture. Trans.]


The
Coehn
An interesting
Process.
experiment of Coehn'sf
the Hoepfner process
of
the
difficulties
of
one
appeared to remove
namely, the need for the use of diaphragms, for which no
with
suitable material could readilybe found
for use
in contact
chloride on the one
side and solutions containingcupric
cuprous
"

"

"

chloride
Ooehn
with

the other.

on

chloride was
electrolysed
cuprous
formed
the
at the
chloride
current-density, cupric

observed
low

when

that

containingvessel in the form


of a solution,of which
the specific
gravitywas higherthan that
of the surrounding medium, and, collecting
at the
bottom, it
formed
If the cathode
a layerof gradually
increasingthickness.
that
this
into
it
were
so
long
dipped
layer,copper became
anode

sank

dissolved

to the

bottom

of the

the
the immersed
the former within
area
; and
without
of
be
effected
could
most
deposition copper
satisfactorily
a
diaphragm with the aid of the apparatus shown in Fig. 167.
from

Cus CI, Solution.


Level ol

Permanent

Liquid.

the

Fig. 167.
carbon

"

Coehn'e

"

anode. A,

is

formed
collecting-trough

celL
single-compartment
electrolyte

used, of
at

the

such

length that

bottom

of the

it

dips

bath, and

into

it is

of sheet copper, K, of only half its


a cathode
suspended opposite
chloride
The
into the upper
liquoris admitted
length*
cuprous
vat, whilst the cupric chloride
part of the deep electrolysing

solution,which
*

streams

[It is claimed

downward

from

the

anode, is withdrawn

for the Street Girard


of resistinff
capable

carbons (EnglishPatent 13,339,


that they may
so
disintegration,
with ciurents
solutions,even
considerablyexceeding
prepared by heating them
sq. in. in density. They are
temperature at which they soften and are converted into

1893) that they cure


be used in aqueous
0*5

ampere

per

to
eleotricAlly

"Translatob.
graphite.

1895, vol. ii.,p.


iZeUschrift/urJSUkirochemie,

25.

272

ELECTRIC

SMELTING

through a siphon from


it collects.
metre

With

of cathode

of copper

the

the erection

several
laboratory,

gave
of

of ultimate
been

have

of the kind

and

already,at his suggestion,


working out of any methods
metallurgicalproducts that
In

success.

made,

which

for extraction

practical
processes
indicated.^

In

conditions

have

to the

ores

these

under

square

deposit
quality

temporary electro-metallurgical

of his students

their attention

promise

20

required

of Borchers'

treatingtroublesome

observations

in which

per
amperes
the
per square foot]
all requirements in respect of both

answers

turned

trough

[1-86amperes

area

quantity. The E.M.F.


amounts
scarcelyto ^ volt.

of

of the

deepest part
of
current-density

and

Since

REFINING.

AND

this way many


led to the
of metals from raw
have

regard to the

extraction

valuable

discovery
materials

of

sulphides
by metallic chlorides rich in chlorine, their experience has
at
always been that the reactions take placevery slowly even
become
and
the beginning of the operation,
slower
the
even
as
available

becomes

chlorine

comparativelyshort
the conditions

which

and

more

diluted,until,after

more

almost

time, they come

to

standstill under

be

readilyfulfilled in practicalwork
viz.,moderately fine crushing,moderate
temperature, and not
of
slimes
But
under
too long a {"eriod
treatment.
stirringthe
which

ores

under

are

can

"

with

available for treatment

not

favourable
especially

conditions,such

chlorides,
except

as

are

able
only attain-

practiceat great cost, present fewer difiiculties in


working, if they are treated in the form of slimes,not with
chlorides,as explained above, but with free chlorine directly
in very dilute solutions ;
applied. Chlorine is efficacious even
chlorine
in
the
of
in the slimes is
and, as
proportion
practice
of chlorine until the
kept constant
by the gradual introduction
attack is complete,the active material is not present in steadily
of the chlorides
above
diminishing quantity as in the case
referred to.
much
chlorine
lower
at
acts
a
Finally,
temperature
than
do the chlorides.
This, in all probability,
points to the
of combining the two processes by usingthe solutions
desirability
and
with chlorine
the higher chlorides for the treatsaturated
ment
of the fresh ore, and completingthe chlorination
by means
of free chlorine after the removal
of the solution first applied.
If the electrolytic
method
should prove to be the best for the
and
o
f
other
valuable metals
the
from
precipitation copper
in

solutions

obtained, there

so

the
treatment

of

process

is

cupricor

yieldedin

Denkschrift der

wijbh the Dusseldorf

Ohemie, 1902"

the

be

no

in
difficulty

chlorine

necessary
the free condition instead

for the

so

ducting
con-

anode

of in the form

ferric chloride.

Applications
*

that

would

of
L

Copper.

"

t. ffochachule

Exhibition, 1902.

^The
zu

uses

of

copper

are

very

in connection
Aachen, published
See also Zeituchrift
fur angewandU

274
the

Among
reckoned,

speiseobtained
copper,
waste

in the

Properties

extraction
the

ores,

sTtrer,
as

and

concentration

of nickel
of

nickel

Nickel.

well

as

of these

must

of

be
and

mattes

ores
smelting of nickel-bearing

lead, bismuth,

the manufacture

REFINING.

above-mentioned

the

in the

obtained

for

materials

raw

besides

AXD

SMELTING

ELECTRIC

cobalt,

the

slags and
products and in

steel.
"

Nickel

(Ni*;atomic

weight

"

58-88 ;

lustrons
specific
gravity 9) is a very clear grey, and brilliantly
which
are
metal, distinguishedby its tenacityand malleability,
like
be
rolled
sheets
drawn
into
so
or
iron, it may
high that,
In its magnetic and electrical properties
it strongly
into wire.
resembles
iron.
The meltingpoint of nickel is about 1,400"C.
It alloysreadily with most
metals
(copper-nickel,
copper-zinoGerman
nickel
Like
nickel,
silver,iron-nickel,
steel).
copper
nickel is capable of dissolvingsome
and
of its
iron, melted
for
the
oxide.
At
own
compounds, as,
example,
ordinary,
oxidises
and even
at comparativelyhigh, temperatures nickel
but slightly
in the air,so that the waste
of scale
in the form
much
than
in
in
hot
in the
is
less
or
working,
produced rolling,
of iron.
It combines
case
readilywith the metalloids,and its
with
and
arsenic,as also the protoxide,play
compounds
sulphur
Nickel
solves
disan
important part in the metallurgyof the metal.
in
and
nitric
in
more
acid,
re^ly
hydrochloricor
slowly
sulphuricacid. Unless an oxidising
agent co-operate with the
solvent,Ni' compounds are always found ; and these compounds
means.
usuallyresult from electro-solution by electrochemical
A great diversity
of treatingthe
is noticeable
in the methods
various
raw
materials,mainly owing to the presence of copper,
affi"rds
cobalt,arsenic, and antimony. But electro-chemistry
here a possibility
of simplifyingcomplicatedprocesses, and
an
will therefore
be given, first,of the electro-chemical
account
of nickel, with
applicableto the treatment
special
processes
the
rendered
references to
simplifications
possibleby them, and
afterwards
a
general survey will be made of the practicalprocesses
of nickel ores and
alreadyin operationfor the treatment
materials containingthis metal.
other raw
It is unnecessary
to refer again to the particulars
given in
the earlier literature concerning the electro-chemistTy
of nickel.
Ruoltz,*^in 1841, depositednickel,like many other metals, from
periments
cyanide solutions,and, in 1843, R. Bottgerf described his exwith the aid of
on
by galvanic means
nickel-plating
and from
nickel-ammonium
that time
sulphate as electrolyte;
down
chemists and specialists
to the present day many
have
of
the
to
electro-nickeling
by using
improve
sought
processes
"

more

suitable

same

time, the

nickel

salts

or

additions

majorityof these

to

the baths.

experimenters,many

At

the

of whose

"

Berzeliiu^ Jahresbericht,
1841, voL xxii.,p. 410.
f Journal furprakt, Chemie, 1843, vol. xxx., p. 267.

'

276

NICKEL.

that the
purely empirical,
ignored the possibility
of
dense
nickel
of
electrolytic
production
deposits
may
pure
depend less upon the nature of the nickel salt used than upon
conditions of working to which
in
they had become accustomed
individual cases, either by experiencegained in other directions
Under
these circumstances
it may
be readily
or
by accident
understood
that one
obtained
observer
satis"ctoryresults only
when
to
one
formula, whilst another observer
working according
different
The
succeeded
when
only
using a
compositionof bath.
existence
of different baths for nickeling
of so largea number
the
be
in
same
explained
may
way.
methods

were

Andre's

Prooess.

The

"

of

first account

electro-chemical extraction

of nickel

are

for the

experiments

to be found

in

German

He
in the year 1877.
mends
recomby ". Andr^*
the followingmethod
of nickel mattes
for the treatment
of impure compounds
and
of nickel, cobalt
speise,or

patent taken
or

copper :
**
The

out

"

material,which

but
only impure alloys,
and
the
in
electricity are,
speise,
form of plates if possible
(or granulated),connected
up to the
form
of
to
leads
means
so
as
binding screws,
by
conducting
dilute
anodes
suspended in a bath of
sulphuric acid. Copper
alone is thus
the
carbon
for which
on
or
cathodes,
deposited
but
the
exclusion
of
the
most
to
not
suitable,
copper platesare
raw

and

mattes

other

conductors.

time,

same

of

nickel,which

The

depositedfrom

is not

is continued

be not

may
conductors

are

an

and

until the solution

nearly saturated with nickel.


a carbon
separated by substituting

The

are

towards

end

the

of the

removed

acid and
sulphate,slightly

the

with

of copper

for the matte

In

and

of copper

nickel

last trace

anode

treatment.

traces

are

passes into solution at the


The
acid solution.
process
the free acid at first present

short

solution

or

time

is

speise

the

contains

last

pure

little iron.

sulphate is obtained from this by adding a


duced
evaporating in lead pans, air being introof
during the process either through tubes or by means
down
it. The iron is thus thrown
an air-blast impelled upon
as
of ferric hydroxide,which
be sepaflocculent precipitate
a
can
rated
The
solution
is
then
or
decanting,
filtering.
by ladling,
nickel
and
the
sulphate is
point
evaporatedto the crystallising
**

nickel

(a)Pure

little ammonia

put

on

"(6)

and

the market
order

In

iron is first

leaded copper,
or

or

nickel,are

substances

German

carbon

Patent

the

solution,the

the nickel

is then

carbon, blackconvenientlyused as cathodes,

most

soon

from

above, and

bath.

which

on

If
employed instead.
will
anode, polarisation
"

pure
described

ammoniacal

an

nickel

obtain

to

separatedas

depositedfrom
other

in that form.

Plates

nickel
or

take

will

of

deposit

may

platinum, "o., be used


place,and the efficacyof

6,048,November

1, 1877.

be
as

the

276

ELECTRIC

plate,or

of

of the

action

prevent

difi^sion.
between
is

the anode
The

nickel
or

from

current.

same

to

be

The

impaired

material

object is

iron

preferably,
a

or,

the

cathode

is drawn

sulphate or

out and sold as


crystallised
method
be applied to
can

siliceous nickel ores, such as


the Urals, after they have been

or

On

zincthe

double

in order

still better

attained

from

of iron-

will dissolve under

as

membrane
from

deBtrojed.

or

made

anodes

use

anode

This

REFINING.

AND

the membranes

at intervals.

**

will

separates the

membrane
solution

machine

it is necessary
such
form or

this account

or

the

from

current

SMELTING

to

if the

off either
zinc

continuously
sulphate formed at

such.
the
those

extraction
of New

brought into

of pure
Caledonia

solution

in

hydrochloricacid.

sulphuric
(c)If it is desired to depositcopper and nickel together,the
other raw
mattes
or
materials)are suspended as anodes
(speise,
ammoniacal
bath
in an
(ammonium sulphate); both metals are
deposited simultaneouslyon plates of carbon or black-leaded
of brushes, the depositis washed
by means
copper ; after removal
and receives further treatment
as
an
alloy. Since the sulphur
converted
into sulphuricacid
in
the
is
in
matte
part
present
of ammonia, corresponding
during the process, a small amount
from
time to time.
The iron is separated
be added
to this,must
in a flocculent condition, as described under
out
(a),together
with
be
When
arsenic
as
lead,which
peroxide.
present
may
is
and
of the
account
on
antimony are present, care
necessary
The
workmen.
of
in the form
copper and nickel co-deposited
be
another
almost
from
one
completelyseparated
powder may
of magnets, and
for this
by withdrawing the nickel by means
or

*'

the magnets of the machines


themselves
be used."
may
it is evident that,so far back
the year 1877, Andre
as
the
of
and
nickel
for the
anodes
mattes
as
use
proposed
copper

purpose
Thus

of metal, an
invention
electrolytic
separation and recovery
which
first
is commonly ascribed
to Marchese, although the
of
latter's
the
have
and
account
experiments
patents appears to
been publishedin 1882.*
Moreover, Andre in his proposalsfor the separationof copper
and
nickel is on
the right track so far as he deals with
the
of alloys; for,as will be shown
treatment
hereafter,copper is
readilytransferred to the cathode from anodes containingcopper
and
nickel by the use
of an
acid sulphate solution,while
the
nickel
be
it can
only into the solution,from which
passes
afterwards by electrolytic
it
is
true
precipitated
although
means,
that it cannot
under
be deposited under
the
any circumstances
It is impracticable,
with
conditions given by Andr^.
the
even
nickel
solutions
of
from
of
use
diaphragms, to deposit pure
nickel-ammonium
sulphate with iron or zinc anodes, because
there

is not

sufficient difference
*

German

Patent

in the

electro-chemical

22,429, May:2, 1882.

charac*

277

NICKEL.

teriBtics of the three

metals

nickel,iron, and

"

zinc

in aqueous

"

solution.
Classen's
this

Experiments.

period, in

the

Among

"

direction

the

first

of

experiments,at
electro-chemical

creating
industry must be included those of Classen,aiming at the
of
to the quantitativedetermination
applicationof electrolysis
and
furnace
in ores
it
is
the
metals
not
products. Although
intention
of the author
in this work
to dwell
on
electrolytic
methods
of determining metals, it would
be right to pass
not
made
of his experiobservation
an
over
by Classen in course
ments
determination
the
of
because
on
nickel,
electrolytic
by its
rendered
it was
means
possibleto produce a good adhesive and
dense
nickel
of
convenient
thickness, a desideratum
deposit
remained
which
had
for a long
to the
secret
a
electroplaters
after the first publicationof Classen's work.
In the
time even
first edition of his well-known
book,* QiLontitative
Analyse dttrch
describes
he
the
for
the
Elekirolysej
followingprocess
analysisof
nickel-copperalloys:
The
analysisof this alloyis extremely simple. A sulphuric
of the two metals is obtained by adding sulphuric
acid solution
acid to the solution of the alloyin nitric acid and
then
rating.
evapothe
from
is
t
depositedelectroly
Copper
tically
resulting
The
solution.
solution,after siphoning off,is concentrated by
the
free sulphuricacid is neutralised
with ammonia
evaporation,
is added.
The
oxalate
is
solution
or
potash,and ammonium
an

nickel

"

''

heated, from
dissolved
in it,and
now

had

Nothing
previous accounts
Kiinzel
of

of

solution

the

In

described, of
is
said

to

although
to

in order

saturated
in

avoid

to

these

at

the

one

best

in

with

the

are

results

is
the

case, the
at

temperature

nickel-ammonium
salt

temperatures.

which

that

in
electrolysis
publicationby

of
crystallisation

first edition

in

of

maintain

electroplaters,
" mention

the

oxalate

of WahFs

excellent

made,

of

use

of

bath

out

many

higher

perature
tem-

recommended

temperature

of

is

100** F.,

or

38* 0.

about

Farmer's

1888

condition

depositingnickel

process
specified.In

give

this

of

processes,
recommended

1883,

year
for

handbook

in

of ammonium

grammes

hot."
electrolysed

said

of

sulphate solutions
out

it is

been

25'' C.

to

been

it had

20** to

Frooess.

IIhad

one

+/Wd.,

An

apparatus

described

noteworthy feature, which

useful for other purposes

*aa88en, QuavL

"

Anal,

also"

namely, that

has
of

au/elektrol.Wege, Aachen,

by Farmer

proved

in

itself

rotatingcathodes.
1882, p.

22.

p. 12.

tAnUL
Ber, iiber die WUmr
Weltaussi, von
1873.
Brunswick, 1876,
1, p. 873.
iii.,
" Wahrs GalvanoplasticManipuloUions^ Philadelphia and London, 1883,
p. 382.

H U.8.A.

Patent

381,004, April 10,

1888.

278

Figs.168

In
used

for the
vessels

these

conductiug
similar

and

169, A

tanks, such

are

of metals.
electro-deposition

In

as

are

commonlj

the

part of
upper
other
wood, stone, or
nonare
rollers,
B,
or
substance, provided with coverings of canvas
made

material, so

withdrawn

REFINIKO.

AMD

SMELTING

ELBCTRIG

from

arranged

rollers

cylinders,E,

hollow

the

that

These

them.

of

in

rollers may
be
to maintain
serve

continuous

slow

easily
the

rotation.

open-ended
of brass or copper, and serve
The cylindersare made
as cathodes
;
C C\ attached
They are kept from lateral motion by the flanges,
to the rollers. The nickel plates,
"',are bent into half-cylinders,
and

used

are

Fig. 168."

as

anodes.

Farmer's

Fig. 169.

"

The

nickel

Farmer'B

metal

arin,

F, which

is free to turn

section).
depositingplant (longitudinal

niokel

depositingplant(cross-section).

jointin a vertical plane,carries a roller,D (also


on
conducting material,and mounted
c),by which the
B B, and is
cylinder,E, is pressedinto contact with the rollers,
connected with the negativepole of the electric generator.
the tanks are
filled with a nickel solution
During electrolysis
the double sulphateor nitrate
in the figures,
to the level shown
of nickel and ammonium
for the purpose.
being recommended
The
current
enters
by the anode, E', of the apparatus on the
right,and passes through the electrolyteto the cylinder,",
about

an

made

of

which
derived
From

elbow

makes

one

revolution

in the

minute,

B B, rotated by
from the rollers,
the cylinder,E, the current
passes

means

the

motion

of the

being

pulley,P.

through the roller,D,

279

NICKBL.

and

the arm, F, to a wire which


conducts
it to
thence it returns
to the oppositepoleof the

and

the

bath

next

generator,either

other tanks.
immediately or after passingthrough one or more
If the object of the apparatus were
merely the alteration in
the outward
the means
of
metals
of nickel),
shape
(especially
would
be found
be likelyto
not
very expensive,and would
older
of metal
and
well-tried
A
combination
methods.
displace
specialshape,
refiningwith the production of articles of some
is made
mention
is conceivable,but no
such as tubes or plates,
of such
in

the
be

well

of nickel.

treatment

(exceptingthe
nickel

would

intention, nor

an

it be
The

preciousmetals

of any service at present


metallic impuritiesof nickel

which

separated by purely electrical

is to

be

in the

obtained

rarelypresent) cannot

are

least,if

at

means,

in the

condition

metallic

operation. With the current-densitythat is necessary for


depositionof nickel nearly all metallic impuritieswould
be separated.
The
have

Basse-Selve

patenteda

Process.

process
in a

of

firm

Tbe

"

Basse

the
also

Selve*

separationof nickel

for the

the

same

from

iron,

containing salts of all these


of
The
solution
neutral
substances.
or
slightlyacid aqueous
mixed
nickel
is
first
with
the
salt,
iron,zinc,or cobalt,together
with a sufficient quantity of an organiccompound that is able to
of ferrous,or ferric,
oxide, zinc oxide,
prevent the precipitation
of alkalies ; a
or cobaltous,or nickelous,oxide, by the addition
solution of caustic potash or soda is then added
in
concentrated
moderate
is submitted
to electrolysis.
excess, and the mixture
With
of 0'3 to 1*0 ampere
current
a
(?per sq. decimetre)

cobalt, and

zinc

solution

The nickel either


iron,cobalt,and zinc separate at the cathode.
remains
in solution,or (especially
electrolysis)
by long-continued
concentration
in
tbe
separates
part as hydroxide,according to
alkaline

of the
the
small

has
To

is

proportionof

the anode
time

liquid.

electric current

with

is very

the solution

the

nickel

separatesout

the alkaline

as

or

black

over),a
oxide

if it be left for

depositvanishes

and

alkaline

moderatelystroug (1 ampere

this black

; but

in contact
been

When

organicliquidafter

on

some

the circuit

broken.

obtain

the

solution,from

which

is mixed

in the

nickel
with

metallic

condition,the

iron, cobalt, and

the

all free caustic alkali into

carbonate,and

zinc

have

carbonate

sufficient ammonium

it is then

alkaline
been

moved,
re-

to convert

electrolysed.

for the electrolytic


It is not necessary
separationof iron,cobalt,
and zinc that the nickel oxide should be dissolved in the electrolyte
; it is sufficient that

entirelydissolved,and
form

of

Either

the

the

nickelous
precipitated
tartaric
*

or

German

citric

metals

nickel

to

may

be

separatedshould

then

be

present

hydroxide.
acid, glycerine,dextrose, or

Patent

64,251, Dec.

22, 1891.

in

be
the

other

286

SMBLTIirO

ELECTRIO

be
may
of
free
presence

REFINING.

AND

organic oompounds

employed

solution

in

alkali,but

the most

separation.
satisfactory

The
Strap Frooesses.
his first patent,*
claims

metals

first named

the

inventor, Jules

Another

"

electrolyse

to

the

retain

to

solution

in

affords

Strap, in

with

matte

t he specifies
submitting the
specification
first to a sulphatising
matte
roast, leaching the product, and
of chalk
solution by means
the
iron
the
in
precipitating
resulting
and
air, converting the nickel sulphate into chloride by the
addition
of calcium
chloride,or other chlorides, precipitating
this compound with lime, and, finally,
reducing the oxide so
It
also
of
carbon.
is
means
possibleto electrolyse
produced by
ammonium
the sulphate solution after adding
sulphate,if the
free sulphuricacid produced at the anode is neutralised by the
oxide
continuous
with
nickel
addition of freshly-precipitated
of the solution.
stirring
A
Prooess.
The
Biokets
process, proposed by Rickets,!
be
nickel
and
from the outset
for the separationof
copper
may
In this
considered
as
having but small prospect of success.
anode

; but

in

later

"

after
electrolysed

the

double

is

the

to
precipitated

of

addition

the

the copper

while

salts of the

of the

the solutions

process

of the

sulphate of nickel

increasinglyinsoluble

becomes

of alkali-metal
the

separated at

bottom

two

metals

cathode, nickel

as

the

the

to

be

sulphates; then,

containingvessel
and

are

alkali

is to

be

in the form
which

metal,

acidity of

the

bath

increases.
The

Hoepfaer

Prooess.

1893,"describes a process
enteringinto the

without

solutions

are

to

be

Hoepfner, in his Englishpatent of


of nickel solutions
for the electrolysis
and
in what way the
of
how
question
"

obtained.

These

are

then

acidified with

acid {e,g,^
citric or phosphoric
feebly-conductant
oxygen
The
anodes.
insoluble
the
aid
of
and
w
ith
acid^, electrolysed
of the
anodes
in cells containing a solution
immersed
are
metals.
chlorides
of more
electro -positive
Vertically-mounted,
The formation
rotatingor oscillating
platesserve as cathodes.
of movable
is prevented by the application
of spongy
masses
motion by
brisk
in
and
the
is
brushes
or
electrolyte kept
pads,
weak

and

of pumps.
that is partlyor
metal
anodes
be made
of some
may
wholly soluble in the solution,in place of those recommended,
which
metal (zinc),
but in that case
more
some
electro-positive
means

The

will not
It is

depositedwith the nickel,must


method
proposed to adapt the same
be

cobalt,zinc,lead,tin,

or

be used.
to the

copper.

*
EnglishPatent 4,396, March 11, 1891.
+ EnglishPatent
16,800, Sept.20, 1899.
X U.S. A. Patent 514,276, Feb. 6, 1894.
" English Patent 13,336, July 8, 1893.

of
separation

382

BLECTBIC

reached

having

step

next

the

this

would

applied

self-evident
crude

the

copper,
copper, and

and

BBFININO.

pointy it is almost
smelting of a

be

contained

ore

of nickel

AKD

81IBLTINO

this crude

advantage.
and
electrolytically,
smelting processes.
with

alloy of

An

treated

metal

with

advantage

Miinsing Process.
Miinzing has
and
nickel
to
mattes
use
pur|x"rts

The

"

alloy

an

be

well

be

can

compared

as

if

could then

kind

this

the

Then,
be

would

method
electrolytic

an

that

metaL

with

patenteda process'^

speiseequally with
crude nickel as anodes, and so aims at solving a problem which
The compositionof
has often been
attacked before.
fruitlessly
with
several
the electrolyte,
in common
other not unimportant
details,is not
divulged. The description,however, contains
the hope that the process
will be
nothing which encourages
successful in practice.
The
and
Nickel
Cobalt.
following
Deposition of Pure
used
to produce the
process! was
by Bischoff and Tiemann
mination
in his determetallic nickel and cobalt used
by CI. Winkler
of the atomic
weights of these elements :
For the production of nickel,a solution of the purest nickel
used, containing 32*84 grms. of nickel per litre.
sulphate was
The electrolyte
prepared with this contained :
which

"

"

"

200

C.C.

nickel

250

salphatesolution.
sulphate.

ammonium

30 grms.
50 grms.

(of0*905

ammonia

sp. gr. ).

water.

cc

platinum is with difficulty


nickel plate,
9*7 cms.
detached
from its surfetce,
a highly-polished
used
with
7*9
as
cathode,
wide, was,
cms.
advantage,
long by
A dynamo
whilst a platinum platewas
opposed to it as anode.
was
placed in the
employed as generator, and a resistance was
circuit,of such strength that a fall of potentialof 2*8 volts
The current-density
corresponded to a current of 0*8 ampere.
As
the nickel deposit
as
soon
was, therefore,0^0^ 0*5 ampere.
it began to peel spontaneously
had attained a certain thickness
Since

nickel

deposited upon

from

the

more

or

of pure

and

less

in the

yellow.

the metal

and

current

it

curled,flakes,and

nickel
of

which

upon

lustrous,but,

tinge
in

surface

as

No

showed
of

course

there

of 20

compared
tarnish
no

was

depositingin thin,
obtained

was

The

hours.

with

cobalt,showed

specks

or

of oxide

loss whatever

when

which

been

dry hydrogen

roll of red-hot

by passingover a
nickel
that the electro-deposited

had

1313

metal

was
a

were

heated

and

grms.
white
distinct

visible,
to redness

previouslypurified
This proved
gauze.
been entirelymetallic in

iron wire
had

character.
Patent
German
fiirEUktrochemie^
81,888, Aug. 15, 1894; cf. Ztitschrift
1895-6, vol. ii.,p. 197.
f Zeitachrift/fir
avorganiscke Chemie, 1895, vol. viii.
"

283

NICKEL.

the

For

productionof cobalt,a pure sulphateof cobalt,mixed


sulphate, was
prepared by heating purple
cobaltic
chloride with sulphuricacid.
The
solution of
aqueous
this contained 11*64 grms. of cobalt per litre;and the electrolyte
with

ammonium

made

was

follows

as

up

100

:
"

cobalt

c.c.

30 grms.
30 grms.

500

cathode

The

wide,

and

strength of current was


density D^QQ 0*6 ampere.
=

grms., of
of
form

which
a

7*319

coherent

brightlylustrous
side it

other

showed

and

lost 0*23
0*56

per

0*32

per
oxide.

as

In

per

; it
On

weight,

cent,

of cobaltic

cent,

of the

second

in

cent,

so

heating

that

c.c.

c.c.

on

the

it
oxygen
contained

pure
have

(CojOg + 2H2O) ;
weight of cobalt had

in other

of:

words,

deposited

been

"

sulphate.
(sp.gr..= 0*905).

ammonium
ammonia

water.

polishednickel plate,9 cms. long by


cathode, and a platinum plateas anode.

was

The

cobalt solution.

30 grms.
50 grms.

was

in

it must

consisted
experiment the electrolyte

250

cms.

tarnished,however,

not

was

oxide

total

250

as

as

platinum,but

to the

next

and

grey
little oxide.

but

5*9

anode.

the current0*7 ampere


at 3 volts,and
The
cobalt
deposited
weighed 8*133

side

the

on

long by

the cathode
in the
grms. separated from
The
metal
and
was
fairlystrong plate.

dull

was

(of0*905 sp. gr.).

platinum plate 9*4 cms.


platinum plate served

similar

ammonia
water.

c.c.

was

sulphatesolution.
sulphate.

ammonium

7*6

cms.

The

used

wide, was

current-strength

of 3*2 volts,and the current- density


at a pressure
0*8 ampere
0*6
The action was
stopped after 30 hours,
D^^
ampere.
afforded 2*9 grms. of metal, of which
2*2 grms. were
easily
"

and

separatedfrom the cathode in the form of thin and curled fragments


of plate. The
metal
obtained
in parts perfectly
so
was
flecked with brilliant tarnished
lustrous,but in many placeswas
On
heating in hydrogen, it lost
spots or tinged with brown.
0*15 per cent, in weight,which
correspondsto 0*36 per cent, of
oxide

cobaltic
whole

of the

(OojOg+ 2H2O). Hence,


cobalt

of oxide
a

little too

ammonium

salts,even

volatilised
brownish
ring of
and

colour,aff
like that

made

high,because

were

heatingin

had

on

been

0*21

deposited

as

per cent,
oxide.
The

of

the

minations
deter-

in this way, however, are


likelyto be
the depositedmetal contained
traces of

after very
heating in

thorough washing ; and these


hydrogen, affording a slight

After
depositin the cooler part of the tube.
hydrogen, the cobalt had a uniformly metallic appearance,
in parts formed
plateswith a beautiful lustre. Its
compared with nickel, was
distinctlybluish-white,

of zinc.

284

ELBCTRIC

The

8XBLTIHO

AHD

REFINING.

Heibling*

^A process proposed by
tbe
electric fumaoe, bj tbe
in
produce ferro-nickel,

to

Heibling

Process.

of tbe

of mixtures

"

oxides

and

of nickel

iron, and

reduction

at tbe

same

reduction
obtain calcium
carbide,by tbe simultaneous
of calcium
oxide or carbonate
witb an
of carbon, cannot
excess
time

to

be said to bave

The
in tbis connection.
prospect of snccess
productionof ferro-nickel does not demand tbe high temperature
which
is necessary
for calcium
carbide.
Moreover, the fluxing
of

the

any

silica,which

fumaoe

is contained

in

products of nickel,would

be

conditions

tbe

that

silicides of

tbe

yielded,in place of the


would
be expected.

almost

impossibleunder
carbide.

production of calcium

iron

is in actual
nickel

and

operation,
thus

be

would

Heibling,

which, according to

metals

and

ores

Le Verrier| proposes
to separate
from
an
follows,
electrolytically
alloy of nickel
he would obtain
which
tbe
furnace-reduction
of
by

I"e Verrier

The

all the

necessary
patent of Rathenau's,fwhich

Indeed, a
shows

fur the

nearly

the

nickel

with

iron

New

Oaledonian

Process.

"

as

It is well known
that under
:
ores
(silicate)
the
in
of
obtaining
electro-deposition nickel,iron
nickel dissolve with
nearly equal rapidityat the anode.
inventor
entirelyto prevent the passage of iron
proposes
the cathode, by using an
electrolyte
consistingof a dilute
"

the conditions
and
The
to

solution
has

of nickel-ammonium

been

added, maintaininga

and
solution

aiding the
by

of calcium

the

which

chloride,to
weak

basic

peroxidationof the

addition,from

time

hypochlorite,
or, if

to

sodium

reaction
iron

time, of

chloride

in the

tion,
solu-

passing into

the

small

little iron

be

quantity
present,by

only
blowing air through the liquid. It is claimed that,under these
from the solution
conditions,the iron is completelyprecipitated
in the form
of hydroxide. Nickel-ammonium
sulphatemay be
used as electrolyte
if sodium hypochlorite
be used as an oxidising
chloride
of
lime.
in
of
place
agent
the use of weakly
The
Kugel" recommends
Kiigel Process.
acid hot electrolytes,
of
the
sulphatesof nickel and
consisting
magnesium, with anodes of nickel mattes or of insoluble materials.
The
solution may
consist of 800 grms. of nickel sulphateand a
like quantity of magnesium sulphate per litre,
at a temperature
a

"

of

90* C.
The

Prasch

tried in
more

Process.

Canadian

success

than

roughly crushed

and

"

The

works,
did

can

the

packed

has been
process, ||which
scarcelybe expected to promise

Frasch

The
matte
process.
in vessels the bottoms
of which

Hoepfner

EngUeh Patent 18,407, Oct. 3, 1S95


t Compare the section on Cartndm* and
Patent
t Engfish
5,781, 1898 ; German
Patent
" German
117,054.
*

,1

Enginetring and

"ilicuUs.
Patent

112,890.

Mining Joum,^ 19"X",vol. Ixjt.,p. 272.

is
are

285

NICKKL.

covered

with

sand, and

this
copper;
solution
strong

vessel,up

the

of

The
of caustic

the

soda.

form

weak

solution

of salt is

The

level of the sand

water

On

of caustic soda.

in the

duced.
prosolution

restingupon

immersed

are

in the

passingthe

current, caustic
the
whilst
of
it is intended
vessel,

in the upper
part
shall form chlorides with

forms

portion

thus

weak

the matte

the chlorine

that

or

of

stratum

the lower

diaphragm

the cathodes

anode, whilst

the

with

into

run

filled with
finally
with
copper plates,

vessel is

them,
soda

to

covered

layer is

The

matte.

solution

chloride

the metals
formed

thus

contained

is then

to

he

or
by chemical means, or it may,
electrolytically
the copper)have
of
the
metals
a portion
present (especially
be
of
been
electrolytically,appliedto the treatment
precipitated
chloride
contained
in
it.
After
the
of
matte
reason
by
copper
leaching,the matte is taken out, and is then, after washing,used
the residue of the
again, and it is only necessary to remove

either

treated
after

miEiteriaL

leached
The

used

matte

14-8, iron

contained, per

25, and

sulphur

31*8,nickel

cent., copper
The solution
24.

first removed

anode

cell contained, per litre,copper


50 grms.,
26*6 grms.
After depositinga
43 grms., and
iron
nickel
portion of the copper and passingthe solution againthrough the
the

from

obtained
which
contained, per litre,
liquid was
nickel
60
and
iron
35 grms.
50
By
grms.,
grma,
copper
that he would
the inventor anticipated
repeatingthese operations

cell,a

anode

solutions

obtain

Separation

of any desired composition.


Reference
here
of Cobalt.
must

be

"

the electro-chemical

proposalsfor
since
oxide,
they are

certain

of

in

use
practical

made

to

separ"tionof cobalt as
of nickel
the purification

solutions.
Vortmann

The

Frooess.

separatingnickel and

Yortmann*

"

under all
be considered as acceptable
of cobalt,like those of nickel,when
of

absence

alkali

the
in
or

such
nickel

these

metals),

circumstances,

time, reversed, the


oxide
time
whole

the

protoxides,separate

time, the

direction

hydroxide,while

black
oxidation

place more
of

of the

cobaltous

"

as, for
*

German

the

current

nickel
oxide

solution

formed

at

contains
1

current

per

cobalt

cobaltous

if,from
reversed, the
brown-

as
precipitated

remains

example, about
Patent

is

current

ultimatelybe

the

rapidlyif the

chloride

of

salts of

If, under
is, after a

nickel

of the cobalt should

in the

of

while the
oxide dissolves,
oxidised to cobaltic hydroxide. Hence

becomes
to

salts

cathode.

the

of

direction

the

neutral
electric

basic

the

at

out

the salts

solution

the

decomposed by
hydroxide, or

are

that

that
circumstances)

in aqueous
sulphates(or of other

alkali-metal

way

of
gives his method
(which,however, cannot

cobalt in the idea

in

solution.

The

the

cathode

takes

small
cent,

78,236,May 10, 1894.

proportion
of

common

286

ELECTRIC

In this

MJt.

case

SMELTING

REFINING.

reversal
oft-repeated

an

the

AMD

cobaltous

oxide

of

the

current

is

into
rapidlyconverted
unnecessary,
small
the
of
oxide
action
the
of
chlorine
eobaltic
by
quantity
or
hypochlorousacid distributed through the solution. Warming
facilitates the separation
the solution gentlyduring electrolysis
of the cobalt in either case.
Any traces of nickel oxide precipitated
with the cobalt may be re-dissolved by heatingthe solution
of the
for a short time to 60* or 70* 0. after the precipitation
is no
cobalt is finished and the current
longer passing. The
as

solution filtered from

nickel

should

cobalt^or

from

the

is

cobaltic

i^ould be

oxide

contain, at most, only

free

of that

trace

metal.

given by Coehn and Salamon, however, shows


The proposal
assumption is not quitecorrect.

account*

An

that Vortmann's
made

there

to

was

separate the cobalt

from
the
electrolytically
the form of peroxide,
but

by depositingit at the anode in


compelled to prevent the depositionof nickel and
they
cobalt at the cathode
by the addition of a copper salt to the
this observation
solution.
from the scientific
as
was
Interesting
the
that
it
of
standpoint, appears
expectation the authors that
does
the process might be turned
to useful account
industrially
nickel

were

been fulfilled,
to have
for, in a later patent,f the
appear
the
of the cobalt by means
recommend
inventors
of
precipitation
and so return
to the old method
of cobalt-nickel
persulphates,
not

accordingto
separation,
from neutral
precipitated

which

cobalt

and

iron

solutions

by means
the agent commonly used
work
or
peroxidesare employed when

In industrial
or

chromates

be

avoided, in

order

to

of

are
successively
oxidisingagents.

is chloride

of

this material

prevent the contamination

of the

lime,
must

liquid

by chlorides.
TJlke's
account

Experiments.

nickel,and
mattes.

by

methods

of the
of

Nickel

"

T.
at

T71ke,tin 1897,gave
that

time

used

for

noteworthy
refiningcrude
a

for the treatment


process of his own
in the first placeobtained
oxide was

smeltingand
tops-and-bottoms

of nickel

tion
by reducchloridising
roastingfrom

pyrrhotiteat the Orford mine at Constable's Hook,


then reduced
metal
to a crude
Jersey. This oxide was
95
0*2 to 0-6 ;
to 96 ; copper,
Nickel,
containing,per cent.
0*25 ; carbon, 0*45 j and sulphur (intentioniron,0*75 ; silicon,
ally
added to facilitate pouring),3; with about
15 grma
of
into anode-platesand
cast
platinum per ton. The metal was
"x"nverted into pure nickel by electrolytic
means
(Ulke believes
baths
in
that cyanide
the works
of the Balbach
were
used)
The refined nickel
Smelting and RefiningCompany at Newark.
Oanadian
New

"

ZeitschriftfOr
SUektroehemie,1898,vol. iv.,p. 501 ; and German
Patent 9,153,April20, 1898.
102,370,March 4, 1898 ; Engliflh
Patent 10,616,Feb. 6, 1899.
t German
t Bngiiuering and Mining Jaum,, 1897i vol. Ixiii.,
p. 112.

Patent

287

NICKEL.

obtained

flo

Nickel, 99*5 to 997


contained,per cent.
0*03
arsenic,
; sulphur,0*02 ; iron,0*1 ; and

; copper,
traces of

"

O'l to 0*2 j

platinum.
For

the direct treatment

followingmethod

the
on

and

mattes
nickel-copper

Anodes

"

per cent., copper,

average,

an

of

sulphur, 13*8 ; with


15 grms.
platinum

210

grms.

cast from

UJke

mends
recom-

(containing

matte

43*4; nickel,40; iron, 0*3;


of silver,
3 to 6 grms. gold,

with copper
ton) are electrolysed
s
uch
as
sulphates,
may be obtained
roasted
If
mattes.
a
gentle circulation of
by the leaching of
be employed,
solution be ensured and a moderate
current-density
will
all
the
metals
alone
be
of
out
deposited
passinginto
copper
When
the nickel has become
the solution.
highlyconcentrated
in
in the solution the copper
the
liquidis removed,
remaining
either by means
of sodium sulphideor by allowing it to pass
nickel mattes.
The
of
small quantity of iron
filter
a
through
older
methods
removed
of
the
or
by one
by the
present is
newer
process of Whitehead, with the aid of freshly-precipitated
residual
the
nickel
solution
there
be
hydrate. From
may
obtained at will either (1) nickel sulphate,by concentration
;
(2)nickel oxide, by precipitation;or (3) metallic nickel, by
electrolysis.
Forster's
in
Forster's
Experiments.
experiments, made
and

cathodes

in

per
acid solution of

an

"

the

1897,*

year
others that
a

dense

confirmed

the most

the

important condition
nickel is the

malleable

observations
for the

maintenance

Classen

of

and

of
precipitation

of

temperature

namely, from 50"* to 90" C. All other


such
of solution,
concentration
as
conditions,
current^lensity,
and the like,fall into the background in comparison with
it,
been
have
of
as
regarded
although they
specialimportance in
and
in
have
the subjectsof
been
cases
electro-plating,
many
invention.
Sulphate solutions,as Bottger showed in 1843, have
themselves
proved
especiallysuitable as electrolytes.Forster,
who
has made
comparative experiments,chieflywith sulphate
and chloride
in obtaining a
solutions,finds greater difficulty
that
found
while
good nickel deposit with the latter. He
with sulphate solutions,containingfrom
30 to 100 grms.
per
a
litre,he could
ensure
good deposit by using currenthigher than

densities
solutions

normal

the

of
had

from
to

50

"

to

contain

300
from

amperes,
50
to

with
120

chlorides
grms.

of

the

nickel

current-densityof from 70 to 300 amperes


in the case
of sulphate solutions
was
Again, whereas
necessary.
is requiredto maintain
but little care
an
approximately
neutral reaction with chloride
the
at
electrolytes,
temperature
the solution of the nickel at the
suitable for deposition,
most
anode takes placemore
quickly than correspondsto the current
at that
that
a
applied,so
point,
depositof basic salts occurs

per

litre,and

"

ZHUch/r\ftfUrmektrocKemU, 1897-8,vol. iv.,p.

160.

288

SMELTINO

BLECTBIC

unlen

ia taken

care

Forster

reaction.
grms. HOI

to

that

REFINING.

the

liquidalways has au
aciditycorresponding to

that

see

found

AND

an

litre

that

and

acid
2*5

order

in

to
was
keep
per
necessHry,
added
this constant, hydrochloricacid must
be regularly
at the
HOI
for each gramme
of nickel deposited.
rate of 0*05 to 0*1 grm.
Forster found that when
and
he used the lower current-densities

dilute

he

obtained

dull-grey
experienceof the electroa
point of treatingobjectswith a
first placingthem
in a nickel-bath,
often
and then carries on the process at a lower current-density,
relate
the
above
of only 30 amperes
All
figures
[persq. metre].
The
of metallic
to the
use
(crude nickel)anodes.
drop of
1
of
current-densities
150
is
at
only volt,and
potential
amperes
the

more

solutions

aboTe-named,

rough deposits; but this


plater,who therefore makes
when
highercurrent-density

is also

at densities

of 200

account

edition

of this work

With

Alloys.

Niokel-Oopper
Dr.

".

kind,

the

supplied by

was

about

per sq. metre

amperes

of

Separation

the

1 *3 volts.
The

"

Wohlwill

for

alteration

which

following

the

German

"

alloys of this

constantly
is a direct result of the process
electrolyte
employed. The separationof the two metals depends in this
the "ct
that both are
case
dissolved,but only copper is
upon
separatedin the pure state at the cathode ; but since the quan"
tityof copper depositedis equivalentto the sum of the quantities
*'

takes

place in

of the

two

the

dissolved

metals

of nickel

every pound
contained
the copper

at

the

passing into
in the

anode,
the

is

solution

it follows

solution

108

that

for

pounds

separated out

of

the

at

cathode, and no copper passes into the solution to take its place.
[Thisis,of course, independentof the anode copper which passes
the solution,and
is depositedin equal quantity at the
into
the
tion
cathode.] Hence, as
quantityof nickel present in the solumust
constantlyincrease, there must, in a given time,
arrive
be

after which

moment

greatlyreduced

so

the amount

of copper present will


that it is impossibleto obtain a coherent

of copper
and
deposit,and at last only a mixture
will
be
hydrogen
deposited.
"When
this period has been
reached, nothing further is
the
introduction
of
gained by
copper into the solution from the
dissolved
must
so
anode, for the amount
always be less than
the
would
the
of
amount
to
correspond
copper to be precipitated.
metallic

dissolved at the anode


copper
recovered
at the cathode in a useful form
i.e., as pure
metal
it is necessary
that copper
sulphate shall be

If, therefore,all

the

"

is to

be

coherent

regularly
quantityequalto that of the copper depositedas the
fore,
When, thereequivalentof the nickel dissolved at the anode.
the separationof copper
and nickel is to be regarded as a
and
not
to
regiilar
industry,
merely to be appliedincidentally
"

added

in

the treatment

of

small

quantity

of

material,the

process

must

290

ELECTRIC

SMELTING

AND

REFINING.

are
used, the addition of the copper sulphate to replace
the copper depositedis stopped as soon
the maximum
as
percentage
of nickel sulphateis approached,and the redaction
in the

anodes

proportionof copper in the iMith is continued


up to the limit at
which
useful
obtained.
When
this point is
a
good
depositis
the
of current-density
after a reduction
towards
nearlyreached
end
which
^the cathodes
lead
are
or copper
replacedby
plateson
"

"

quantitiesof less pure and less


insoluble
deposited,and, finally,
platesare

considerable

cohesive copper are


substituted
for the

for this purpose,


be used
plates may
of
the
is such that the
electrolyte
composition
The
of lead peroxideis excluded.
of the formation
possibility
has observed
that this is the case
writer [Wohlwill]
in working
if
the
with nickel-copper
contain
even
a relatively
alloys,
alloy
small quantityof iron.
The solution of ferrous sulphateobtained
in such a case
protects the lead so completely that the same
unlimited
for an
anodes for the purpose
serve
as
platesmay
absence
the
the
of
In
the
from
solution
iron
complete
period.
lead anodes are
rapidlydestroyedunless the water used is free
condition
chlorides
which
from
is rarely,
if ever, to be met
a
in
Each
increase
with
of chlorides
in practice.
the amount
favours the formation
of lead peroxide,
present in the electrolyte

anodes.

soluble

Lead

provided that the

"

and, therefore,the

but

extent;
addition

of the

destruction

of ferrous

sulphate in

providesthe

the

in

even

no

lead

anodes

to

an

ordinary
extra-

of chlorides,an
presence
considerable
quantity
very

protection.

necessary
of the copper
be removed
from the solution,
may
electrodes
and
the potentialdifference
at both
gas being evolved
The
now
solution,
alteringaccordingly.
containing iron, but
'*

bulk

The

evaporated to the crystallising


point,the
mixed
by
crystalsof copper and iron compounds are separated
the
and
nickel
chemical
after
finally
sulphate,or,
means,
pure
is
addition
of ammonium
sulphate,nickel-ammonium
sulphate,
obtained
by repeatedcrystallisation."
little copper,

only a

Review

of

will have
methods

of

of art,

or

indeed, even
the

As

from

FrooeBses

Industrial

Standpoint.

"

It

that the most


foregoingaccount
made
to apply electro-chemical
attempts have been
all products,whether
of nature
treatment
to almost
contain
which
of
nickel;
appreciablequantity
any
the impossiblehas not been left untried.

been

determined

is

from

seen

the

result of the work

has been

that

done

it may

now

be

said thai^
direct electro-chemical

(1) The
for
to enable

no

it to

cell
electrolytic

(2)
and

The

ore
nickel-bearing

known
be
or

treatment

is
electrolysis

treated,either
in

an

of the

treatment

as

ore

is rich and

anode

or

is

pure

impracticable,
enough

otherwise,in

an

electric furnace.

of the

ore

by

out
practically

combined

of the

system of leaching

question.

Silicates

are

291

NICKEL.

not

soluble
sufficiently

and

arsenical

so
carry
many
but in many

cases

the
as

so

available

beyond

which

that

only

not

is

which

solvent

consume

dissolvingthe
permissiblein view of

the cost

Moreover,

present.

in

; the sulphide
time
at the same

nickel,and

valueless,that

are

of nickel

amount

mentioned

solvents
little

constituents

is increased

ore

the

in

contain

ores

of

it must

be added

of the

Hoepfner process, a not


speaking
proportionof the nickel in sulphideores is present as
in the gangue-stuff,
and is therefore
almost completely

silicate
withdrawn

from

the action
it has

present known,

With

of the solvent.
found

been

all the

ores

the first step towards

that

of the nickel is a process of fusion for matte


or
recovery
No
has
in
succeeded
more
leachingprocess
extracting
yet
50
the

per cent
has
ore

reduce

of the nickel contained


been

little nickel
much

crushed

fine

as

in
as

speise.
than

sulphideores, even though


possibleto
practically

it is

surprisingwhen it is remembered
matte, which, in comparison with ore, contains
in the form

of

at

the

This is the less

it.
crude

even

that,
siderable
incon-

has
silicate,

been

not

found

to

that
but

yield

more.

of

Biattes.
Concentrated
been put forward, there are

Treatment

have

obtained

"

Although
no

accounts

many
positions
proavailable

of concentrated
practicein the treatment
If further experiments in this direction were
mattes.
to
the
be tried it would
be desirable in the first placeto determine
limits economicallyattainable in the enrichment
of the sulphides.
It is possible,
to obtain a concenby blowing [inthe converter],
trated matte
in which
the proportionof nickel is greater than
The NiS contains about 65 per
corresponds to the formula NiS.
of nickel ; but by Bessemerising it is possibleto obtain
cent,
mattes
containingover 75 per cent.,and it is hoped that it may
of any

results

be concentrated

even

mattes

the
up to 95 per cent. Ni, but in that case
of the following
to be regarded as consisting

"

75 per

Ni

c"nt.

80
o5

,,

,,

,,

,,

,,

,,

"

""

an

alloyof

71 per cent.
57

=
,,
,,

28

,,
"

"

14

it is

in the

NiS

)}

ji

,,

,,

,,

",

,,

"

43

90
95

But

have

would

mixtures

in

impossibleat present
slagsor what would be

29

43

57

72

86

per cent.

Ni.*

,,

,1

It

i"

,,

,,

"

"

predictwhat would be the loss


the cost of producing these high

to

concentrations.
For

materials

containingcopper the cost of Bessemerisingdoes


to be prohibitive.According to Ulke,t at the works
not appear
of the Canadian
Copper Company the cost of concentrating by
the Bessemerising process
matte
a
containing 40 per cent, of
*

Stated

in round

t Engineeringand

numbers

per

cent.

Mining JouriLy 1897,vol.lxiv.,p.

9.

292

ELECTRIC

BMELTINa

REFINING.

AND

with 43 to 44 per cent.


to a matte
copper and nickel,oonjointlj,
works
T"f copper and 40 per cent, of nickel (84 per cent, in all),
whilst
50
60
lOs.
the
marks
to "3) per ton ;
out at from
to
("2
in the

concentration

carrying30

of

matte
a poorer
80
to one
+
averaging
per cent. Ni
The
to be only 8 marks
(Ss.)per ton.

cent.

same

waj

Cu

Ni

Vogt*
doubt, too
Vogt is, however, without
the cost of the blast and
scarcelycover

low
the

On

is stated

per

by

figurequoted by
8

would

marks

power

for

necessary

the converter.

highly and ti-eatingelecquestionof concentratingmore


nickel
matte
trolytically
containingcopper need not be considered ;
For
the process
is only suitable for non-cupriferousmattes.
such material
it is only necessary
to determine
whether, and at
be
worked
what degree of concentration, a given matte
more
can
reduction
or
advantageouslyby electrolysis
by the well-known
So far as experienceis at present available,the latter
processes.
method.
still be considered
the only practicable
as
process must
The

It

that

is true

the

bulk

of the

iron

be

can

removed

from

by Bessemerising,and the matte at the works


Oopper Company contains, after blowing,only
0-3 per cent, of iron ; but the further reduction
in the quantity
of iron by prolongedblowing must
necessarilylead to the slagging
off of a large quantity of nickel, and
it is open
to
question
whether
free from iron could be obtained
a material
()ractically
cupriferousmatte
of the Canadian

within
But

the limits of concentration

if it is found

in actual

attainable

permit the

to

necessary
presence
quantity of iron, it is certainly needless to go so
hitherto
deemed
been
requisitein the concentration
In

mattes.

copper
shown

fact,

that the treatment


of iron is

contained

the latter

anode

iron

as

or

as

has

of nickelhas

results.

From

does

matte

material

to

all that

separation

requirethe

not

be leached.

The

of

use

matte

be smelted
to a nickel-copperrather,after dead-roasting,
chief
difficulties
which
in the way
the
of
means
alloy,by

treating the
removed.

matte

The

contained

matte

from

15 to 20 per cent, was


obtained
an
alloywas

nickel, were
Such

as

far

by Borchersf

that the electro- chemical

in the

certain

containing quitea largeproportion

with good
practicable

gone
of the metals
should

process
of matte

before,it is evident

has

described

])ractice.

of

present

by

electro-chemical

selected

as

the

direct
are
processes
of
certain
subject
ments
experi-

60 to 70 per cent, of metal, of which


from
iron.
After roasting and then reducing,
in which
in

the

the

metals, iron, copper,

proportion of

and

by weight.

alloy,when used as anode in an acid solution of copper


sulphate,yieldsa solution of nickel sulphateand ferric sulphate,
Andr^
whilst
the copper
is deposited at the cathode.
and
Wohlwill, as alreadyexplained,had attained this point. It is,
an

"

SfaJil ttnd Eisen, 1894, p. 23.

t Jahrfjiftericht dtr J^tktrochemie^1897, vol. iv.,p. 305.

293

NICKEL

therefore,only
had

reduced

been

the

that

a
electrolysis
good
gave
of
the
in
solution
proportion copper
less than
1 per cent.
Wohlwill
has explained

the

of this natural

cause

and

present,

copper

to

add

to

necessary

depositof co])per until

has

reduction

recommended

the

in the

of

amount

addition

of copper

sulphate,in quantityproportionalto the nickel (andin this case


The
to the iron in addition),
currententering into solution.
150 and 200 amperes
and
density varied between
metre,
per sq.
the potentialdifference between
0*5 and 1'2 volts,accordingto
the quantity of copper in the electrolyte.
the electrolyte
When
has become
saturated with the sulphates
and

of iron

nickel,the

residue

of copper
of iron

be

present may

most

The

method

for the Separation


of Iron
Borcliers' Process
and
The difficultiesin the separationof iron and nickel

Nickel.

by
scrap.
and many
others of precipitating
the
by Andre
with
the
aid
of
insoluble
is
not
electrolytically
anodes,
copper
suitable with solutions
of mixtures
of salts such as
practically
As the proportionof copper
here obtained.
are
present becomes
B.M.F.
and
less the
the
required increases,
current-efficiency
if the current-density
diminishes
be reduced
to a correeven
sponding
conveniently

removed

means

recommended

extent.

"

have

undoubtedly
is,however,

been

an

hy Borchers.*

under-estimated

by

easy matter
this process

means

sulphates

The

hitherto.

tion
separaprocess devised
sulphateis added to

of

ammonium
By
quantity equivalent to the nickel sulphate
and
the liquidis carefully
crystallised,
taking care that
present,
is always maintained
below
of the solution
the concentration
ferrous
nickelof
solution.
A
the crystallising
sulphate
point a
best
at
ammonium
a
sulphate solution crystallises
density
18**
the
Be.
1*143
of
about
boilingpoint)
(=
(measured at
sp.
ferrous-ammonium
iron
whilst
or
an
sulphate
sulphate
gr.),
at 31" Be. (1-275 sp. gr.).
solution
only begins to crystallise
is maintained
either in the neighbourhood of
The concentration
of
18" Be. or is allowed to exceed
this,accordingas the amount
the

solution

nickel

in

salt is

small

great or
5"*B4

within

; but it should

of the

be

never

specific
gravityat

allowed

which

to

the iron

approach
When
the proportion of iron present is very
salt crystallises.
nickel
and
of
iron by the first crystallisathe
separation
tion
large,
but
but there has never
been
will be anything
satisfactory;
of
the
in
iron
by
difficulty reducing
quantity
any metallurgical
the
the
in
fusion
to
transference
slag
preliminary
refinery
-

process,

hand,

it

even

down

was

shown

the method
that of iron.
*

1 per cent.
the experiments,in which

fraction

by
proved to

was

results

to

On
the

the
success

Jahre9htricht

be

other
of

factory
that solutions gave satispossible,
nickel
of
was
equal to
proportion
be again dissolved
after washing,may
crystals,

in which
The

of

the

der EhJdrochtmiey

1897, vol.

iv.,

p. 306.

294

ELECTBIC

and

freed from

8MELT1HG

REFINING.

AND

(introducedfrom mother-liquor
or
them) by precipitationwith chromates
persulphates. The nickel-ammouium
sulphate solution may then
be used as the electrolyte.Experiments have, however, been
made
by K F. Giinther in Borchers' laboratorywith the object
these
of introducingthis process into copper-nickel
works ; and
obtain
that
it was
not
possibleto
experiments showed
quite
sufficient concentration
of electrolysis
if the
for the purpose
of iron

trace

any

clinging to

double

salt

the double

used.

was

into the

It

was,

singlesalt.

therefore,necessary
It is well

Uiat manufacturers

known

of ammonium
the

sulphateby
to

salts prepare
ammonium
the addition of soda.
It was,

soda

use

directlyin

these

convert

to

from

carbonate

able
undesir-

however,

experiments

the

because

sulphatein the double nickel salt would have been


replacedby sodium
sulphate. But, since it is not desirable to
its
nickel
from
of the
precipitatethe whole
electrolytically
poverished
imof nickel
in the
solutions, the residue
electrolytically
solution is precipitated
carbonate
as
by the addition
ammonium

of

carbonate, and

sodium

the

decomposition of the

which

its

is

by

ammonium
same

for

the

during

the

by

of

that

process,
be present when

to

be used

would

it is necessary
the salts are

Utilisation

of

Anode

Beaotions.

"

The

entirelyprevented
to

transferringthe liquidto
be effected by the methods
may

removal

be the

carbonate.

solution,before
The

sulphate,
sulphate and

be

cannot

is

nickel

ammonium

the solution

so

may

apparatus

manufacture

absorption of iron
that

The

into

obtained

so

nickel-ammonium

converted

means

carbonate.

as

csrbonate

nickel

appliedto the

remove

any

iron

again brought into


cells.
the electrolytic
mentioned

The

above.

author,

in

the

previous editions of this work, has frequentlystated that, in


all cases
of electrolytic
deposition,if no suitable material is
present which
from
care

that

solution

into

in
electrolyte

be taken

must

work

will pass

the

that

is there

there

useful
is

the

at

anode

some

during
practicalreturn
*

Rontschewski

expended.
experiments

successful
brilliantly
this was
possiblein the
by the production of

of zinc

case

lead

be

or

the

form

had

rated
sepa-

process,
for the

shown

by

Borchers'

laboratorythat
electrolysis,
ss, for example,

in

peroxide without

the

aid

of

phragms
dia-

E. F. Giinther
has experimented with a view to
; and
producing various lead pigments, such as white lead, chrome

yellow,or
nickel.
with

zinc white

So

success,

and copper

far, however,
inasmuch

and
precipitation,

more

as

the
the

carbonate,simultaneouslywith
results

have

not

been

attended

requisitefor nickel
necessityfor maintaining

conditions

the
especially

with those
well be harmonised
cannot
high bath-temperature,
the
for
of
requisite
precipitation good lead, zinc, or copper
in obtaining solutions
of
pigments. He, however, succeeded

"

ZtiUchriftfurElektrochemie,1900,

vol. vii.,pp. 21, 29.

295

NICKEL.

lead chlorate
over

could

by

in the

anode

cathode

into

the

then

be obtained

treatingthe

cells without

solution.
of

any of the lead passing


lead
pigments desired

The

high purity and

resultingsolutions

outside

good coveringpower
cells.
electrolysis

the

lead

sulphatewhich depositson the cell-walls in the


into more
coatingmay be readilyconverted
useful compounds
The
difference
of lead.
with
a
potential
of
metre
current-densityof 400 to 500 amperes
per square
did not
cathode
surface
exceed
3*5 to 4 volts, although the
the

Again,

form

of

felt like

Fig. 170.

Fig 172.

Fig.171.

Fig. 173.

Apparatus

for the preparation of lead chlorate at the anode


and nickel at the cathode.

was
relatively
high,and althoughclaycells were
current-density
used,and in spite of the deposit of lead sulphateon the latter.
Experiments are still proceeding in the direction of obtaining

other solutions

in the

anode

Figs. 170, 171, 172,


has

been

used

for the

diaphragms; they
Royal
525

mm.

Porcelain

were

coll.

and

173

show

form

above

Clay

purpose.
obtained
of suitable

Factory at Berlin, each

high,and

120

to

140

mm.

wide

of

525

ins.

as

the

long,
J ins. x

mm.

20

that

used

are

qualityfrom

about

[20J

apparatus

cells

296

4}

ELECTKIC

5}

to

RMELTING

ins.].With

the

illustrated

AND

REFINING.

exceptionof
in the

these

cells,however, the

sketches,exhibits

speciaUy
are
used, similar
points.
those employed in copper
to
refining. These may be either
The arrangein
vertical
cross-section.
or
rectangular triangular
ments
the
solution
and
for circulating
for suspending the electrodes
the same
for copper electrolysis.
are
a^
apparatus,

as

Lead-covered

novel

of

Beview
review

assistance

in the

I. Boasting
is made
that

"

with

ores

and

of
to

shaft furnaces

which

Provision

no

Nickel

of

Copper

any

present.
it is available for
and
metallurgical

It consists of the

followingstages :
Sulphide and arsenical ores are
an
incompleteoxidisingroast in heaps,calciners,
(pyritesbumera), or reverberatoryfurnaces. The

products.

submitted

in

possesses the advantage that


of all nickel-bearing
and
ores

process

Boasting

Smelting Process
Separation from

the

be

may

future.

near

for

treatment

waste

Extraction.

special
experiencegained within the last ten years will
that electro-chemistry
has been of great service
and
that
it
is
industry,
likelyto be of further

suffice to show
to the nickel

This

in Nickel
of
possibilitiestreatingnickel

employed

Processes

of the

no

tanks

to the

reference

the

wooden

the

Ores.

"

"

productsof the roastingare :


(1) Sulphurous acidy which

"

for the manufacture

(2) Arsenic,
various

(3)

arsenical

which

of

is available

be

may

under

stances
circum-

some

sulphuricacid.
utilised

for

the

preparationof

compounds.

Tfie roasted

material^ consistingof oxides, salts,and

undecoroposableoxides, sulphides,and arsenides of


It is further treatecl
in the ore.
follows
contained
as
The

the

metals

"

mitted
(3) is subto a reducing process by fusion in blast furnaces (rarely
with slags(8 and 15),refuse nickel products,
in reverberatories)
oxide
nickel
with
nickel
with
oxide
ore
(especially
ores, or
such as garnierite)
additions
mixed with sulphidising
silicates,
black
fusion
This
results in :
ash, or sulphates).
(pyrites,
in
be
w
hich
are
rare
instances,
SlcLgs,
rejected,
(4)
or,
may
worked
stones.
into
building
up
bismuth
and lead are
present in the ores
(5) Metals, When
in
the
metallic
out
these metals
state; they contain
separate
and
these
latter
be separated
the preciousmetals
present,
may
furnace.
in the cupellation
which, in addition to
(6) Crude nickel matte or nickel speise,
nickel sulphide,always contains
iron sulphideor araenides
of

Smelting

for

Crude

Matte.

"

roasted

ore

"

these

metals, and, if

the

ores

contain

copper,

copper

sulphide.

398

SMELTING

ELECTRIC

AMD

REFINING.

(12) Cvhe-nickdy which may be melted in crucibles,placed in


and
into the
run
or
regenerativegas-furnaces,

wind-furnaces

of either

form

(13) Granulated nickel,or


(14) Nickel bars or plates.
According to another process,
nickel
copper-bearing
and

with

fused

which

oxides,the

the addition

is

specially
applicableto

mixture

of acid

oxides

of

fluxes,either

is reduced

in crucibles

In this way there are produced


(15) Sla^scontainingnickel and copper, which may

or

in blast furnaces.

be worked

up by adding them to the charge in smeltingfor crude matte, and


(16) An alloyof copper and nickel. This alloymay have a
limited sale,as it is produced. The remainder
to
is submitted
first
in
which
the
of
Eleotrolysis
sulphate solution,
copper
product is
Electrolytic
Accompanying this is an impure
copper.
Nickel
sulphoUesolution,which is purified
by chemical
18)
the precipitation
of the last traces of copper
processes, effecting
and the separationof iron,and is then electrolysed
(preferably
recoveringelectro-chemical by-productsat the anode),yielding
nickel.
(19) Electrolytic
Any preciousmetals that may have escaped separationwith

!17)

lead and

bismuth

(20) Anode
worked

II.

(5)will
slimes

in the lead and

up

in

Frocesses

during
This

which

the

in the

be found

which

and

Copper

Boasting

and

Nickel

Separated

are

Smelting

are

Stages.

suitable for the treatment


specially
process has been found
from the
of the Ciinadian
magnetic pyrites(pyrrhotite)
district

Ontario, containing nickel


however, up to the stage at which

Sudbury
This

in the Hafod

forty years

Co. in Swansea.*
The

first

for Process
The

Isha

Works

It has nevertheless

stages of the

process

are

been

in

been

for

use

of Messrs.
similar

the
H.

copper.
nickel is

thirtyor

H.

Vivian

patentedrecently.!
to those

described

I.

Boasting

productsas

and

of

process,
refined by electrolysis
(seebelow) has
"

which

(17), and
accompany
silver refinery.

in I.

the

of

Ore

is

conducted

in

heaps, the

being
acid,which, in view of the nature of the
SulpkwroiLs
(1)
roastingprocess used, can obviouslynot be utilised.
(2) The roasted ore (oxides,salts, undecom posed sulphides,
and gangue
subjectedto a process of
stuff). This is now
in blast furnaces, yielding,
for Orude
Matte
as
Smelting
in Process
"

"

I.,

Vaughan, Engineering and Mining Joumcd, 1893, vol. iv.


Patent 91,288, January II, 1893 (granted1897).

+ German

29^

NICKEL.

(3) Slags,which
(4) Crude

thrown

are

matter which,

and

away,

the method

departingfrom

employed

in the

first process, is now


in blast furnaces
under
conditions
Smelted
reducing
admixture
with sodium sulphateand carbon, yielding

(5)Mixed

matie^ which

separates into

in

layersin the slag"pots


solidifying.These layersare
specific
gravity,
and can
be readilyse2)arated
the
block
mechanicallyby striking
after cooling. It thus breaks up into
of low
(6) Tops^which consist of a copper-iron-sodiummatte
and
specific
gravity,
of higher specific
(7) BottomSy which are a matte
gravityand
rich in nickel.
the
free
not
Since,however,
suflficiently
tops are
the bottoms
from
both products are
from
nickel,nor
copper,
before

two

of different

re-smelted.
is conducted
of the
by smelting the
Tops
weathered
and
somewhat
after
have
been
[a
(12),
they
tops, (6)
with
solution
hastened
treatment
(21)],
by sprinkling them
The

Smelting

with

mixed

crude

conditions.

(8)

matte

(4) in

In this way
there
which
is
matte^

Mixed

reducing
produced
separated mechanically as before
blast

furnaces

under

are

[see(5)]into
(9) doncentratedtops, which
copper,

(10) Bottoms,
to the

are

poor

rich

nickel, but

in

in

and

process

Smelting
sodium

which

are

mixed

with

bottoms

(7)and

submitted

of
the

in blast furnaces

Bottoms

sulphateand

This

carbon.

the addition

with

of

produces

into
(11^ Mixed matte, which is separated,after solidifying,
which
which
in
but
in
the
are
nickel,
(12) TopSy
poor
copper

percentage must be increased by re-smeltingwith


(6). Meanwhile, however, the

(13) Concentrated
rich in nickel
of the

to

bottoms

warrant

are

their

in copper and
extraction

the

latter metal.

The

Leaching

of the

Concentrated

(14) A solution of sodium


evaporating ofi*the water, are
matte
(4),and

(15) A residue,which
contains
then

sufficiently
poor
treated
for
being

previoustops

almost

submitted

which

used

treatment

consists

well-known
which

in

the

(19) Gold.

yields

latter,after
of crude

chieflyof copper sulphide,but


gold present. This residue is
process 6f
there is obtained

Copper, by
(16) Copper containingpreciousmetals,which
Electrolysis, yieldingfinally
(17) Electrolytic
copper.
(18) Silver,and
Smelting

for

water

compounds,

all the silver and


to the

with

Tops

are

separatedby

300

ELECTRIC

SMELTING

Chloridifling Roasting

of

REFININO.

AND

the

reverberatoryfurnaces,followed

Concentrated

in

Bottoms

by

Iieaohing, have the effect of carryinginto solution the copper


and
of metala
part of the platinum group
By precipitating
this solution

with

cop|)er, there

obtained

are

pUuinum group of meUdSy which are separatedfrom


one
by recognisedmethods.
(21) Cuprie chloride soltUum^ which
is, in part, used to
hasten the weathering of the tops, (6)and (12),and is in part
of iron,from which is obtained
by means
precipitated
(22) CemetU-copper,
haUts consists mainly of
(23) The residue /roni the leacIUiig
nickel oxide, with
little silica,sulphur, copper,
a
iron, and
From
this
obtained
is
platinum.
by
(20)

The

another

Reduction

in

(24) Crude

nickel

which

are

eruoibles

ftirnaces, a

blast

with

the

(23),

in

impuritiesnamed

separatedby
in

Electrolysis
Anode

(25)

or

mixed

into
solution
for
is treated

cyanide

-mud^

which

the

recovery

of the

metals.
platinised

(26) Fragment* of

ilye anodeSy which

are

with

re-melted

the

(24),and
nickel.
(27) Electrolytic

crude

nickel

CHAPTER

III.

SILVER.
Silver

alloyed
gold,copper,
(hom silver),
AgCl ;
;
mercury
and iodide in bromargyrite (AgBr) and in iodargyrite
bromide
as
(Agl) ; as a sulphidein silver glance,Ag",S,both in a free state
ctjmbined
with
and
other sulphides e.g.y red silver ores and
be regarded as silver tbioantimonite and
fablerz
which
may
thioarsenite respectively.As a sulphide,
in more
too, it occurs
less noteworthy quantitiesin nearlyall sulphideores.
or
Silver (Ag ; atomic weight 108;
Properties of the Metal.
specific
gravity 10*5)is a white, highly lustrous,tough,and
malleable
of crystalline
metal
structure
(inthe regularsystem)
and with a low degree of hardness, intermediate
in this respect
between
and gold. Its conductivityof heat and electricity
copper
Its meltingpoint
is higher than that of any other metal.
approximates to 1,000"C, and it is volatile at high temperatures,
Occurrenoe

in

with

Nature.

"

or

as

occurs

native;

or

chloride

"

"

"

"

and

hence

it may

be distilled in the

electric

arc

and

before

the

X"A!

8ILVEB.

301

.'

and one
of silver,
oxyhydrogen blowpipe. A special
peculiarity
and
with
the
of
notice
connection
in
worthy
refining
working of
the metal, is its capacityfor dissolving
when in a state
oxygen
of fusion.
of solidificationthe oxygen
At the moment
escaping
from the still liquidinterior metal forces its way
through the
and
solid
rise
to
often
of
crust
a considermetal,
superficial
gives
ahle loss of silver by the projection
The
of small particles.
the spitting,
o
r
as
phenomenon is known
yegetation
sprouting,
of silver.

Among metals which


mention
special
may be
Silver is
or

low
Of

of

of those metals

one

in, or dissolved by, silver,,


lead,mercury, copper, and zinc.

soluble

are

made

which

be oxidised

cannot

high

temperatures,either in moist or dry air.


the metalloids,
have
and especially
the halogens,
chlorine,

the most

active

direct with

combine

tendency to

also be
united
with
sulphur by direct
may
sulphurcompounds, hydi*ogen
sulphideattacks
The

energy.
and

at

best chemical

solvents

silver ; and it
fusion.
Among
this metal

nitric acid and

are

with

trated
concen-

sulphuricacid. Various metallic chlorides (CuClg,HgClo,


Fe^Clg)readilyconvert silver into its chloride,and thereby

render

it soluble

soluble in water, are


its
silver,

haloid

Eztraotion.

"

waste
following

processes

salts;and

in other
formed

by

double

the action of

are

metallic

cyanideson

salts,or its sulphide.


addition

In

to the

intermediate

or

utilised

are

alreadymentioned, the

ores

the latter

other

productsfrom
for

the

derived

turing
manufac-

of

extraction

Pyrites
residues,regulus,
slags,
sweepings,and
Chief among

salts,which

silver:

"

alloys.

numerous

from

copper and lead


ores, and
containingthe precious metals, as black copper,
argentiferouslead, and the alloysof lead, zinc, and precious
metals

obtained

processes.
The extraction

from

those

are

argentiferouslead

is effected

accordingto

by

concentration

of the

one

following

principles
:

A.
1.

"

EXTRACTION

SOIiTJTION

OF
OP

THE

CRUDE

SHiVEB

THE

SILVER.
IN

ANOTHER

METAIi.
with
This process consists in converting
Treatment
Lead.
the silver,
other
in the ores
or
raw
material,into an alloywith
lead. When
the silver content
is low (less
than 10 per cent.)
the ore, "c., is smelted alongwith lead ores ; but when
the percentage
"

of silver is

immersed in molten
in order to

minimise

higher,the
lead.
the

material

In the former
loss of

to

be

desilverised is

event, it is necessary,

to
silver,

aim

at

aproducing

302

SMELTING

ELECTRIC

silver-lead with
the

lead

not

than

more

treatment

be

must

AND

RRPININO.

1 per cent, of silver,and therefore


followed
centration
by one of the usual con-

(the Pattinson
processes
alloyingwith zinc). The concentrated

crystallisation
process, or
silver-lead alloy,
silveror
lead-zinc alloythus obtained
is afterwards separatedinto metallic
lead and zinc oxide (or metallic zinc)by oxidation
silver and
distillation.

and

Attempts have been frequentlymade to effect the electrolytic


but, so far,without any
separationof these concentrated alloys,
permanent
but

in these

As

success.

lead

the

and

zinc

that

attempts it is
take part in

silver,

electrolytic
experiencegained in this connection
relegatedto the section dealingwith the electro-chemistry

only

reaction,the
will be
of those

recital of the

metals.
The

preciousmetals
ordinary temperature,as they are

Amalgamation.
at the

Silver

metals.
be

"

need

not

be in

even

extracted

are

soluble in mercury
readilyfusible

in all

free state in the ore, since


all ores
or
metallurgical

from

by mercury
productsin which it is present as a haloid salt.
working conditions,free silver sulphide also
it

the

not

the

can

that in the treatment

It is evident

mercury.
^chlorides and

requiredto

a
sulphides,

these

convert

of

suitable

Under
is acted
ores

by

on

containing

will be
of mercury
compounds, unless other metals, such
suitable

amount

added for this purpose.


Hence
copper, zinc,"c., are specially
of ores and metallurgical
in the amalgamation treatment
products
such
have
do
with
chemical
electrosilver
to
we
an
compounds,
containing
as

yet

not

The principles
of this process, however, have
process.
been fullyelucidated,
although Krohnke, in describing

which
has
ores
process for desilverising
used in Chili,Bolivia,Peru, and Mexico
since
^extensively
his well-known

"

"

expresslyrefers to the electro-chemical

nature

been
1863

of the reactions

involved.*

Whilst

external

no

amalgamation
Krohnke

based

process, numerous
to facilitate
electrolysis
reaction

the

of
preparatory treatment
have, however, been obtained.

with

is concurrent

No

ores.

order

is drawn
electricity
upon in the
the
same
on
principlesas the
propasalshave been made to utilise
amalgamation in processes where this
of

source

methods

the

In
practicalresults
this
of
the
most
noteworthy processes
repetition,
be described
in dealingwith the amalgamation of gold

to avoid

type will

section the reader is referred.


amalgam obtained by one or other of these

ores, to which

The

Solution
the
a

of

"

the

preciousmetals

part of the

the

and

distillation into mercury

separatedby

Silver

and

silver and

in

copper
most

by-productthat

contains

B.

Un

Krohnke,

Metho

zur

Copper.
are

an

When

impure
ores

is

silver.

containing

treated

of the
the

"

methods

by smeltingprocesses,
gold are liable to pass into

copper,

EntsUbfnnuj

iwi

and, therefore,under
1900.
Erzeti,Stuttgart,

303

SILVER.

certain
the

preciousmetals

theymight be with
silver alloyedwith
preciousmetals

are

those

Copper productscontainingthe
treated accordingto systems (2)and (3).

the

copper.

SIIiVEB

THE

OF

CHEMICAIi

OP

Ziervogel

The

not

are

8EFABATION

2.

itself. Ores containing


copper
with copper
thus smelted
ores, as
of lead,in order to obtain the gold and

circumstances, into the

Process.

PBOCESSES

BY

SOLUTION.

"

is

The

matte

smelted

from

in the

first

roasted that

the

ores
so
stage,
argentiferous
copper
in
whilst
the
other
is
formed,
products,
sulphate
copper
among
the
second stage (after
of
roasted
matte) a
previouscrushing
double decomposition takes place between
sulphateand
copper
of silver sulphate. The latter
silver sulphide with the formation
roasted
of hot
from
the
salt is then
extracted
chargeby means
acid solutions of copper
and
water
sulphate,and the silver is
the
from
finallyprecipitated
resulting liquors by metallic

and

copper
The

iron.

Ausiuitin, Patera, and

sabmitted

S^iss

Processes.

"

The

ores

are

roast, and the silver chloride is


chloridising
brine,in the
Augustin process by concentrated
sodium
Patera method
thiosulphatesolution,*and in the
by
Kiss modification
In the first
by calcium thiosulphatesolution.
the
metallic
the
is"
silver
i
n
state
case
by the use of
precipitated
metallic copper, in the other processes it is obtained
as
sulphide
the
soluble
of
addition
or
sulphides(Na.,S Ca(HS)2).
by
A
Process.
Dietzel's
descriptionof Dr. DietzeFs process
the
second
German
edition of this work
based on
in
was
given
him.
the patent specifications
and privatecommunications
from
Dr. Dietzel has publishedadditional particulars
of his process,!
and as these data are
based
recent
on
undoubtedly
experience
theywill be employed in the followingpages.
and
silversmiths'
The approximate composition of jewellers'
from
waste and the yellowishor bronze-coloured alloysrecovered
follows
is
:
as
metallurgical
products
extracted

to

in the

"

"

Au,
Ag,

.5-7

the
Consequently,
copper

per cent.

22-50

"

main

in the metallic

state ; and

of
electrolyte
consisting
*

[This salt

iflstill

objectis
a

weakly

which

commonly
properlyto
is requiredby the modem

text.

Translatob.

belongsmore

term

"

Zn, Sn, Pb,


Cd, Fe. Ni,

to

"^

the

acid solution

5 per cent,

this is effected

gold,silver,and
by the aid of an

of copper

nitrate.

knoMm
as
hyposulphiteof soda, but as this
the name
different compound altogether,
nomenclature
is
of
adopted in the
system

^Z.f. EUhrochemie,

recover

about

1899-1900,vi.,81.

304

SMELTING

ELECTRIC

REFINING.

AND

and
dissolved at the
silver are
copper
remains
undissolved; the copper being then
cathode and the silver outside the cell.
The

Solution

run

the'

depositedat

gold
the

off.

Fig. 174.
The

anode;

and supplementaryappawhich
in Fig. 174,
represents a cross-section of
dissolvingvessel. K K are the rotary, cylindrical,
copper

arrangement

of the

electrodes

i-atus is shown

the

cathodes, coated
which

the

with

thin

layer of

grease

on
graphite,

or

the
takes place. As
soon
as
copper
the
the dendritic form, it is knocked
as
and,
off,
The
smelted
with
charcoal.
it is
a little oxygen,

depositionof

deposit

assumes

copper

contains

copper

cylindersare

suspended

on

flangedcontact

friction between
in motion, the rolling
are
This method
causingthe cylindersto rotate.
set

rollers which

the

two

surfaces

presents the

vantage
ad-

that the
with

the

conductors

and shafts are out of contact


drivingmechanism
be oiled and used as
while
the bearings can
liquor,
for

supportingthe
hard

the cathode
material

to

current.

be

treated,S, and

or
rubber, celluloid,
glassplatesset

necessary, the bottom


The
*.
r, and rails,

is

loose

bottom

for

is constructed of

in wooden

frames.

If

arrangedto run on porcelainrollers,


P, are providedwith platinum wires,
plates,
with
insoluble
such
conductive
material
some
or
as
platesof
minals
resistant carbon, or even
of
strips chromium, forming the terof the insulated line wires.
That chromium
can
playthe
part of a preciousmetal has already been shown
by Hittorf.
These
inverted
roof-shapedbottom platesare well covered with
the material to be treated, which is now
usuallycast in the form
can

be

B06

SMELTING

ELECTRIC

AKD

REFINING.

the silver is all


the circulation of the electrolyte,
vessel but one is reached.
before the last precipitation
to

be demonstrated

deposited
This

can

hydrodiloricacid test. Nevertheless, it


possibleto prevent the small loss of silver
In practical
traceable in the granulatedcopper.
working,
finally
allow for a loss of 0*03 per cent, of silver,
must
one
though,in
the author's own
the
silver content
of silver
experiments,
average
in the copper
1
in
10
kilos.
was
only gramme
In its passage
from
vessel to another, the liquorfinally
one

has

not

by

becomes almost
dissolved iron

when

neutral,and
is

deposited as

under

material

the

fer been

so

is reached

iron,

the

tiie
the

Should

ferric salt.

much

contain

treatment

almost
precipitated,

this condition
basic

latter is

aerating vessel

an
(not
Fig.)provided with beaters,and is retained by a
filter. The
liquor next flows into a collectingtank, and is
pumped thence, or forced by compressed air,into a storage tank.
Here
acidified with nitric acid and returned
it is slightly
through
The percentage of copper
glasspipesinto the cathode chambers.

shown

in
quantitatively,

in the

in the solution

2 and 5 per cent.,and that of free


ranges between
nitric acid between
0*05 and 4 per cent.
The
current is
average
with
of 21
about 150 amperes
tension
mean
a
per square metre,

specifically
heavy mixture of gold ancl
silver,
generallyaccompanied by traoes of copper, remains behind
carriers.
The
residues are
dark
to deep
the anode
brown
on
The
black in colour,and
of granular to amorphous structure.
to 3 volts in the bath.

successful

exhaustion

to the fturt that

of the

raw

in this process is due


conductive
surface instead of

material

it is

supportedby a
beingfreelysuspended. Odd piecesof thick imperfectly-corroded
alloyare included in the succeedingcharge. The sediment also
contains

lead

(as peroxide)and tin (as basic nitrate or stannic


zinc, cadmium, nickel,iron,ifec,
pass into solution,

acid),whilst
where
they mostly
recovered

in

(except the iron). The gold is


by boilingthe sediment in dilute nitric

remain

pure state
acid, dissolvingthe residue
a

in

nitro-hydrochloricadd, filtering
stannic acid,and finally

off the lead chloride,silver chloride,and

precipitatingthe
thrown

down

with

metal

by

iron

in

the

chloride.

ferrous

of

process

Platinum

recuperatingthe

is
iron

solution.
of separationis
difficulty

According to earlier reports, the


proportionto "he amount

increased in
are

not

at
predpitable

anode.
fraction

Of
of

of associated

the cathode, but

become

these, zinc

in

particular

the

in

the

power

consumes

anode

of copper.
equivalentprecipitation
counteracted
be
electrolyte
by
may

insoluble
an

currents, and

This

that

metals

at the

appreciable
causes

an

impoverishment of the

slightly
increasingthe aciditj
of the store of desilveriaed
liquorbeyond the degree otherwise
most
advantageous ^namely,to an average of not less than 0*2
"

per cent.

Under

these

circumstances,copper

is dissolved at the

307

SILVER.

cathode, and

in the

precipitatmgvessels after the silver has been


deposited. Moreover, iiiepercentage of nitrous acid in the
liquor is diminished, the result being to retard the cathodic
of copper to such an extent
that it does not exceed
precipitation
the amount
and
introduced at the anode,
the electrolyte
is not
It is worthy of note
here that the
impoverishedin this metal.
of copper

presence

nitrate retards

the reduction

of nitric acid

to

be detected in the liquor


with
the low amperage
in
here
question. At the end of a year
the liquor is so rich in zinc and
other non-precipitable
metals
that it must
then worked
be renewed, the old liquorbeixig
up.

ammonia;

ammonia

least,no

at

can

lead and
metals, especially
tin,do
the
three
the
of
a
percentage,
separation
^proceedswith
principalcomponents
gold, sUver, and copper
So

long

the associated

as

exceed

not

small

"

"

the cost
uniformitythat the gain in copper not only covers
of the process, but even
whereas, a few years ago,
yieldsa profit^
such

this

metal

factor.
Even
with
regarded as a troublesome
and expena dailyquantity of only 130 lbs.,
sive
very difficult alloys,
the
does
exceed
of
usual
the
cost
not
steam,
separation
5d. per lb.,without
of about
making any allowance for
average
of
the
The
richer
the
gain
alloys in silver,and the
copper.
the
t
he
more
formity
since, in conthey are,
profitable
separation,
purer
with its high equivalent,
silver is deposited3-4 times as
for gold always ensures
The dry method
a
quickly as copper.
that the cost of refiningthe gold sediment
need
so
high profit,
be considered.
that the profitswill
And
it is evident
not
increase out of all proportionthe largerthe dailyoutput and the
was

the utilisation of the available

better
Andre

power.

the

separationof similar alloyslong


and
worked
the principleof dissolving
before
also
on
Dietzel,
and silver at the anode, precipitating
the silver on copper,
copper
the
of the electrolytic
and
the
cathodes
at
finally
recovering
copper
experimented on

apparatus.

of the

Most

Andre's

reports on

patent in

the

as
merely repeat the wording of the specification
the
With
and
nickel.
to the separationof copper
regard to
the following
of
and
he
makes
silver,
gold,
separation
copper,
s
tatements
:
interesting
The alloysor semi-manufactured
productsin question,in the
of granules or plateswith clamps, are
to the
form
connected
and
conductor
suspended,as anodes, in a bath of dilute (1:10)
acid.
the anode
and
Between
cathode is placed a
sulphuric
frame, which fits perfectlytight againstthe walls of the vessel,

technicskl press

"

*'

and

is covered

membrane.
one

on

either

side

with

cotton

fabric

this way the bath is divided


into two
for the anodes, the other for the cathodes ; whilst

itself

is

In

or

filled,between

granules,ifec. Under
"

German

the

the

Patent

with

membranes,

influence

of

6,048, Nov.

the

porous

chambers,
the

copper

frame
scraps,
and

silver
curreni^

1, 1877.

308

SMELTIHG

BLBOTBIC

diasolved

are

copper

admixtares
with
and

copper, on
the copper

In
the

copper,

cathode, the

the way

to

solution

arrivingat

in the frame

the

passingthrough

other

and

filled

the frame

deposited,

depositspure

consist
may
When
the

completely coated

is almost

gold

silver is

cathode

the

cathode
there.
The
copper
other
suitable substance.
or

metallic

copper
frame

ihe anode, whilst

at

behind.

remain

BBFIMIITO.

AHD

with

carbon*

of

granulated
silver,the

adhering to
recharged with copper, the cement-silver
washed
off
and
^j^ranules
being
cupellated.
This method
the consumption of acid
of separationreduces
furnishes
and
to a
minimum,
saves
labour,
chemically pure
of an
instead
for
electrical
suitable
purposes)
(very
copper
of
inconvenient
mass
copper sulphate.
is

the

"

""The

arrangement
from

"^The

the

cathodes

vessel,and

granular or
formed
by
such
"

over

principleof
are

the process
laid fiat or aslant

them

in

another

plate form). The


a

membranes
Here

modified

be

may

membrane
with

of low
a

small

again the current

"

the

on

come

of the

bottom
the

of this second

porosity,or

anodes

(in

vessel is

preferablyby

free space between.


of silver and
a solution

causes

parting
de-

vessel

bottom

follows, without

as

two

copper

uninterruptedlyremoved
at the bottom
of the vessel and
replacedby fresh,dilute acid
the
into a
The
silver
and
at
entering
top.
copper liquoris run
vessel below, where
the silver is depositedon granulatedcopper.
this vessel the desilverised liquor passes
From
into another
vessel,and is freed from copper at the catiiode.
Finally,the
is
drawn
off
from
into
this
vessel
a storage tank
liquor gradually
solving
below, and is returned to the anode for use over
again in disthere.
The
silver and
be
arranged
plant may
copper
mounted
stances.
terrace-wise
in a tower, according to local circumor
To
between
two
the
the
prevent diffusion,
liquor
v4ih
Lb run
and re-united
membranes
off,slowlybut continuously,
the silver and copper
be high or
the
Whether
terrace
liquor.
lowest
level always contains
three collecting
tanks :
low, the
No. 1 to collect the effluent liquor.No.
2 for the desilverised
solution,and No. 3 for the decopperisedliquor (dilute
copper
each
tank
is a pressure
vessel,from
sulphuric acid). Under
which
the liquorscan
be forced by compressed air up into the
three correspondingtanks on the uppermost terrace.
The vessels may
be of stoneware
wood
or
(petroleumbarrels
do very well),and the pressure
vessels may
be of wood, with
iron hoops,provided the pressure requireddoes not exceed that
of the atmosphere. For
higher terraces, small, lead -lined
used."
are
copper cylinders
to form

at the

anode,

which

solution

is

"

"

309

SILVER.

SOIiUTIOK

3.

OP

THE

CONSTITUEITTS

THAN

OTHEB

SILVEB.

Besides

the

Freiberg process for the


of copper mattes
treatment
by sulphuricacid,the Hai*z sulphuric
acid extraction
for
black copper containingthe precious
process
metals,and the Bossier process, by which the metals other than
removed
silver are
as
sulphidesby a smeltingprocess, electrolytic
Wohlwill's

methods

Prooess.

have

refer to

"

found

now

extended

an

the

It

use.

will

described
refining,

suffice to

electrolytic
length on
copper
also to the electrolytic
of crude
treatment
pp. 187 to 272 ; as
nickel and
of nickel-copper
::75
to 296.
explainedon pp.
alloys,
at

of zinc skimmings
treatment
Experiments on the electrolytic
of argentiferouslead will also be described in the chapters
dealingwith zinc and lead respectively.
The
for the treatment
introduced
of
by Wohlwill
process
of the electrolytic
alloys rich in silver after the manner
copper
with
the
of
and
is
use
sulphate as electrolyte,
refinery,
copper
worthy of specialconsideration,contrasting,as it does, with
and

the
silver
process, in which
solution
into
together. Wohlwill

Dietzel

the

carried

applying
The

that the silver

process
it was
present to

when

even

to

his

following

remarks

Borchers,

Dr.

in this work

verbal

copper
succeeded
in

quite

of about

extent

permission for

their

per

cent.

by him
publication

whole

of

small

quantity

of

gold, silver,and
by the

black copper
be recovered
platinum present
may
what
maximum
electrolytic
process, the question arises,to

proportion of

may
without

so

"

in

the

are

undissolved

30

privatelycommunicated

were

with

remained

the

the

"Since

the

and

preciousmetals

in copper
such a method

limit

alloysextend

rendering their separationby


impossible.
had
of
I [Wohlwill]have
an
opportunity
dealingwith this
the
1877-78, the
problem on a practicalscale,since, in
years
Confedeiuted
States
silver coinage of the German
small
was
in, and

was, for
for treatment.
Affinerie

called

the

most

By

the recovery

of the silver

obtained

sulphate. But,

large

as

quantitiesof

the

part, sent

the method

from
in

material

to

the

Norddeuisdie

commonly employed for


kind, the copper is
of the necessityto treat

alloysof this
view
in

short

space

of

time,

the

lytic
copper, such as is possibleby electrooffer
treatment, appeared to
specialadvantages. Experiment
the silver alloy,rich in copper, when
showed
that)in practice,

direct

used

I'ecovery

as

an

of metallic

electrode

sulphate,differed
in that
after

sponge

the

metal,

and

copper
that

from
rich
had

material

for

the

of
electrolysis

copper

argentiferousblack copper anodes, only


in silver remained
adhering to the anode
been

the sponge

extracted

covered

from
up

that

the

surface

part

of the

of

the

alloy

SIO

SMKLTIHO

ELECTRIC

which

below

M'a8

the

continuing

on

moreover,

surface,and

the

passed into the solution,and


with

covered
of

it

sm^ German
namely, the
"c.

^was, at

"

been cast into


"

coins sent

be

time, submitted

the anode

The

could

greater part

no

"^

the

for

Institute

separation
schillings,
pieces,
after
having
process,

6-kreuzer
this

to

that the cost of the ordinary

increased

considerablyby

considerable extent
to

secure

to
more
plate once
treatelectrolytic

plates.

It ia evident

must

th"t

Hamburg

way

coating by

and

rubbing

groschen,3- and

silver

that

cleaned

silver
became

natural

the silver

treatment.

to the

action;

the

of

sulphate. The

found

was

longerbear the mechanical

further

the anode

time

remove

the
the

continue

alternatelyuntU

"

short

to

submit

to

means,
and to
electrolysis,

to

in

sUver
difficultly-soluble

mechanical

checked

so

some
electrolysis,

was
obviatingthis difficulty

ments

REFIKINO.

AKD

necessary
full and
as

study

process

the

necessitated

of this kind.

conditions,and

fore,
there-

It was,
endeavour

to

to

action
as
electrolytic
of
silver
the
permitting any

an
long-continued

as

at the

without
possible,

in

electrolytic
process

the hand-labour

time

same

to pass into solution.


'" If
small quantity of silver
a very
even
solution with
the copper, difficultieswould

pass into the


arise,not only from

should

the
liquid immediately becoming milky, but also from
altered.
In
that
propertiesof the deposited copper becoming
dense
adhesive
and
instead
of
a
deposit,
reguline copper
case,
be thrown
down
liocculent clear red precipitate,
there would
a
containingsilver as well as copper ; and this would form a spongy
coating on the cathode. The operationof a bath that has so
deteriorated must
be suspended until every trace of silver has

the

been

removed

from

also
as
difficulty,

which

Uie

necessary
solution
black

good

copper
to

to

the

In

solution.

prolongas

much

is dissolved

and

order

to

it
precipitated,

and
apply a lower current-density
than
is
sulphate
employed in

to use

the

But, above
of the

this

the periodduring
possible

as

of copper

copper.
working

obviate

was
a

found
weaker

refiningof

essential
it was
everything,
anodes
that
freshly-scraped
process

to

the

should

less
be used side oy side with those on which there was
or
a more
the anodes of every
tank were
heavy coatingof silver. Hence
three groups, each oi which
divided into two
or
could, in its
the
of
be
submitted
to
mechanical
turn,
cleansingof the
process
Under
these
surface.
circumstances
the current
always divided
itself between
the anode platesof each bath in such a way
that
which
thinnest
the
silver
those on
became
subjected
depositwas
whidi
with
the
to the strongest attack, whilst
those on
even
the
thickest
of
s
olution
the electrolytic
depositwas
copper

proceeded graduallyto
being attacked.

silver

therefore,the

extraction

an

increasingdepth without any of the


By adopting such an
arrangement,
of the

copper

could,

on

the

whole,

be

311

8ILVBR.

preaaed farther

than

by

the simultaneous

treatment

of

similar

anodeplates.
''Alloyscontainingupwards of

30

per

cent,

of silver could

be advantageously
treated. As the proportionof silver is
increased the periodat which the spongy silver must
be mechaniit is possibleto
caUy removed is attained earlier. Similarly,
ascertain
the limitingcomposition,
beyond which the principles
of copper refining
applicable
i^pear to be no longer economically
of
with
other
of
the comthose
meUiods.
as
position
compared
Alloys
of the 5-gro8chenpieces (with about
50 per cent
of
be
this
could
not
treated
method.
silver)
advantageously
by
How
fiirthere may
be an advantage in alloyingsuch a material
with black copper in order to reduce
the proportionof silver to
that at which it may be convenientlyused for electrolysis
must
be determined
in each instance after takinginto consideration all
thus

the

circumstances

B.
In

of the case."

PRODUCTION

far

the

older

OP

FINE

have

SILVER.
for

their

object the
preciousmetals,gold and the
of the platinum group, they have been replacedby electrometals
lytic
in
works.
It
will
most
stood,
underbe
large
readily
processes
old
of refiningby fire,and
however, that the
process
Rossler's
improvements in the direction of removing the last
of bismuth
from
and
other base metals
traces
the cupelled
silver by fusion with silver sulphate,are always conducted
as
so

as

separationof silver from

processes

the other

heretofore.
ailyer containing
introduced
gold was
and
Moebius.
The
differs
from
practiceby
process
others used in refining,
in that the metal is not depositedin the
The

of

eleotrolymi

Wohlwill

into

form

usual

of

plates. Silver

if it be in the form
therefore be concentrated

loss,even

may
of a

be

fused,and without
easily
powdery deposit.Attention

the depositionof
effecting
as
since, owing to the relatively
rapidlyas possible,
metal, it is of the greatestimportance
high value of the prtK^ious
under treatment
that the periodduring which it remains
shall be
may
fine metal

upon

It is therefore desirable to work


reduced to a minimum.
with
the highestdensityof current that ia permissible,
without causing
and without
heating of the electrolyte,
risking
that
be
the
in
anode
impurities
present
may
from the
in tne electrolyte,llie growth of the silver crystals
or
cathode
until they reach the anode, and so form
short-circuits,
from
the cathode
be prevented by detaching the crystals
must
either intermittently
or
continuously.

an

unnecessary

the

depositionof the

Wohlwill's
Silver.
in

the

"

Gold
of
firom
Separation
the
made
1871,
experiments
early
year
silver electrolytically.
of separatinggold and

ProcaBs

Wohlwill,
direction

as

for

as

the

312

KLECTRIC

AMD

8MBLTIMG

RKFIKINO.

suggestionof the Board of the NardAffin"rie(under the directorshipof M. Salamon),


experimented first with the object of employing the current,
instead of the metallic copper hitherto used, for the decomposition
of the silver sulphate formed
by boilingthe metal with
acid.
My idea was to obtain metallic silver and strong
sulphuric
decomposition of the hot
sulphuric acid by the electrolytic
the acid being then at once
solution of silver sulphate,
appliedto
that time

At

*^

I,* at

the

deuUche

the solution

of

fresh batch

as
before,and
electrolysed

way, to be
showed
that in

of silver in the chemical

Experiments
using platinum electrodes,a large proportion of the
dissolved silver might be recovered
chemicallypure. The silver
of loose crystals,
which are
is deposited in the form
readily
separatedfrom the cathode,and in part detach themselves during
the process of deposition. But when, the solution being heated
become
to 100" C, the proportion of silver has
considerably
addition to
acid
in
be
to
reduced, sulphuric
decomposed
begins
and
with the result that sulphur,silver sulphide,
silver sulphate,
this
the
silver
out.
is
to
Up
sulphide separate
point
copper
in a pure white condition,and the darkening of the
precipitated
indicates that the practical
limit for the electrolysis
in
colour
deposit
If fresh silver sulphate
of the solution has been attained.
obtained by crystallising
out
the solution
obtained in the
added
to the electrolyte,
the precipitation
separatingvessels be now
this

so

on.

way,

"

"

of pure

silver

re-commences.

silver

The contamination
readilybe avoided, since

deposit by copper may


sulphate is only slightlysoluble
acid.

The

the current
but

process
for the

above

in hot

described

does

concentrated
involve

not

of the
copper

sulphuric
the

use

of

lyte,
productionand replenishmentof the electroof
obtained
solution
a
decomposition

restricts it to the

by chemical

means.

"Two

years
experiment with

later,in November,

1873,

it occurred

to

me

to

purely electro-chemical process for the separation


as
containing gold,using the same
electrolyte
before
^namely,a hot solution of silver sulphate in strong
then
not
of any
aware
sulphuricacid. As I was
satisfactory
for extractingsilver from
argentiferouscopper, I
process in use
and electrotyping
considered that as in electroplating
the strength
of the solution used was
kept constant
by using anodes of the
under
metal
out
treatment, a way might be found for dissolving
be
refined
the metal
which was
to
chemical
electroan
by substituting
method
of solution.
for a purely chemical
It appeared
probable that the precious metals could be separated if silver
should
be soluble,but gold insoluble,in a suitable electrolyte.
of pure
silver dissolved
Experiments proved that an anode
witiioutevolution of sulphur dioxide in the hot solution of silver
of

silver

"

fiummer

From

personal comniunication

of 1901.

from

Wohlwill

to

Dr. Borchers, in the

314

BLECTRIC

was

platinum,for
anode
oould

no
even

in the acid

safely be

however,

It

wires.

plfttinaiii-oovered
copper
tihat there

AND

SMELTING

need

the

for

REFINING.

was

found, however^

soon

protectionafforded

wire
pure copper
silver solution was

in contact
so

with

by the

the silver

attacked
slightly

that ii

the moment^
the purpose.
At
from mutual
removed
contact
is stronglyattacked,^m
which it is evident that the

when

the copper
with
eontact
This
lasta

for

employed

the two

the

metals

are

affords

protectiveinfluence while it
to further
observation
experiments in the
the auriferous silver to electrolysis
direction of subjecting
while
silver
in the granulated condition.
Granulated
placed in a
dish
the
whilst the
to
connected
dissolved,
positivepole
oopper
dish lost relatively
little in weight. In the same
it was
way
found
to work with the granulatedmaterial contained
practicable
with perforatedsieve-like walls, yet
in vertical copper receptacles
the advantages of using the anode
material in plateform was
at
that time
*'

nlver

led

apparent

Experiments

solution,to treat
such

also

were

14- and

made,

using

silver.
12-lothig

hot

With

silver

sulphate

material

rich, in

removal
of silver took
superficial
not
a
was
because,like the
possible,
used
for the suspension of the silver anode, the
wire
copper
the
in
alloy in contact with the silver is either
present
copper
but slightly
A higher electromotive
not attacked
force is
or
so.
and
then
of
soluble
a
difiicultly
layer
necessary,
copper sulphate
copper

place,but

is formed
"

of

as

this,however,

action
satisfactory

which

covers

tiie anode

prevents further

and

action.

The

of a hot solution
experiments sufficed to prove the utility
silver sulfate in sulphuric acid as the electrolyte
for the
of the silver from

the

The
results,
cupellingfurnace.
in this direction that it was
were
so
satisfactory
moreover,
decided by the directors of the JSorddeuUche Affinerie
to order an
electro-chemical
of
dynamo
larger output. Our requirements,,
which were
considerable,having regard to the positionof the
electrical industryat the time, were
that the machine
should
be
of silver hourly,
capable of depositing10 kilogrammes [22lbs.]
then stated whether
it was
not
although it was
expected that
this quantityshould be depositedin a number
of baths connected
in series,or in one
tank, or several coupled in parallel.Gramme^
who
understood
the requirement in Uie latter sense, and
fore
thereof
of
t
he
about
current
as
2,500
necessitating
production a
demand
of
not
hitherto
dismay^
was
a
by
magnitude
amperes,
unheard
of
of,but was prepared to undertake the manufacture
the requireddynamo.
Although the dynamo,^ when completed
treatment

"A
speoialdescription(with
EUectrolyw (Paris, 1888, pp. 229

to

of what
Fontaine
necessary
says on
actual
of
In
the
machine.
output

quoted bj' others,

the

intentions

in H.

oocurs
iilnstration)

an

of

Some

231).
p. 231
tnese

the

of

Fontaine's

correction, however, ia
the

book

statements,
manufacturer

concerning the

which
rather

have
than

been
the

315

8ILVEB.

the

give the full current of 2,500


deposit10 kilogrammes of silver
amperes,
in the hour, it was
capable of depositing60 to 70 kilogrammes
lbs
150
to
[130
J per hour with the baths suitablyarranged. At
all evente, it afforded me
the opportunityby the most
searching
oi
the
obtain
clear
of
method
to
a
investigation
conception
conductingthe industrial separationof gold and silver on the
above described.
principles
in

spring of 1875,
and

But

little remains
The

in the first

use

not

gation.
with i-eference to the investiacid
concentrated
demanded,
sulphuric

to be added

of hot

place,the employment

Lead,

which

was

tried

strongly attacked.

Iron

power.
very

did

did not

therefore

enamel,

such

as

were

obtained

of vessels
the

in

vessels
from

of

specialresisting
experiments,was
protected by suitable

earliest
the

Karlshiitte

Holler

in

enamel
mained
reRendsburg, gave unexpectedly good results.
after
and
attacked
the
iron
not
until,
was
undecomposed,
in continuous
a
long time, the acid of the solution (whichwas
use) had become too weak by the absorptionof water ; it seems
that unless the material
is proof against the action of strong
acids. Six
sulphuric acid,it is rapidlyattacked by the weaker
vessels of this kind, each holding 200 litres [44 gallons],
were
water
bath, and
arranged as silver baths, placed in a common
The
maintained
at a temperature of 100" C.
by steam-heating
baths
sometimes
as
a
rule, coupled in series, but were
were,
in
two
joined up
parallelrows.
Precipitates
ranging up to 2*5
The
kilos. [5^lbs.]
of silver were
obtained
hourly in each bath.
the
effects
of
directed
to
chiefly examining
experiments were
current-densityand the proportion of silver in the solution.
The

Both

exerted

marked

of the silver

increased

influence

precipitate.The

the iact that the

the

on

character

importance
of

and

of the

ness
adhesivelatter

acid
strong sulphuric

was

made

by
impossibleto isolate the anode, and therefore to keep apart the
from the two electrodes.
fragments falling
After some
2,000 kilogrammes [2 tons]of silver containing
gold had been treated by the method just described,the further
The
abandoned.
on
applicationof the process was
principles
based had been proved sound, and the
which the separationwas
of obtaining
of the separatedmetal in
possibility
largequantities
a short time
by the applicationof the current was convincingly
demonstrated
on
a really
large
; but the experiments conducted
use

it

^*

actual resulta

there given of the proceas


the account
given ; siinilarlj^,
in
the
conducted
Norddeutacht
aa
(which had
Affinerit
copper refining
had a still wider
also
inaccurate.
be
must
as
quite
currency)
regarded
of givinga complete insightinto the work, Fontaine
Under
the appearance
of individual statements
reallygives only an inconsequent combination
ooUectM
from many
which I [Wohlwill] had given him on various occasions
of ten years, but which
(mostlyin orderingmachines) in the course
by no
the
the plant had
that
to
means
same
during that
applied
object,seeing
time been subjectedfour or five times to radical alterations."
of

are

316

ELECTRIC

flcale showed

BMBLTING

there

that

AND

REFIHIMG.

practicalobjectionsto it.
the most
under
Moreover,
was
even
impossible,
of working, to prevent a part of the prefavourable conditions
cipitated
silver from
fallingto tliebottom of the vessel during
the progress of the electrolysis,
and, more
lifting
especially
so, on
the

caUiodes

although in
detached

were

found

it

of

out

much

solution, whilst at the same


quantity,a part of the slimes

the

smaller

the anode

from

many

be

to

and

found

time,
became

into the bath.

its way

The

in
of scrap, in part containing,and
resultingmixture
part
had
of
then
be
without, gold,
subjectedagain to the
necessityto
of a minute
The occurrence
refiningprocess.
proportionof gold
in the actual
silver
of
also
showed
that occasionally,
deposit
cally
mechanicarried
finer
even
w
ere
over
ciuring
electrolysis, particles

direct from

anode

the

cathode, and

to the

rendered

so

the

fine silver
of

the production
impure. Further, in order to ensure
cohesive
the
deposit,
thoroughly dense,
proportionof silver

in the

bath

solutions

had

to be maintained

requiredabout

fairlyhigh (each 200-litre


[13 ozs. per gallon!
compared with the usual

of silver

kilogrammes
and this,when
throughout the process),
be
regarded as a distinct drawback.
processes, must
There

'*

when

no

work,

17

had

one

difficulties to

other

also

were

had

which,

practicalexperience in

greater importance

present knowledge, would


**
be desirable
It may

attacned

was

than, in

to

to

reallyfallacious.
cupric

1872,

certainlyhave
nitrate

and

It

book
the

to

silver

two

that
the
upon

an

it

lightof

our

from

Lehre

solutions

for

electrolyte,
owing
At

ix"n

Gal-

later date

improbable

was

efiect that

nitrate

of nitric acid and


ecjuivalent
out

as

i.,p. 563).

recognised that
was

the

of silver nitrate

in Wiedemann's

statement

(editionof

vanismus

should

in

electro-chemical

appeared to be necessary.
I refrained
that
here
state

even
a
substituting,
experimentally,
of silver sulphate in sulphuricacid
one

faith

time,

have

solution

blind

that

at

mixed
is

and

solution

decomposed

of
;

equivalentof oxygen separates


the
whilst
at the negativeelectrode
at
the
positiveelectrode,
1

depositedin such quantities


correspondto exactly 1 equivalent,
relative proportionsof the metals in the depositdepending
the composition of the solution and the density. According
metals

"

the two

copper

and

silver

"

are

togetherwould

Becquerel,copper and silver are depositedin equivalent


the solution contains
quantitiesat a given currentdensitywhen
67 equivalentsof cupricnitrate to 1 equivalentof silver nitrate.
With
than
more
a smaller
proportionof copper salt in the liquid,
half an
of
silver
is
Before
equivalent
an
always deposited.
of obtainingpure
experimenter could contemplate the possibility
of nitrate solutions,it would
silver by the electrolysis
obviously
be necessary
for him to regard these statements
as
or
erroneous,
at least as suspicious.Since the material usuallycontains copper,
the solution
from
which
the silver is deposited must
become
to

317

SILVER.

constantlyricher in copper as the depositionproceeds,unless, as


in the process
of
previouslydescribed,a separate precipitation
be
silver could
take place. In this case, pure
should
copper
obtained
considerable
be
if
of
could
a
only
proportion
copper
without
the purityof
with
interfering
present in the electrolyte
the deposited silver. The statement
referred
to, however,
just
woidd

lead

also
Becquerel's,

expect

to prove

that there

EUmena

d^ Electrochemie

silver nitrate
nitrate in

and

was

misconceptionhere.
is explained that if

some

it

2, 4, 8, 16, 32,

solution

to the action

the

contrary. Another statement of


publishedlong since,would have been sufficient

to

one

of

100

in

and

BecquereFs

1 molecule
of

molecules

64

of distilled

parts

In

of

copper

water, be exposed

ordinarystrength,the
does
not
nitrate
begin to be decomposed until it is
copper
the
the
solution
in
in
present
proportionof at least 60 molecules
of the silver nitrate.
to 1 molecule
Although this statement
be
it
contains
clear expositionof
not
a
universallytrue,
may
that behaviour
which is based

of

continuous

of silver

mixture

the

of

current

of the
possibility

and

new

nitrates

copper
of

process

on

separating

silver."
The process,*
The
Moebius
Process.
patented by Moebiua
in several countries
in the year 1 884, was
first put into operation
in Mexico, and
then in the most
important separatingworks in
"

result".
America
and Germany with satisfactory
the Deutsche
Gold- und Silber-Scheide A natalt,which
Rossler's works
at Frankfort-on-Maine, has worked
and

the
which was
As

following

describes

the

In

this process,

that

practiceat

Germany
occupies

now

installation,,

under the care of Dr. H. Rossler.


have stated,!the apparatus has
several publishedaccounts

been to some
but they do not show any changes
extent simplified
in the principle
of the apparatus as described in the patent specification.
The

consist

vats
electrolyte

pine,tarred

the

on

at

present

inside, about

measurement)

and

of these

is divided

by

and

compartment

vats

compartments,
anodes

and

four

3*75

every
cathodes.

The

to

forwards
break

anodes

on

U.S. A

Patent

the

rim

off the silver

scrapers
the surface of the cathode, so
serve

tanks

of

pitch
(inside

width

contains
are

bags,the cathodes merely hang in


are
supported from frames, which
scrapers
backwards and

in

transverse

cotton

or

long

12 ft.] Each
length [2 ft.
partitionsinto seven

in

metre

of

0-6 *metre

that

of

suspended
are

the
as

free

vat;

of

rows

the baths.

crystals

all

three

in

linen

Wooden
to

travel

and

these

they grow

of the
possibility

upon

current

310,302 and 310,533, January 6, 1885 ; English Patent


Patent
16, 1884 ; German
36,610, December
12, 1884.
tMayoard, in the Engineeringand Mining Jottmal (New York), 1891,
voL IL,
fur Berg- und ffiUtenp. 556; Roasler,in the Oesterr. Zeitachri/t
der MetcUlhuUenkunde,
vol. i..
Vff^en, 1892, p. 288 ; Schnabel, Haiuihuch
Beeember
16,554,

^18

KLKCTRIC

SMBLTIliO

AND

becoming shortrdrcuited is avoided.


covering almost the whole floor area

[Fig.175.

"

The

Moebius

REFINING.

Under
of each

apparatus, showing anode

and
the electrodes,
section of the vat,

compartment

in half

section.

Fig. 176.

"

The

Moebius

apparatus

"

section

showing cathode^

319

8ILVBR.

is

deep tray with a linen bottom, which is intended to receive


principalportion of the crystalsdetached
by the scraper.

the

By

of

means

tc^therfrom

frame,

the vats

all these

arrangements

in which

be

lifted

The

silver

may

they
suspended.
a
anode-plates,
(Fig.175),which are
thick.
6
10
These
to
to
mm.
are
usually
[1 f in.]
suspended by
3iown
the double
from
in
metal
hooks, A,
a
frame, R
Fig. 177,
both as a support for the
serves
(Figs. 175, 177, 178), which
and
with
the current.
of
connection
For the
as
a means
plates,
latter purpose, it is placedat one
side,in direct contact with the
the
whilst
other
side it is separatedfrom the
on
conductor, P,
negativeconductor, N, by the insulatingsheath, I. In order to
be

to

refined

Fig. 177."

The

is cast

Moebius

are

into

apparatus"

section

through A

prevent the undissolved gold,which is left at


of a brown
powder, from mingling with

the

the

woven

cathodes, the

anodes

filter doth, which

(Figs. 175, 177);

frame,

are

and

are

enclosed

stretched

this

in

turn

on

is

(Fig.178).
anodes

in the

the silver brushed

form

from

RCE

in

the

bags
wooden

suspended

of

closely

support,
from

the

R.

The

soldered to
cathodes,k, consist of thin rolled silver plates,
which
in
is
horizontal
rod,
a
suspended
position. At
copper
each
end
of this rod, where
it projects beyond the edges of
a

i^e

silver

suspend

plate,is attached

the cathode

conductors

of the

supportinghook,
from the positive(P) and

bath

; the

hook

on

the

one

t?, which

serves

to

the

negative(N)

side

is therefore

320

SMELTING

ELRCTRIC

direct

placedin
but that

P,

shown

as

while

only one

in

with

connection

Fig.

is used

Fig. 178.

The

176.

conductors

both

REFINING.

side is insulated

the other

on

is that

ment

metallic

AND

The

the

available

supports,

as

the current.

Moebius

apparatus

"

plan.

N ( ),are thick copper, brass,or


rods ; and these rods must
not be only thick enough to
obviouslybe capable
carry the requiredcurrent, but they must
and their supports.
also of bearing the weight of the electrodes,
in number, are
The several sections of the vat, usually seven

The

conductors,P ( + ) and

from

made

are

to convey

"

negative lead,N,
tor,
positiveconducthis
of
advantage
arrange
the

bronze

coupled in series,as
electrically
sketched in Fig. 179.
The
and

arrangement

178 ;

provided
embrace

they are
for

the

each

shown

in the scheme

of the scrapers, ", is shown


in
wooden
which
of
slats,
simply

cathode-plate.They

cathodes

frame, F, shaped like

from
a

above,

and

grid-iron,
by

are
are

which

of

tions
connec-

Figs.176, 177,
two
pairsare

forked,

so

as

supported by
the

necessary

to

the
re-

322

SMBLTING

ILBCTBIC

that

as

the

nitric acid

percentage

of

AND

proportion of

the

increases

copper

be also raised ; the

REFIMINa

be lowered

should
currenirdensity

per sq. in.].


from
1*4 to

to about

The
1*5

200 amperes
[0*13ampere
per sq. metre
electromotive
force requiredwill usually vary

volts

cell.

per

Figs. 176

to

179

In

each
of

current

the

of
150

shown

compartments
(with

amperes

in

available

an

sq. metre,
sq. ft.)should suffice to
of silver from the anode to the cathode
transfer 21*6 kg. [47J lbs.]
in 36 hours.
Now, if three rows, each with five anodes of the
above-named
dimensions, be suspended in the baths, about 1*5

cathode

of 0*75

area

or

kg. [ 3*3 lbs.]of silver will


(or,in other words, almost

be

dissolved

from

anode-plate

every

of the silver introduced


stated.
will have been carried over
to the cathode) in the time
of
It is,therefore,possibleto treat quiteconsiderable quantities

silver within

small

area

whole

the

; moreover,

the

metal

only locked
very important
is

up in the apparatus for a short time, which is a


consideration
in dealingwith the preciousmetals.

The

cost

of

high,as may be easilycalculated from the data


complete; and,
separationof gold is practically
of gas.
the operationis conducted
without
finally,
any evolution
the heatingof the solution
In spiteof the high currentdensity,
of the
t
hanks
the
conductance
electrical
to
is very slight,
high
and especially
movement
electrode and electrolyte,
to the constant
of the solution caused by the motion
of the scrapers.
At intervals of 24 hours the whole of the apparatus suspended
be lifted out by
in the bath, includingthe silver trays, should
of
frame.
After
its supporting
means
allowing the trays to
drain into the bath they are
separatedfrom the electrode frames
be
that they may
and
taken
to the washing plant in order
emptied of silver deposit. This emptying is done, as already
indicated,by removing the pins which hold the bottom grids
cloth to the sides of the trays. The silver is
and the filtering
The
washed, pressed by hydraulicpower, dried, and melted.
the
anode cells are emptied once
to
twice
or
a
week, according
The
proportionof gold in the silver that is being refined.
will
further
of the anode
treatment
depend upon its
depasit
composition. (See Gold,)
the process is not
given above ; the

[The PennsylTania
introduced

1886, and

in

not

the

valuable

into

all in

in most

seven

use.

respects to

those

The

surface,and

solution

franklin

were

14

details of the

of

was

*[Joum^

^This Company

process at their PittsburgWorks


of their practicewas
given by

account

used
current-density

p. 356.]

"

tanks,each of which was


but that they were
cells,
separate electrolytic

constant

with

Plant.

Company's

It is stated that there

Faunce.*
divided

Lead
Moebius

the

0*125
of

Frankfurt

ampere
per
silver and

Ingtit.,18d5, and

Mineral

plant were

similar

installation.
sq. inch
copper

The

of cathode
nitrate

Industries,1895,

voL

con-

iv.,

323

81LVEB.

1 per cent, of free nitric acid,and a space of If inches


that each kilogramme
reckoned
the electrodes,it was

taining| to
between
of silver

other

80

The

depositedrequiredabout f H.P.-hour ; in
the equivalentof 1 H.P.-hour.
of silver was

ozs.

of 70

baths

(which

before

outturn

metal

other

and

to

had

been

use

less than

it contained

amounted

run

anode

The

fine.*

refined

per

diem,

average
and
the

by cupellationuntil
lead,copper, bismuth,

purifiedby the electrolytic


afforded a metal
ingots,
after
sljmes,
being granulated

far

so
impurities)was
when
crystals,

999|

ozs.

in all of

2 per cent,

that the

process
999 to

33,000

words,

into

parted,yieldedgold that should be 996 to 998 fine. When


much above 4 to
the proportionof copper in the electrolyte
rose
the vats and purified
off from
the solution was
5 per cent
run

and

to

the

remove

should

copper
would

tend

lead
and
copper
be present in the

this

otherwise

anodes, as

The

the silver.

depositedwith

to be

little

But

that it contained.
cost

metal

of labour

staff of three men


a
by
comparativelyslight,
whole
the
work
of
in
the
f
or
by night sufficing
the
the
of
well
the
with
for
connection
as
plant,as
management
addition
the
In
the
of
the
and
of
silver
gold.
refining
melting
to these hands
a
employed dailv in repairingand
carpenter was
number
of tne whole
renewing the tanks (about one-seventh
and a
and
of
for
thrown
out
a
mason
use
repairs),
beiiigalways
also required about one
machinist
were
day a week for general
in the process
day and one

work.

"

was

Translator.]

Accoitiingto Titus Ulke,t the cost of the complete installation


of a Moebius
plant for the dailyseparationof 933 kilogrammes
auriferous
of
silver,containing98 per cent, of silver,
[2,057lbs.]
The
of the
New
delivered
owner
in
York, is not quite"600.
patents guarantees
for the

gold,at
royalty of 0-1
such

an

in

was,
Later

of

per
if

oz.

for the

of 999

of 0-25 cent

cost

cent

apparatus
1897, about
Form

fineness

The

payable in

silver and

IJd.]per oz., exclusive


for the
fee demanded

one

instead

sum,

of

of 990
of the
use

of

by royalty,

"2,000.
Moebius

Apparatus.

"

In

newer

form

of

has
Figs. 180, 181, and 182, Moebius
band
endless
depositedupon an
which
of sheet silver,C ^^ in. thick],
constantlytravels over
in
the rollers,B, 6, in the direction indicated by the arrows
the depositedsilver
this moving cathode-plate
Fig. 180. From
of the tank. A, by the conveyor-belt,
is carried out
D, and

apparatus,t

shown

in

arranged that the silver shall be

The
the aid of the scraper, S.
pulley outside the vat and the chain-

delivered into the vessel,R, with


rollers

belt,n

are

O.

actuated
Within

by

the frame, E,

are

the

anodes, G, of gold-

[99-9to 99-95 per cent, of silver.]


f"hig. and Min. Joum,, 1897, vol. bciii,p. 211.
t [English Patent 469, Jan. 8, 1895, and 17.S.A Patent
*

1895.]

532,209, Jan. 8,

324

ELECTRIC

silver

bearing

SMELTING

placed

filter cloth,or

woven

AND

REFINING.

permeable support of denselyclayor the like. The electrical

a
upon
of porous
the anodes

between
and the conductor, K, is effected
the wires, M.
These
wires (compare Fig. 182) are
made
of
with
other
a platinum cap, pr, beneath, any
copper
portioiiof the

connection

by

wire

that

caoutchouc
between
aqueous

will

be

immersed

bath

the

in

being protectedby

to make
sleeves,r.
contact
the negative
cathode, 0. An
solution of potassium nitrate,acidified with nitric or

The

brush, F, is used
conductor, L, and the

"^^J5P|

-The Moebius

Fig. 181.

"

The

later form

process

form

; latest

Fig. 182.

Moebiiis
process;
of apparatus.

of apparatus.

The

"

connection

Moebius

care
sulphuricacid, is employed as electrolyte
; and
that the liquid is always sufficiently
taken
acid, and

neither too much

contains

[The

Perth-Amboy

Company
account

(ofwhose
has

been

Perth

it

"

New

to

from

erected

that

Jersey.

tanks,* forming eight groups


*
[This note is taken
vol. iv.,p. 356.]

that

little silver.

too

given above)

Amboy,

be

must

copper nor
The Guggenheim Smelting
Installation.
installation of the Thofehm
copper process an

plant,similar in the main


in

anode

(new form).

the

of
account

improved Moebius

an

just described,at their


Thei-e
six

were

each.

in the

48
Each

Mineral

works

electrolytic
tank

was

Industry,1895,

325

SILVER.

about

14 ft. 3 ins.

made

of

long,by 16 ins. wide, by 7 ins. high, and was


coated
with acid-proofpaint. In order to
pitch-pine,
the
economise
tanks were
floor space
placed in three tiers,one
above
the other, with a space of 1 ft. 6 ins. between
each pair,
the top of the uppermost tank being 5 ft. 6 ins. from
the floor
level. Every group of three superposedtanks was
separatedfrom
the remaining three of the series by a floor spcbce of 1 ft. 3 ins.,
and from
of another
the nearest
series by 4 ft. The
group
floor of the buildingslopedto a collecting
cement
pit 30 ft. long
by 4 ft. by 4 ft.,in which was a tank for the preparationof the
electrolyte.The lattef* should contain 4 to 5 per cent, of copper,
with
about
12 ozs. of silver per cubic foot (0'13per cent.),
and
about
0*1 per cent, of free nitric acid.
As
the electrolysis
ceeds,
prothis free nitric acid becomes
gradually neutralised by
copper
without

the

from

acidity;

those

silver treated.

of

anodes
On

an

of

contain
average

In

as

each

18 ins.

each

that

1,000

months

in four

once

of

ozs.

dor6

fresh

liquor to

portion

prevent undue

to copper.

there

six frames

(E, Fig. 180),18 ins. by


diaphragms, and every frame was

were

1 in.,with muslin
to hold four anodes
as

by

requiringthe
1^ lbs. of

copper
found

was

normal

The lead in the electrolyte


removed
was
by the
littlesulphuricacid at intervals to the solution in

tank

in

separate compartments, the


anodes
measuring 15 ins. by 3^ ins. by ^ }n. each, and being
composed of silver dor^ 980 fine,containing0*3 to 0*8 per cent,
so

of

divided

most

for

the

maintain

to

it

necessary

tank, whilst about


collecting
the liquid was
replaced by

enrichment

time

to

which

(1*35 sp. gr.) was

addition
the

time

from

acid.

of most

add

copper
passes into the solution
the cathode.
Fresh
nitric acid is,

being depositedat

therefore,added
use

which

anode,

wide, and

silver

The

gold.

coated

was

cathode-belt
once

was

fortnighton

31

ft.

long by

the outer

ins.

15

surface

with

of the
graphite composition,to prevent the firm adhesion
depositedcrystals. The belt travelled at the rate of 3 ft. per
of guttarpercha. The electrolyte
minute, the rollers being made
circulated through each group of tanks by gravity,
was
ultimately
iJbe
from
which
back
it was
into
collectingreservoir,
flowing
pumped into a distributingtank at a higher level after it had
been made
up to the rightcompositionfor use.
The generatingplant was
largerthan was requiredfor actual
but
in
at 90 volts and
1895, producing 220 amperes
needs,
was,
The
tanks
were
nected
condepositing24,000 ozs. of silver per diem.
of 1 ^ to 2 volts ; and
in series,each requiringa pressure
each receivinga depositof 660 to 700 ozs. of silver per 24 hours.
of engine and dynamo, the prime cost of the plant
Exclusive

necessary
at

to

treat

86,000, and

(tu^-)
P^""

^^-j

the

30,000
cost

of

ozs.

of silver dor^

refiningis reckoned

day
to

is estimated

be about

including the materials, interest, fuel, Ac,

|c.
and

326

SMELTING

ELECTRIC

REFINING.

AND

by night and of one


excludinggeneralcharges,
per
and royalty. A detailed estimate is given,but
superintendence,
to be
is not reproducedhere, as the figures
not considered
were
the
that
the
short
time
to
reliable,
owing
process had
perfectly
been in operation. Translator.]
the services
melter

of three

by day and

men

two

diem),but

(each at $2.25

"

Moebius

and

Nebel's

Apparatus.

It

"

would

that

appear

not altogether
experienceobtained with this apparatus was
would
because
it
seem
that, according to many
satis"ctory,

the

accounts, the

support
rupture
obviate

the

of
this

thin

film

apparatus
is drawn

crystalsadhered
exerted by
pressure

silver
the

that

"

band.

and

Moebius

difficulty
by keeping

the

scraper
endeavoured
Nebel

caused
to

coated

silver band

they use
forming an
trough,as in
long electrolytic

silver

often

the

of oil, for which


purpose
A cathode of sheet silver

through

the

firmly to

so

the

witii

following
band

endless
the

previously

the trough it in
the band
described apparatus. Before
enters
The
at O in Fig.183.
of the arrangement shown
oiled by means

Fig. 183.
silver

crystalsare

the

of

Moebius

"

swept

apparatus by

pressure.

The

and

off into
of

means

cells

anoae

are

modified

Nebers

apparatus.

receiver at

the

brush

working
suspended above as
a

oppositeend
at

definite

in the other

apparatus.'^
These
two

forms

of band

largeAmerican

apparatus

works

of the

have

been

used
chiefly

Globe

in the

and

Smelting
Refining
Company in Denver, Colorado, and of the Guggenheim Smelting
and
Refining Company in Perth Amboy, New
Jersey,respectively.
They, however, do not appear to be any longer in
of the
where
latter company,
the
operation in the works
apparatus working with scrapers is again employed. This
has
works
120
tanks
of
operated by a current
electrolytic
and
240 amperes
133 volts.
2,177 kilogrammes [over2 tons]
of fine silver are
obtained daily,correspondingto a monthly
and it is intended
output of 62,200 kilogrammes [over62 tons],
to bring the output of the plant up to 93,300 kilogrammes [over
93

tons]per

plates 5

'

this works

At

mensem.

ins. wide

by

12

ins.

U.S. A. Patent

the

anodes

long,weighing

are

between

592,097, Oct. 26, 1897.

cast

3-110

into
and

327

SILVER.

residue,
kilogrammes [100 to 111-8 ozs.]. An anode
the
after
left
is
from
2
3
to
to
electrolysis
amounting
per cent.,
tanks are joined up into groups
is completed. The electrolytic
of six,each group
forming a block about 13 ft. long, 25^ ins.
wide, and 22|ins. deep (insidemeasurement). A six-cell group
of this kind yields124-4 kilogrammes [nearly
2^ cwts.]of silver
of copper
in
5
3
cent,
from
to
daily. There are commonly
per
3-477

the

dor^
the

in

the

silver.

To

prevent

about
electrolyte

solution

450

undue

from

withdrawn

are

an

to 500

accumulation

litres
the

to 110

of copper
of
gallons]

[99
dailyand

tanks

replaced

present in the
by a
copper.
on
liquiddrawn off is then precipitated
copper platesin a special
vessel. The gold slimes are boiled in porcelain
pots
precipitating
each
provided with glasscovers, placed in a separate laboratory,
pot being capableof holdingabout 9-33 kilogrammes [20^ lbs.]
The silver solution thus obtained
of the slimes.
by decantation
with copper anodes.
the finely-divided
from
gold is electrolysed
of gold 990
about
The
24-88
kilogrammes [800ozs.]
plantyields
to 993 fine per day*of 24 hours.
fresh

solution

Fig. 184."
The

House-Symon

The

free from

tank.
electrolysis

Balbach's
Frooess.

silver

"

^Another

form

of

apparatus

by House, House " Symon,* but nothingis


its
known
use
exceptingthe statements of the patent
concerning
The
of
new
arrangement offers no simplification
specifications.
with
the
older
of
the
as
connections
or
moving parts, compared
will
therefore
suffice here to give references.
and
it
type,
^An apparatus patentedby Balbach f
Balbach's
Apparatus.
lysis
is simplerand has no mechanicallymoving pai*ts. Flat electrolined
with
and
184
the
metal
A
are
185),
cells,
(Figs.
forms
this
and
the
cathode.
is to be.^posited,
which
lining
are
Anode
suspended in the tanks,
cells,B, with grill-bottoms
has

been introduced

"

"

EnglishPatent

[See Joum, Soc. Chem. Ind


16,002,Auajust 22, 1894.
Zeitschriftfur Elektrochemie,1894, vol. i.,
1068.]
^^
588,524,and Englishi

1894, voL

xiii.,p.

p. 367.
+U.S.A

Patent

Dig^'fed^bvXiOQ

328

SMELTING

KLBCTRIC

AND

A, in the positionshown

in the

with

are

REFINING.

figures. The frames, C, covered


placed in B ; on these are

filtering-cloth,
Cp
arranged the metal bars,S, which are
again,at rightangles there is rested
whilst

contact-block,D,

the

metal, is placed either


the apparatus has been
the mud
time

now

which

to time

on
so

the first or

may

be found

unquestionablypossesses

be made

may

of

the second

on

the

is removed

from

necessary.

The

the

these,
bars,
same

After

run

bottom

Balbach

advantages claimed

the

row.

is
prepared,the electrolyte

separates out

as

which

be

treated ; on
second
of the
row

to

in and
from

apparatus

for it

by

the

-:%i
Fig. 185."
inventor

; but

it must

Balbach's

not

disadvantagesas compared
it is designed to displace. The
in the
of the

high

Moebius

the

such

therefore

rise to

this is of
as

be

Moebius

apparatus, which

scrapingand

apparatus give

and
electrolyte;

cun^ent-densities

that it also has certain

be overlooked
with

used

tank.
electrolysis

are

removing
a

very

brisk

devices
ment
move-

great importance with

here

desirable.

with

Balbach's

a
provided
specialarrangement
be necessary
and it may even
electrolyte,
to employ a man
constantlyin withdrawing metal, which would
add considerably
to the labour chargesof the process.
Silver is not very extensivelyused
of Silver.
Applications
in the pure
condition
of its inferior strength. Exaccount
cepting,
on
therefore,for the productionof pure compounds of silver,

apparatus
for

must

the
circulating

"

330

ELECTRIC

0*00003

cent,

per

of

SMELTING

AND

REFINING.

suffices to

antimony)

destroy the

malle*

abilityof gold and to make the metal weak and brittle.


In its chemical aspect,goldis one
of the most
stable of metals.
Its oxides and sulphidescan
and
be
only
produced indirectly,
chlorine and
easilydecomposed. Halogens,especially
these
which
evolve
bromine, and mixtures
(like(tqtta reffia)
the
thiosulattack
Certain
such
elements,
as
salts,
gold readily.
phates and cyanides,may form with metallic gold double salts
that are
soluble in water
(SNa^S^O, + AuS^Oj + iHjO; and
the
form of thiosulphate,
gold does not
KAuCyj). Excepting in
tend to play the part of base to oxygen
acids,but its oxide may
are

very

act

as

acid and

an

form

aurates, with

salts,termed

Sulphide of gold dissolves readilyin


sulphidesto form thio-salts.
Gold

the

possesses

be

lowest

precipitatedfrom

of

solutions

other
the

bases.

alkaline

of all metals.

solution-tension

the

its solutions

It

weakest

by even
may
reducing agents, and is thus separated in the metallic state
through the agency of hydrogen,phosphorus,arsenic,antimony,
carbon, by nearly all metals (exceptingfrom cyanide solutions,
from
which it can only be depositedby zinc and metals
more
the
metallic
than
electro-positive
zinc),by
sulphides,by
protosalts of iron,tin,"c., by hypophosphites,
and sulphur
sulphites,
and by arsenic, oxalic
dioxide,by the lower oxides of nitrogen,
and
substances.
acid,
organic
many
Extraotion

of the

the extraction
be

in the
crude

other

from

gold
arranged in

of

of most

case

but

for
processes
very numerous
and other materials containing

The

"

ores

fundamentally different ways.


to extract
gold first in
metal
to one
or
form, and then to subjectthe impure
the different refining
processes.

it, may
As

Metal.

of

few

metals, it is usual

EXTRACTION

A.

OF

GOLD.

CRUDE

impure gold is effected almost exclusively


by
followingmethods, in all of which the application
less success.
of electricity
has been attempted with more
or
The

of the

1.

its ores,

Ore.

and

"

The

the

extraction

work,

TREATMENT.

All

propertiesof
applicationof mechanical

immediate
this

MECHANIC
of the

Treatment

of

of the

extraction

one

manner

the

metal
methods

in which

gold occurs
itself,
permit the
of

treatment

to

in
tended
ex-

the

Having regard to the scope


impossiblehere to discuss the

of the metal.

however,

it is

of such as are
of these mechanical
principles
processes, or even
These
in character.
are
exhaustively
principles
electro-magnetic
extraction.
treated in many
treatises
on
good special
gold
The
has hitherto
found but isolated applielectric current
cations
for
in the
mechanical
and
electro-magnetic
processes

331

GOLD.

of auriferous
^for example, in the treatment
treatingthe ore
sands.
like
those
of
Processes
Noad,"^
Baker,t and
magnetite
of electroothers are not adapted to effect a generalapplication
Noad
treatment.
the
to
coat
proposed
magnetic
gold particles
in the ore with iron by electrolysing
slimes in which
iron
ore
tungstate had been dissolved,and then to separatethese particles
the other hand, proof electro-magnets.Baker, on
by means
posed
with an
iron amalgam, in order that
to treat the gold ore
the gold contained
magnetic
in it might be made
subject to electro"

influence.

SOIiUTION

2.

OF

THE

IN

GOIiD

OTHER

METAIiS.

it will
Concerning this method
of
suffice to refer to the remarks
the correspondingmethod
on
In
where
the
silver.
is
cases
adopted (and
extracting
system
that is,of course, where lead smelting is in operation)the gold
treated
ores
uniformly contain a far largerproportionof silver
is also present a part of the gold
than of gold. When
copper
such as the matte
always passes into the copper-bearing
products,
with

Treatment

and

metallic

and

the

the

Silver.

on

here

It may
immerse

the

solution

of the

be

mentioned

auriferous
sent

which

it

of

ore

that it has

to

by

due to

it,are

proposed to
to

hasten

the

electrical means,
electric
an
it rises through the lead
as

through the ore


has been
plunged.

givingeffect

also been

lead, and

in molten

preciousmetal

being

beneath
means

"

of poor work-lead
The
concentration
copper, "c.
described
in
have been sufficiently
process of cupellation

Chapter

current

Iiead.

This
an

invention, and

American

of the

tlie
name

of Cable.*
of gold
of Amalgamation.
In the treatment
the amalgamation is generallyassociated with the processes
of mechanical
preparation. As has been stated above, gold
in the free condition in the majority of ores, and, unlike
occurs

Principles

"

ores

silver

in many
of its ores),
it is therefore capable of
being submitted direct to the solvent action of the mercury, at
least when
with the mercury
is
the contact of the gold particles
not

(asit occurs

prevented

or

rendered

too

of the metal

from

difficult

in its gangue,
the crushingof the ore.
The

and

division
subby a very minute
in the slimes which result

can
applicationof electricity
where
service in cases
the
scarcelybe expected to be of much
size of the granulesof gold is fairly
that
the
of
large,so
particles
metaJ
laid bare by the process
of crushing to
are
sufficiently
enable
that
to
at
begin even
amalgamation
stage. In experiments
been
with
the object of hastening,or
that have
made
*

EngUsh

t U.S.A.
+

U.S.A.

Patent

Patent
Patent

6,810, 1886.
537,336, April 9, 1895.
274,083, 1883.

332

8MELTIHG

ELECTRIC

otherwise
means,
nature.

of

improving, the

the action

by electrical
process
of an electro-chemical

amalgamation
has been

of the current

Whether

REFINIKO.

AND

intentionally
so,

otherwise,the originators

or

gold
liberated
treatment
amalgamation
would
be capableof dissolving
either
by
electrolytically, directly,
of the gold with the anodes, or indirectly,
the contact
owing to
the action of solvents produced at the imodes.
In either case,
the dissolved
of the
surface
would
the
gold
precipitateon
these

processes
during the

created

under

conditions

which

ihe

and

mechanical

which
is connected
mercury,
up as the cathode in the cell.
those
In
Eleotro
therefoi'e,
Amalgamation.
processes,
which
be grouped together under
the heading "Electromay
-

"

Amalgamation,"

have

we

of auriferous

treatment

electro-chemical
of

or

mercury

deal

to

chieflywith the electrolytic


the gold is dissolved
by
depositedon a cathode of

ores, in which
and
is then

means,

contained

amalgam

in the

appaitktus.

same

The process patented by Molloy * forms


Frooess.
In this process the ore is
of the few exceptionsto this rule.

MoUoy's
one

"

brought

in contact

cathode

of

sodium

with

dilute

salt,or

film of mercury

pulp

on

plate acts

bottom

the

forms

of

The

ore

the

the

the

same

time

as

as

of the

contains

on

The

anodes.
mercury

one

or

its
ore

cathode.

proposed by Molloy to
of one, resemblingthe
description
into the

hopper,T, which
bent

upwards

a circular rim ; it may


it is attached
to which

spindle,W,
hangs suspended

a
way
either of the

suflSce.

(Fig.186),through
This plate is
the plate,
B.
80

that

been

have

is introduced

to be treated

and

function

surface

upper

Mill, will here

that it forms

by

means

mentioned,

apparatus

the mercuiy
solutions of

flat vessel filled with

plateswhich

the

over

to

cover

above

but
accomplishthis object,
old Chemnitz

speak,of

aqueous
decomposed in such

condition

pure

the

as

lead

or

passed

Various

to

separatedhydrogen. The
electrolytically
the cathode
forms
is,with this objectin
horizontal
of
clay. This
plate
porous

solutions

carbon
is

which

view, supported
of

back, so

acids,are

the mercury
is kept in
sodium
of
or
deposited

porous
other

the

cell in which
electrolytic

an

vessel,
electrolysis

forms
at the

be rotated

by

cross

the

centre

of

circumference,

by

means

bar, so

of

that it

at the
layer of mercury, K, that serves
upon
for the current
solvent for the gold and as cathode
a

by the stirringmechanism, 0,
platewhich is taperedoff at the
mercury
part below the hopper ; owing to the rotation of the plate,the
the surface of the mercury
take a spiral
now
course
over
particles
the edge of the plate
until they reach the annular
space between
and the wall of the vessel. Here
they are kept in motion by the

The

particlesof

between

the

ore

are

and

driven
the

German
Patent 28,452, Jan. 8, 1884.
[English Patent 143, Jan. 1,
Patent 36.S,411, Mav
1884.] U.S.A.
24, 1887.
[English Patent 15,206,
Nov.
22, 1886.]
*

335

GOLD.

stirrers,
o',attached

to the

are

discharged
finally

on

circumference

which

diaphragm,D,

of the
of

is made

plate,and

The

rim, G.

the outer

over

they
rests

mercury

clay,cement, leather,

wood, from which the resin has been extracted,or other suitable
material,and which forms a tightjointboth with the outer rim
of the

vessel

Anodes
of the

with

and

of carbon

vessel,G,

or

and

the

sheet

socket

lead.A,

of dilute

are

sidphuricacid,of

at the bottom

and

the

S, serve

diaphragm,
respectively

which
electrolyte,

of the
caustic

spindle,W.

shaft

introduced

the space between


them
sand.
The tubes,Z and

is filled up with
for the supply and the removal

D,

the

of

of

soda, or

consists
salt in

sodium

during the
from the
be made
to slopeslightly
process, the diaphragm must
outlet
centre to the cireumference,and, at the highestpoint,an
the conducting
and
P are
must
be provided for the gas.
N
solution.

Since

is evolved

oxygen

wires.
The tube, R, is intended
from the cathode compartment.

Fig. 186.

Tho

"

the

at

anode

for the removal

of the mercury

MoUoy amalgamating pan.

and
Process.
Breakell
Hayoraft's
By far the greatest
of processes proposed for electro-amalgamation
are, a.s
concerned
with
and
stated above,
working conditions
apparatus
"

number

aiming
suitable

at

the

electro-chemical

have
electrolytes

been

treatment

dissolved.

of ore-slimes

in which

According to Webber*

the first
made
who
and

of this kind were


experiments in electro-amalgamation
Breakell
and
in
1882,
Australia,
by
Haycraft,
the
bottom as cathode,
employed vats containingmercury on
providedwith a stirrer which not only kept the slimes in
in South

motion, but itself acted


made

as

to the nature

Barker's
same

year.

of the

Process.
In this

provided with

Mectrician, 18d8

"

anode.

No

indication

added
electrolyte

Barker's

apparatus

invention
launders

is, however^

to the slimes.

patentedin the
carrying slimes were
was

rifflescontainingmercury,

cross

p. 552.
t German
Patent
June 28, 1882.]

as

and

immediately

cf. Zeitschrift
fur Elektrochemie,1897-8, vol. iv.,

22,619, October

26, 1S82.

[English Patent

3,046,

334

ELECTRIC

above

them
also

were

AND

rollers,with

were

REFINING.

stirrers

attached.

two

for

purpose

they

the way

led

patents

which

to

series of

the

of innumerable

use

The
electrolytes.

as

time

the introduction
of a long
conceivable arrangement for
of

ores,

of the

variations

number

were

originallyintended.

were

apparatus,embracing every
and amalgamation
preliminarytreatment

uKed

stirrers

this way the launders


employed
into an electrolytic
apparatus, whilst at the same

serving the

the

The

In

anodes.

as

converted

These

SMELTING

of substances

and

volving
in-

salts to

available

be

must

Naturally,the only salts that can be used


those of which
the anions are
are
capable of forming soluble
such
with
salts
are
compounds
gold;
chieflythe haloids and
cyanides. The most varied mixtures of these salts have been
recommended, with the objectof settingfree combinations of the
themselves,as well as the solvent for the gold.
halogens among
It is scarcely
with
that deconsonant
the object of this work
tailed
of
should
these inventions
accounts
be given here, as
they have not progressedbeyond the experimental stage. So
to the author, experimentalplants on
far as is known
a
large
been
scale have
put down only in the case of the followingprocesses

obviouslybe

small.

:
"

1.

Adelaide, for

In

already referred
with

the

on

the

Breakell

and

Haycraft

this process an
iron
heatingarrangement is employed, and a
bottom

to.

"

In

of the vessel
of

solution

serves

salt,and

vessel
electrolyte
layerof mercury

cathode.

as

is

Process*

The

in motion

ore

is

pended
sus-

mechanical

kept
by
and are
spindle,
providedwith
The
o
f
carbon blocks as anodes.
largerparticles gold in the
and
become
sink readilyto the bottom
ore
amalgamated as in
whilst
the
extraction
lighterand smedler
ordinarygold
processes,
the
of float-gold
chlorine liberated at
dissolved by
are
particles
the resultingsolution of chloride is electrolysed
the anode, and
by the current, the metal being depositedupon and dissolved by
is effected at a boiling
cathode.
The
the mercury
electrolysis
in

stirrers,which

are

attached

to

out
temperature. After about an hour the ore-slimes are run
from which
into a reservoir,
they are led to a percussion-table
of recovering any detached
of mercury
for the purpose
particles

that

amalgam

or

here

may

be

caught in

them.

reservoir

are

and

to

are

for
Afirica,

Process

of

tailings
passing
ore
particles
separatedfrom them

in which

conveyed
whilst the clear solution
deposited,
againbrought into use.

from

The

is

the

Hannay t uses
the liquidbeing con^
potassium cyanide solution as electrolyte,
tained in amalgamating vats of very simple construction.
His
different methods
of carrying
contain
two
patent specifications
2. In South

"

Engineeringand

English

1894.

Patent

Hannay's

"

Mining Journal (New York), 1895, vol. lix.,p. 490.


19,181, Nov. 25, 1890; and U.S. A. Patent 529,263,

335

GOLD.

out

his

anodes
in

kept

188). In each of these the


and the slimes are
funnel-shaped,
of a revolvingscrew
them
by means

object (seeFigs.187
are

made

hollow

circulation

and

around

and

Fig. 187.

Fig.

188.

rata.
Hannay's electro-amalgamating

stirring apparatus.

In

one

of them

upper

platearranged
copper
part of the vat, whilst in

ridged on
the

bottom

its upper surface


of the vat.

the

cathode

is

an

mated
amalga-

in the
partition
filtering
the other it is a copper
plate,
and covered with ^le^cury, restingon
behind

336

KLSCTRIC

SMELTING

AND

REFINING.

3. At

CrippleGreek, Colorado, for a Process of Bailey's* for


trough amalgamation using iron anodes in potassium
pan and
solution
cyanide
containingoxidisingagents,or in strong sodium
chloride

solution.

for a Process of Rae's t using


Douglas Mills,California,
anodes
vat amalgamators with
attached to stirrers,and
with
cathodes
solution
in
of
a
as
amalgam
cyanide electrolyte.
4. At

5. In
for

Denver, Colorado,and later in Rossland, British Colombia,


of

Clerici's.tThere is but little


the
apparatus employed in carryprocess
ing
Like many
of their predecessors,
it out.
the inventors
use
bottom
of
which
the
the
on
are
cathodes,
amalgamators,
Process

Pelatan

in the
originality
vat

of
consisting

and

"

and

mercury

and

These

salts

whilst the
amalgamated copper plates,
the cathodes.
over
anodes, attached to stirringmachinery,move
Various
salts are specified
in the different patents,and mixtures
of potassiumcyanideand sodium
chloride are ultimately
selected
the

as

best.

solution

which

solution

density,which
the

used

are

in the

of

form

an

aqueous
of

and

containing0'2

1 per cent.
per cent. KCy,
The
3 parts are used to 5 parts of ore.
must

be

regulatedaccordingto

about
16 amperes
As the
surface.
of
catiiode
amp. per sq. ft.]
interested
and
are
by
parties,
process are

electrolysis,
averages

NaCl,

current-

the progress

[1-5

sq. metre

per

of

explanationsof the

unaccompanied by
them.
experimental evidence, it is not necessary to mention
who
has
the
Pelatan-Clerici
with
Witter,"
experimented
process
in the Government
bility
laboratoryat Hamburg, confirms the possiof from
of obtaining an
75 to 95 per cent,
extraction
from

oi-es

the

by
time

which, however,

cyanide process

he alludes

to

the

hereafter

suited

well

were

referred

for

to, but

disadvantagesentailed

treatment

the

at

by

the

same

use

of

In
required for. the process.
large quantity of mercury
which
50
of
tons
in
ore
experimentalplant
3,000
were
daily treated in 10 amalgamating vats, about
have
been
must
stantly
kilogrammes [3 tons]of mercury
kept conthe

the

abovenamed

in
6. At
for

use.

Process introduced by Motz.

amalgamator
true, shows
with

of the Utah

the Works
and

sluice for

that the inventor

these difficult

and

Mming
"

the

slimes.

has had

problems than

had

Redaction

Company,

has constructed

Motz

more

most

barrel

The

it is
former,]]
experiencein dealing
of his predecessors
;

"U.SA.
Patent 531,269,of 1894.
i Electrical Heuiew (New York), 1897, vol. xxiii.,p. 3.
U.S. A
Patents
XZeitschrift
fiirElcktrochemie,1898, vol. iv., p. 552.
528,023, of 1894; 553,816, 567,503, and 568,099, of 1896; and 623,822
and 627,442, of 1899.
English Patents 2,493, Feb. 5, 1895 ; 24,803, Dec.
27, 1895 ; 22,256, Sept.28, 1897.
%ZeU6chri/t/ur Elektrochemie, 1898, vol. v., p. 23.
Patent
IIU.S.A.
582,077, of 1897 ; c/. also ZeUdchriftfur Elektrochemie^
1897, vol. iv., p. 259.

338

e"|uallysuitable

is

8MELTIKG

KLBCTRIC

and

for

the

REFINING.

AND

direct

of slimes

for the after treatment

from

Imttery slimes
amalgamating

of

treatment

other

apparatus.
7. A

of Jor^B/

ProceSB

above,

has

author

has

given

results

on

large scale, but

the

where

ascertained

not

described

the invention

from
differing

favourable

trials

made.

were

the
The

a
amalgamated copper
to the direction
suspended close togetherand parallel
of the flow of pulp. Only the finest portionsof the ore
are
allowed
to flow,suspended in water, through the sluice so
pared,
prethe plates
an
alternatingcurrent being passed between
the
the platesthrough which
meanwhile.
The space between
0*5
the
flow
is
slimes
mm.
[0-02in.].
during
battery
process
is stamped
The chief condition
for this process is that the ore
fine as possible
and is run
as
through the sluice in the form of a

apparatus

of

consists

sluice

in

which

met

with

platesare

The

thin slime.

has

author

not

further

any

statements

results.
practical

of

IiEACHING

3.

been

With

the restricted number

in the

PROCESSES.

be also classified in this group


processes which
may
the head
of Electro^malgamation.
referred to under

Several
have

PBBCIPITATIOir

AND

of solvents

metallurgical
industry,two

which

processes

can

have

be

employed
generallybeen

employed.
Chlorination.
John

by

E. Rothwell

at the

use

Plattner chlorination

The

"

in the

present time,

text-book.

United

is described

and

process,

perfected

as

States,is in

extensive

very
in every metallurgical
been made
to produce

experiments which have


either within
or
by electrolytic
means,
necessary
the chlorinating
have
without
led
not
to the supervat,
yet
session
methods.
The
of chemical
electrolytic
separation of
The

the

chlorine

from

chlorine, even
; and

of

slimes

ore

chemical
A

way.

ores

few

processes and
which
The

of

Cassel

of

that

culties
diffi-

so

in the

suitable for chlorination

are

examples taken

Process.

the

this kind

apparatus of
still stand

from

"

ExtractingCompany t

"

that

^has been

and
publicin exhibitions^

largenumber

will

in the way of
One
of the

"

the

salt,offers many

the

apparatus proposed namely,

Gold

of

greatlyincreased by the introduction


electrolytic
apparatus, that the purely
producing chlorine is always preferredfor

are

into

method

with

use

these

solutions

clear

to show

serve

ordinary
patented
the difficulties

chlorination.
electrolytic
least useful
of

Cassel

most

and

of the forms
the

brought
journals.

often

in the technical

of

Cassel
before

Engineeringand Mining Joum., 1894, vol. IviiL,p. 440.


t U.S. A Patents
Patent
300,950 and 900"951, June 24, 1884; [finglish
^yS7Z, August 6, 1883]; U.S.A. Patent 362,022,April 26, 1887; German
Patent 38^744,
May 14, 1886; [EnglishPatent 8,"74,July 16, 1886].
t Inventions

Exhibition,London,

1886.

339

GOLD.

dram

polygonalcross-section was made of


that it might be rotated
so
porous
which
about
its long axis,
the
was
placed horizontally
; within
rods placedparallel
drum
of carbon
to the walls,
were
a number
and about half-immersed
in a vessel containinga liquidin which
cathode
a metal-plate
was
suspended. The gold of the ore was
be
the cylinder and
within
chloridised
to
deposited on the
cathodes
outside.
The
solution
of common
was
a
electrolyte
It
be
suit rendered
alkaline
lime.
by
safelyrecognised
may
that the apparatus is not of practical
if it be i*emembered
utility
that it might have to be used in the treatment
of ores
containing
A

of

or
cylindrical

mounted

material,and

some

less than

hundredth

or

thousandth

gold ; that, in order to obtain a


weight of gold,from 5 to 50 tons
might

have

to be introduced

within, and
clear

in

solutions

of

destroyed,would
of about
that

formed
space

only
with

of

of

ore

the

atus
appareven

quickly

are

the

last out

traction
ex-

of ore;

1 ton

and, finally,
largecapitalwas

company
and worked

of

pound

anodes, which
salt

cent,

into,rotated

dischargedfrom,

; that the carbon

part of 1 per

this process

for the

year.

Body's process and


apparatus* has alreadybeen described in
the Chapter on Copper, It testifies to a
of the diflSculties to
better appreciation
lie overcome.
Although the patent shows
Process.

Body's

distinct

in

cases

"

advance, it will

where

ores

have

be found
to

be

better,

extracted

with
ferric solutions,to treat them
the liquidoutside the electrolysing
vessel.
with

The
forms
Stolp's Process.
pai-atuspatented by Stolpt have
"

of

apseveral

Fig. 191.

Stolp'sgold-extraction

assuming that in
apparatus.
all other respects,
includingthe yield of
fulfil its object,
it could scarcely
faultless,
owing
metal, it were
to the rapid consumption of the anodes
largecarbon cylinders
and plates which are too costly. It must
not be forgottenthat
for every 1 lb. of gold recovered, some
100,000 lbs. of foreign
material
be passed through the apparatus, and that this
must
hard
material
is often
in character,and
likelyto cut
very
through the soft anode-platesvery quickly. In one apparatus
(Fig. 191) the anode consists of a vertical carbon cylinder,
The cylinder
C, which may be rotated around its long axis,W.
good points, but

even

"

"

is closed

above

and
"

U.S.A.
t German

below,

and

beneath

Patent .333,816,June
Patent 41,061, Nov.

is connected

5, 1886.
12, 1886.

with

340

H.
projection,
is placed a

conical

8MELTIXG

KLKCTKIC

6,

with

hopper
the

is

shows

192

so

another

of

The

metallic

surface

"

modification

number

"l'c. Above

the

length

and

width

the

the
over

On

the

the

end,

apparatus.
towards

C, Cj,C.^,
plates,

vessel, B, which

cone,

rotatingcylinder.
sheet copper.
Fig.

of carbon

platesis

into

the
of

of

fed

chloride,passes

of

cathode

ore,

inclined
long vessel, A, slightly

is laid any convenient


each of these

H,

part is clawed by

upper

of

the

over

REFINIXO.

hopper, F.

solution

diaphragm, and

bottom

the

and

cone,

The

which

on

AXD

has

the

corresponding carbon

plate.
by the diaphragms,
which
the copper
are
D, above
pended
susplates.El, E,, E^ "fcc.,
whole
from
the rods, F, Fj, F^, ic. The
horizontally
in the solution of a metallic salt,but only
apparatus is immersed
to such
a
depth that the liquidcannot flow into the vessels,li,
which contain pure sodium
chloride solution in sufficient quantity
least
the
E.
The ore
at
is introduced
to cover
through
plates,
the hopper,F, and, the apparatus being gently shaken, it flows
down
the slantingfloor towards
the tailingsflow
H, whence
same

The

bottoms

of

these

as

vessels

after extraction.

away

In all modifications

"

which

pass

that

so

libei*ated at

anode

the

arrangement.

the ore
particles
upon
them
into chlorides,
converts
acts

their surfaces,and

over

of the

St olp'sroodifled apparatus.

Fig. Ift2.
the chlorine

formed

are

free chlorine

no

escapes.
Eisner's experiments,*
Frooess
The
:
Cyanide
Theory.
conducted
in the year 1844, on
the solution of gold in cyanide
of the following equation to
solutions, led to the enunciation
"

the reaction

express

4 All +

The

need

after
Mac

it

Arthur-

later

"

8KCN

for the
had

Forrest

controverted
It

patents.
of

may
of the solution.

t proved the

to

4KAii(CN)2 +

was,

as

of

was

thus

Bodlander

throwing lighton

and
the

Christy
progress

temporary production of hydrogen

peroxide,of which the quantitywas found


rapidityof solution,brought about by the
t

4KH0.

explained,
of the
specifications
however, confirmed
by

oxygen
in the

those

which

referred
specially

Bodlander

02

co-operationof

b?en

experiments,
be

2H.,0

to increase

with

finer sub-division

Journ./ur pral'L Chem., 1844, vol. xxxvii., p. 133.


Zeiti^chrift
Jiir awjticandte Chemie, 1896, p. 583.

tlie
or

341

GOLD.

the

of
greater porosityof the gold. In spiteof the instability

the

hydrogen peroxide,which

easilyreducible even
by gold,
70 per cent, (varyingwith the
over
conditions
of the experiment) of the quantitytheoretically
sible
posthe
on
assumption, which is quite a possibleone in the
lightof his experiments,that the solution took placeaccording
to the followingequations:
Bodlander

found

from

is

60 to

"

An., + 4KCN

Auj

2HjO

4KCN

03=

ILjOj

2KAu(CN)a +
2KAu(CN).. +

2KH0

B^O^

2KH0.

of the

action

Any

the oxidation

is not to be feared,since
peroxideon cyanogen
to
to the equation,
cyanide oxamide, accoi-ding

of

2HCN

ILA

CANaH^,

by Radziszewski,* beginsonly at 40' C,


sluggishly.
the end
of a long paper
At
f who
Christy,

observed

research

exhaustive

the

into

electromotive

of

Deyelopment

the

then
made

of

metals

Bodlander's

Frooess.

very

has

force

cyanide solutions,gives the preferenceto


this subject.
Praotieal
of the

and

an

in

views

on

tion
In the introduc-

"

cyanide process into the metallurgical


industry,the
Siemens
and his
service has been rendered
von
by Werner

chief

A.
colleagues(especially
and

Halske,
1887, in

MacArthur

the

of

course

observed
deposition,

von

Garnet),of

and

Forrest.

the

firm

Werner

experiments
gold anodes

some

that

the

Siemens

von

in

"

of Siemens

industrial

continued

in

electro-

to dissolve

passing,and
led to institute experiments on
the extraction
of gold
so
was
On the strengthof these experiments,
from Transylvanianores.
four experimental plants were
put down
by Siemens " Halske
in
in Hungary, one
in Siberia,and one
two
as
early as 1888
the
did
conditions
America.
of
not
Although
original
working
in all these instances,the results were
lead to success
in general
in

when

cyanide bath, even

the

curi'ent

not

was

"

favourable

so

that

Transvaal, where
for

patent

Werner

for the

concentrated

firm

Cassel

undertook

of

gold

ores

whose
has
same

the

on

first to

apply

by cyanide. The
experiments with
alreadybeen made,
time.

19th

Forrest,
October, 1887, took
[MacArthur
of
for
the extraction
out
an
English patent (14,174 of 1887)
on

gold by a dilute solution


of the metal
precipitation
This

patent

results

Company
*

was

followed

BerkhU
t Tram,

followed
from

applied the

the

the

was

Extracting Company, to
electrolytic
process reference
cyanide extraction about the
and

its attention

Siemens

von

extraction

Gold

Gassel
the

the

the

cyanide,and
of
by means

zinc.

later

dates, and

great

skill

with

of cyanogen
or
a
fi*om the solution

by

others

energy

process

in

at

and

which

the

the

practice.]

d. d, ehem, OewtUchaft, 1885, vol. xviii.,p. 355.


Ametican
Inst, of Mining Engineers, 1900, vol. xxx.,

p. 864.

342

ELECTRIC

In

SMELTIHO

AMD

RBFINIKO.

respect both firms, Siemens

one

Arthur-Forrest

Company,

stajrted

neither availed

themselves

in any

When

EUUske

"
the

on

and

the

of the assistance

way

Mac*

in that
principle,

same

of electricity.

it is remembered

treated in order

of material have to be
that masses
small
to separate the
quantityof gold contained

that the main consideration


in it,it will be evident
in designing
the
cyanide system must be
working an extraction plant on

and

the

to arrange

so

the

to

transport

enormous

The

demands

which,
from
The

in

to conduct

and

plant and

from

of useless

mass

of power.

apparatus,and
the

material

of
application

shall

the process, that both


of the
treatment

the

the minimum

consume

to the
electricity

leachingprocess
complicationsof plant and precautionsin working
than outweigh the benefit accruing
most
cases, more

its use.

rapidityof a solution process


is naturallydependent upon

contact

between

the solvent

and

of

areas

the substance

under
the
to

tion
considerasurfaces

of

be dissolved.

to be
gold
complete will be the solution.
that the cyanide process forms
the most
of gold
of completing the treatment
suitable means
have
which
t
reated
been
ores
by wet-crushingand
preliminarily
and
dressing methods
by amalgamation. The basis of this
is
well
consists in catching the gold in
as
known,
treatment,
while
the accompanying
it is being separated from
mercury
of a current
of
lower
of
means
gangue-stuff
specific
gravityby
But
the
of
water.
one
hand, larger grains
lighter
as, on
have an equal
materials and smaller grainsof heavier substances
of water
when carried in a current
tendency to deposit(i.e,,
they
sink to the bottom
together)so, on the other hand, the specifically
reduced
heavier
to a finer grain, may
material, when
remain
in suspension along with
particlesof lower specific
the
the
gravity. Hence,
proportionof the gold that
greater

the

finer the

of the kind
the

division of the

in the material

Hence,
extracted,the quicker and more
It can, therefore,be understood

exists

in

state

of

fine

sub-division

the
but

smaller

But
exclude

tliere
the

may

also

be

chemical
from

the

will

be

the

be
amalgamation process,
the
the accessibility
of
float-gold
escapingamalgamation to the
action of solvents contained
in the water.
Large grainsof gold
in which
dissolve
the
and
time
to
ores
naturallyrequirea long
for treatment
in this form are, therefore,unsuitable
gold occurs
the
by
cyanideprocess.
of the
efficiency

influences

greater will

which

applicationto

would

cyanide
ores, even
In exposed or
though the gold may be very finelydivided.
outcropping ores, or those which are only at a short distance
below the surface,acid compounds of iron and other substances
which
absorb or decompose,cyanides may
be formed
by the
and
of
antimonides, or by the
weathering
sulphides,arsenides,
decay of organic matter, and the presence of these substances
treatment

343

GOLD.

entails
means

and

unduly high consumption


cheap, or restricts its action

an

zinc

ores,

acids

also,which

often

are

injuriouslyaffect the
and

of the

iron

salts may

with

ore

soda, caustic

of

solvent

very

present

as

by

such

soda, or

of

carbonate

as

of

the

reducing action of
oi^nic and other substances may be counteracted
by the addi"
tion of such oxidisingmedia
as
peroxides,permanganates, ferricyanides,and the like. Pyritescontainingarsenic and antimony,
also tellurides give satisfactory
results only after the ore
has
as
been

milk

of
ill-effects

preliminarywashing

containingalkalis

water

The

of solution.

process
be obviated

is

that

by no
appreciably.Copper
sulphidesin pyritous

lime, and

roasted.

Modem
ores

follows

are

which
able
suiton
principles
by amalgamation and cyanidingare as

Fraotioe.

Cyanide

treated

now

"

The

"

(a) Ore-breaking. This

is

"

the well-known
construction

now

almost

effected by
universally
the same
of
principles

stone-breakers,for which

adopted by

are

most

differences are,
which

plateswith
that specialcare
so

the

of the
found

however,
powerful jaws

should

be directed

manufacturers.
in

of the

the

machine

this

portant
Im-

quality of

the

lined,

are

point in

selecting
roughly
to fall on
a
percussionor
which
the
from
which
falls
cylindricalscreen,
portion
through
the screen
after
is delivered, usually direct^but occasionally
further
crushed
shoot
into
a
by passing through rolls,
being
of a current
of water
to
through which it is carried by means
for use.
The
material
the machines
is caused
broken
in the stone-breaker

the

The

stamps.

is returned

coarse

material

to

which

which

has

been

fails to pass

the

screen

to the stone-breaker.

(b) Fine-crashing. The

crushingand

the^imultaneous

amalgamation process
here to
is,however, unnecessary
stamps.
the arrangement of the battery of stamps, in

refer in detail

further

"

of

commencement

the

It

the

is

introduction

of

is conducted

which

the

in
to

gamation
amal-

and

of
begun by
mercury
described
works
in many
amalgamated copper plates. They are
and
the
of
treatment
on
on
on
milling,
gold and
metallurgy,
What
has
been
in
stone-bi*eakers
is also
said
silver.
regard to
here.
There are
of this comparatively
makers
applicable
many
the necessityto use
the
realise
but
few
simple apparatus,
only
material of sufficient resisting
for the wearing parts,such
power
as

shoes and

dies.

amalgamation is continued on flat


The
amalgamated copper plateson the bottom.
in the battery
pulp passes on to these platesthrough screens
In works
mortars.
on
depending solely
amalgamation, pan
amalgamators and settlers are added, but in cyanide practice
the sluices, is prepared for the
the pulp, after passing from
(c) Amalgamation.

sluices

"

with

action of the

cyanide.

^The

344

ELECTRIC

SMELTING

AKD

REFIMINO.

formerly the well-known


(d) Dressing Machineiy. While
W.
B.
Fnie
and made
by Frazer "
designed by
vanner,
obtained
ChalmerH, was
generallyused, better results are now
with the Wilfleytable which in Germany is made
by Humbold,
and
with the newer
made
The
vanner
pnlp
by Grusonwerk.
from
the amalgamation sluices contains three main constituents,
which
the differences between
are
partly chemical and partly
would
difficulties in
rise
to
mechanical, which
give
many
unless
cyaniding
previouslyseparated. Only one of these conKtituents is separated by the vanner
namely, the specifically
with
which, however, largergrainsof sand remain
heavy pyrites,
mix"^. The mixture
sand is commonly
of pyritesand coarser
known
of
the pyrites is of
The
cancentraU$,
as
separation
specialimportance,because this substance is liable to become
oxidised and to form cyanideKM"nsumingsalts during the further
with cyanide,in which, as shown
treatment
by Eisner's equation
under
the
of
air
the
material
to
treatment
access
quoted above,
is necessary,
auriferous
whilst, on the other hand, the coarser
the
material
for
of
time
extraction
its gold
a
requires longer
than does the liner grainedconstituent.
and
Clayey
(e) The Separationof the Finer 'Sand (taUingB)
Matter
These
found
mixed
constituents
are
(Blimes).-"
together
in the matter
flowingaway from the concentrators, and it is of
the greatest importance that 'they should
be separated before
such a separation,
cyaniding. Without
layersof sand and of
would
be formed
when
the
almost
mud
impermeable clayey
and
these would
filled,
cyanide vats were
entirelyprevent the
material.
of
of
uniform
the
Moreover, on account
leaching
the difference in the degree of fineness of these two constituents,
different times are requiredby them
for the
entirely
respectively
solution of the gold,and during the periodof solution they must
"

Frue

"

be

treated

of solution

in different

Thus, whilst a filti-ation process


ways.
the
so-called
is possiblefor
just as it is for
tailings,

the concentrates

necessityroasted beforehand),the
must
by stirringthem with the solvent and
then
solid
the
separating the resultinggold solution from
The
for
the
three
constituents
particles.
necessity
separating
above-named
before beginning the leachingprocess is convincingly
be

slimes

shown

Constituent

(which are

in the

under

of

treated

followingtable

Treatment.

:
"

Conceutmtion
Solution

KCy

of

]le"ittired.

per

Time

uecessary

the BolnUon
the Gold.

for
of

cent.

0-01 to 01

2 to

3 weeks.

Tailings,

0-01

5 to

Slimes,

0-01

8 to 12 hours.

Concentrates,
.

days.

346

in the

industryconcerned

examine

permitted to

of the

large wooden
120

225

to

staves

the

depth

inside

planks, 75

vats

being

mm.

The

by hoops

cut

and

of 25

of
300

and

75

[3 ins.]

mm.

[1 ft.]longer than

mm.

is also constructed

bottom

The
225

each

pitch-pinestaves,

ins.]wide

wide,

with

the

staves

of
and

tongued
firmlytogetherby screw-

mm.

bound

planks s^re

(Figs. 193, 194,

formed

about

of the vat.
thick

grooved joints.

made

are

[4f to

mte.

thick, the

bolts

the

arrangements.

The
about

REFINING.

AND

plant possesses for the whole


leachingof ores and products,it may
more
closelyinto some
general details

of the interest which

In view
be

SMELTING

ELECTRIC

and

195), whilst

mm.

[1 in.]round-iron.

held

are

These

hoops

couplingswhich

of several

gether
toare

allow

lengthsjoinedby screw
The
construction
tighteningof the hoop as a whole.
the basis
the iron tanks shown
in Figs. 196 and 197, is,on
of the

Fig. 197.

Fig. 196.
Construction

Park's work,*

bottom, both
to

support
Slats,25 to
are

and

follows

and

of the wooden

tanks.
se^iarating
:"

The

iron tanks

bottom,
filtering

which

ringprovidedat
on

these

floor of

nailed to

are
a

the

space 25 mm.
then covered

grid,the
vat

The

latter

is covered

[1 in.]wide
with

of ix)pe
*

stripsof

cocoa-nut

(or in the

Cyanide

case

Process

wood

25

25

the

the inside,serves

is formed

thick and 75
40 mm.
[1 to li ins.]
placededgewise at intervals of 150 to 300

placedlike

means

of iron

as
substantially

the

of
of

mm.
mm.
mm.

as

follows

:
"

wide,
[3 ins.]
lli
to
ins.],
[6
[1 in.]square

lengththat the whole


annular
with
the exception of an
around
the periphery. The gridis
matting,clamped firmlyin placeby
of angle
of the iron tanks by means
being of

o/Oo/d

such

Extract

ion ^ London,

ISRM.

347

GOLD.

the inside oi
left around
groove
filter
the
tanks, have
unlike
the vat wall.
The separationvats,
overflow arrangements, either in the fonn of a channel
running

iron;wedged

Section and

around
several
raised

the

plan

edge of

small

by

the circular

into

means

of

Fig.199.
vat, showing Butters

the vat

shaft-like
of

(Figs.198

channels

in

and

and
the

Mein's

199),or
wall,

of
planks during the filling

distributor.

in the form
one

the

of

wall

being

tanks

with

348

ELECTRIC

AND

SMELTING

REFINIMO.

sand.
Butters and Mein have constructed
layersof deposited
a
rotatory distributor (Figs,198 and 199), with the objectof
more
introducingthe tailings
uniformlyinto the tank.
out through
the tank has been filled,
is run
After
the water
the
sand may
that
connected
with
the
bottom, so
dischargepipes
the

Fig.201.

Fig.'JOO,

^--

Fig. 2Qr2.
Bottom

mo8t

extra

labour

"
"
"

"

--f'*-''-'

Fig.2U3.
for
di.scharge-doors

tanks.

This removal
of the sand
leachingtanks.
works, regarded as very important,in spiteof the
entailed
by it, because it guards most effectively

be transferred

is, in

^^

to the

349

GOLD.

of very impervious
against the dilficulties introduced
by the formation
which
form
too
to
are
readilyduring
layers
only
apt
the filling
of the vats.
for the tailings
are
Discharge-doors
vided
proboth
in the separating and
the leachingtanks ; in the

Fig. 205.

Fig. 208.

Fig.207.

Fig. 206.

Fig. 204.

Fig. 209.
Details of side

discharge-doorsfor tiiiiks.

Fig. 210.

350

SMELTING

ELECTRIC

AND

REFINING.

they are usuallyconstructed in the bottom, in the latter


are
discharge-doors
they are also placed in the sides. Bottom
in Figs.204
shown
in Figs.200 to 203, and side discharge-doors
former

to 210.

the residue of the tailings


though the cost of transferring
from the separating
is amply comvat to the leachingtank
pensated
it will be
for by the results of the cyanide extraction,
clear that this cost should be kept as low as possible. Hence, it
tions
is essential that,unless actuallyimpossibleowing to the condiof the site,the separatingvats should be placedat a higher
be
level than the leachingtanks, whilst the latter must of course
allow
of
treated
sands
removed
with
the
to
high
being
sUfHciently
With
the large
the smallest
possibleexpenditure of power.
be taken
tanks used at the present time, especial
in
must
care
and supports,especially
of the tank
regard to the foundations
bottoms, in order to avoid interruptionof the work owing to
hints on carryingout this
these becoming damaged. Valuable
*
and Park's t books.
work are given in Elissler's
constructive
In the earlier days,a number
of systems of extracting
plant
were
developed. Of these many have been entirelyabandoned,
been kept in operationfor some
whilst others have
speciallocal
because
they were
designed on a largescale,and
reason, or even
considerable
of
a
build
expenditure
capitalwould be requiredto reobsolete
which
them.
the
those
are
systems, or
Among
the leaching
now
recognisedas quiteunsuitable,may be named
formed
in pitsor
in poolsartificially
No
by dams.
separating
There
in use a larger
tanks
were
are
provided in these cases.
number
of plants(some of them of considerable
w^ith
efficiency),
separatingand leaching tanks arranged in various groups in
Even

series with

or

without

difference of level,
in

one

case

even

with

the

separatingtank standingat a lower level. Many accounts of


plant,both on this and the latest systems, accompanied by
from
illustrations taken
photographs,both of entire works and
of separatedetails,
are
given by Yates and Jennings,t
The
This
be
divided
Process,
as
Leaching
process
may
"

follows

:
"

Preliminarywashing with
ores

water

or

alkaline

solutions

if acid

drainingof the water

under treatment, followed


by the
of the tank.
the solid contents
with strong potassiumcyanidesolution,
Treatment
the
are

from

strength
gold solutions are to be
with zinc,a higherdegree of concentration
treated subsequently
(up to 0-6 per cent. KCy) is used. After drainingthe solution
again from the sands, and while still wet with cyanide solution,

of which

has

alreadybeen given.

If the

"
AfetallurgyofOold, 6th Ed., London, 1900.
t Tke Cyanide Proce$i of Gold Extraction,London, 1904.
atid Economics
X Pre^rU-day MetailnrgicalEngineering on the Band
the Transvaal
Oold-Mining Industry,London, 1900.

of

351

GOLD.

left for

they are
hastened

by

used

been

time

exposed

of the

means

assist in

to

air,the opei-ation
being

which
pumps
off the solution.

vacaum

drawing

sands

treatingthe

the

to

with

already

After

quently
subse-

solution

cyanide

weaker

have

the

gold originallypresent will have been extracted.


leachingoperationis in many cases repeated once
twice, after the air has been allowed
or
again to act upon the
the
sands
washed
material
for a time.
twice
are
Subsequently
from the tank.
with water, and the residue is finally
removed
The
in
of
slimes
is
tanks
effected
leaching
provided with
stirrers,as alreadyexplained,the action being assisted in some
instances
by the introduction of air with the aid of a steam jet.
The gold solution is separatedfrom the slimes by decantation.
From
the above
descriptionit will be understood that, in
addition
of
to the separating and
leaching tanks, a number
the
and
for
tanks
reservoirs
production,
dissolving
collecting
bulk

of

This

further

the

distribution of the solutions

storage, and

form

must

part of the

cyanide plant. The number, dimensions, and arrangements of


and
these are given by Eissler,Park, and Yates
Jennings in the
books
alreadyreferred to.
Of the processes for the preThe
Precipitation
of tlie Gold.
cipitation
of gold from
cyanide solutions,the electro-chemical
"

have

methods
kind

the
"

used

Halske,

Siemens'

on

now

Halske

gave

put
Reduction

from

in

was

the author
down

the

them

by
Company at

the whole

LiabilityCompany
that

the

preparationthe
followingaccount
the

"

firm

In

the

(" H.

[German]

of Siemens

"

of the first installation

of the

works

in

Plant

second

in the Transvaal

Worcester

Band

Rand

Central

:
"

Central

Beduo-

plant the gold solution


four precipitating
of
tanks

this

is treated

works

The

first process of
that introduced
by Siemens

United

at

Works.

Company's

was

best.

the time

At

SiemeuB-Halske

The

the

by

Electrolysis
").
of this work

be the

to

large scale

owned

edition

tion

found

been

in

[20 ft. x 8 ft. 3 ft. 9 ins.l each.


7 ft.
each
are
suspended sheet-iron anode-plates,
long by 3 ft. wide and j in. thick ; and lead platesof the same
frames
The
cathodes.
size are
as
supported on light wooden
laid lengthwisealong the rims of the
are
principalconductors

6,000

2,500

1,155

mm.

these

Within

vats, and

promote

connection
the

is made

circulation

of the

them

To
way.
liquidin the vats, the electrodes
the bottom
and
on
suspending

with

in the

usual

so
arranged (by restingsome
others)that a space is left alternatelyabove and below them,
through which space the solution may pass. The electrodes are
kept at a distance of about 1} ins. apart by stripsof wood
are

attached

and
sides of the
the bottom
densityis about 60 amperes
per sq. metre
at

an

The

to

E.M.F.

vats.

The

[5-6amps,

current-

per sq.

ft.]

of 4 volts.

cathode

material

must

answer

to

the

followingrequire-

352

KLRCTRIC

ments:

(2)

The

(1)

"

in order

thin

SMBLTIXG

AND

deponitedgold
the

r^Kluce

to

REPINING.

plant it must

or
layerH,.sheets,
plates; (3) it must
gold subsequently; and (4) it must

from

the

than

anode

material.

c*ostly,
especially
having regard to
selected

has been

extent

be worked
The

up

the

positive
electro-

more

be too
mercury
lead
low current-density,
would

As

the

Carbon

is not

for

tanks
electrolyte

month

easilyseparated
be

not

anodes, and iron is therefore used ;


attacked,but it forms Prussian blue, which
again into potassiumcyanide.

durable
suDiciently
to some

be

suitable substance.

the most

as

adherent to it;
be used in

remain

must

of the

cost

kept

are

cathodes

leaden

locked

up, and

removed,

are

at intervals

at

one

it is

time,

can

of

without

the current, and


replacedby fresh plates. The old
interrupting
coated
2 to 12 per cent, of
have
")een
with from
will
cathodes

gold, which
lead
a

cost

of the

separatedby cupellation.The

is

of about

7')0 lbs. per meimem^


After
lid. per ton of ore.

gold,the

solution

amounts

about

to

is retumetl

make

adding sufficient potassiumcyanideto


extraction and precipitation.
The

results of

decomposed
other

working
in

only

not

metals, but

als("

by

are

the
the

follows

as

the

to

proe;
action

corresponding to
the

precipitation
leachingvats, after
good the loss during

Potctssium

"

of

ss

of

consumption

cyanide

dissolvingthe

is

gold and

of carbonic acid in the air.


in different cases, and depends

The

proportion c*onsumed varies


of the ore or tailings.In
upon the conifiosition
which
3,000 tons of tailings,
containing 5 dwts.

instance

one

of

gold

in

per ton,

treate"l per vieyisem^ the consumption of cyanide anion


ntetl
to i lb. per ton of tailings.
be reckoned as follows :
The labour and power
recjuired
may
were

"

capableof treating3,000 tons of ore a month


five labourers
requii-ed
(native)and two supervisors.
5 H.P.
for
This plantcalls for an expenditureof about
of the gold,and about 25 H.P. for the whole
the electro-deposition
and electrical power
transmitted
work, includingelectric lighting
For

installation

an

would

there

for the
The
the

be

stirringmechanism.
of

oost

necessary

installation, in i-espectof the vats, and


niu.st
apparatus for extraction and precipitation,
the

diftei'ent in different

obviouslybe

very

be estimated

to
accoixiing

treated.
with

It

its full

be

may

the

places; it may, however,


quantity of ore or tailingsto be

assumed

that

and
charge of tailings,

every day ; and that from


accordingto the character

exti*action

is charged and

to six such

three
of the

ore

the

and

vat

work.s

emptied once
employe

ve.ssels are

the number
and

of

leachingn

the

electrical
required.
restricted
installaticm
of
be
of
the
to the
portion
ooui'se,
may,
of the gold ; but it will be found advantageous
actual deposition
The

to

generate

lightingof

at

applicationof

each

the

the whole

same

time

dynamos

curi-ent

establishment, and

sufficient for the electric


for the

electrical trans-

354
70

since

per

REFINING.

520

recovered, about

of this is

cent,

AND

SMELTING

ELEGTBIG

ozs.

of

gold

should be recovered.
of unrefined

J"1,850

gold,
Deducting working charges,"fec.,

520

ozs.

....

700

VraOt

this must

"1,150

per mensem^

be deducted

from

the

manager's salary,leaving,however,
dividend.

interest, amortisation,and

of the

the value

But

tailingsand
ample margin for

an

The

above-named

Bond

Ore B^duction
Central
has, in the first year of work at the
of 25 per cent, even
Worcester
installation,paid a dividend
after writingofifa considerable
sum.
Co.

of

Comparison
Prooesses.

advantage
compared with

as

Chemical

and
of the

Electrolytic

The

"

the

Precipitation

of premethod
electrolytic
cipitation
chemical
is very considerable.

the

of

comparativelystrong
liquidsthat the
only
with
gold can be precipitated
any degree of completeness by
metals like zinc.
The electrolytic
process is, however, capable
The
weaker
solutions.
of being used with
consumption of
be
also
is
as
reduced,
gathered from
considerably
cyanide
may
In
MacArthur-Forrest
the
the followingcomparison.
process
solutions containing0*3 per cent, of KCy are used, whilst in the
0*05 to 0*08 per
Siemens
process the strongest liquorcontains
cent, and others with only 0*01 per cent. KCy are also employed.
of tailings
A planttreating3,000 tons per month
by the former
The

latter method

necessitates

cyanidesolutions,because

use

from

it is

such

cyanideto the value of J"220 per mensemy whilst


process consumes
similar plant worked
penditure
by the Siemens system requiresan exof only "75 in the same
time for the same
quantity

of

raw

material.

that the

It is true

of weaker

use

solutions

for

longerperiodfor

a
and, therefore,
solution,
largerinstallation of leachingvats ; but this is of less importance
than the largeconsumption of cyanide. A further advantage
of the Siemens
of
process is that the gold is obtained in the form
whilst by chemical precipithe leaden plates,
a solid depositupon
tation
the gold is recovered as a loose powder mixed with particles
of zinc.
of the gold on lead the
Further, by the precipitation
troublesome
and
purification
separationof the powdered gold
"me
the
zinc boxes is dispensed with; and
in
at the same
the cupellation
gold is
process for the separationof lead from

extractingnecessitates

conducted
whilst
process

the

by

without

separationof
solution

the

in acid

or

the loss of both zinc and


The

economy

enables the lead to be recovered,


zinc from
the gold in the older

and
difficulty

of the

Arthur-Forres^
process

in other

chemical

sitates
reagents neces-

acid.

as
compared
electrolytic,
is clearlyshown
by the

the Maofact that the

with

Fig. 21a.
nioBtration

of

tanks for use


electrolytic
cyanideprocess.

in the SiemenB-Halskc^
Digitizedby

LjOOQIC

356

KLECTBIC

of

cost

SMELTING

treatment

per

with

tons

100

from

REFINING.

in a work
capable of
tailings,
is
the
former
diem, by
process
it ranges, according to Eissler,*

of

ton

dealing
only 3s., while by the

AND

per
latter

7s. to 8s.

of electrolytic
now
as
Although the principles
precipitation,
do not differ from those just laid down, the apparatus
practised,
has undergone some
in the arrangement
modification,especially
of the electrodes.
This is illustrated by Figs.211, 212, and 213.
In order

to make

the

illustration

clear,it

will suffice to describe

k
in operation by the firm of Siemens
plant shown
Reduction
and the Rand
Central
Halske, Siemens Electrolysis,
in the
Exhibition
and
in
the
Paris
of
now
1900,
Company
Institute of the Technical
Metallurgical
High School at Aachen
model.
Iron
as
a
plates,
a, are, as before,used as anodes, whilst
the cathodes
consist of lead strips,
are
suspended in
c, which
in
three rows
rolled into spiralform
from
the carrier,D, and
The
order
to provide as
area
as
possible.
large a superficial
section in Fig.2 1 1 and in
in longitudinal
tanks, which are shown
of cells,through
plan in Fig. 213, are divided into a number
which
the electrolyte
from below upflows in series,
in each case
wards,
each
down
cell
the
channel, t, and
by Lp passing
entering
to the long axis
leavingby Lj. The electrodes are hung parallel
of the tank, and are completelyimmersed
below the level of the
solution.
The
anodes
are
supported beneath on ledges,and
held in place by c.
Like electrodes are coupled in
are
laterally
the connections
in Fig. 212, the wires, ",
parallel,
being shown
with
the
and
the cathodes.
with
h
anodes,
Mercury
connecting
a

small

contacts

used.

are

0-6 ampere
[nearly 0-05
per sq. metre
and
this
of
surface
is
electrode
used,
requires
amp.
per sq. ft]
It
the electrodes.
a
potentialdifference of 2 volts between
A

of
current-density

be reckoned
generallythat
may
in length,1*5 metres
in
7 metres

[23ft. X

5 ft.

that, under
of solution

gold in

its

into

run

3-3

ft.]will

so

doing.
from

take

breadth, and

1 metre

measuring
in height

and
of 100 amperes,
current
cb.
cb.
50
metres
ft.]
[1,800
and
yield
daily
apparatus
up

conditions,about

will pass

removed

are

these

tank
electrolytic

an

the

bars,which

through
The

the

lead

stripswith
tanks
precipitating

contain

about

their
once

depositof gold

month

1*5 to 10 per

cent,

and
of

are

gold,

ing
cupelled. The lithargeproduced during the meltdown
which
rolled
is
metallic
is
reduced
lead
to
again
process
and thus made available again for use as cathodes.
to thin strips,
The crude gold obtained
time has a fineness of 85 to
at the same

and

are

then

90 per cent.,and contains


silver and a little lead
0*5 per cent.). It has therefore to be refined.
It is natural
have

stimulated
*

M.

that

the

further

success

of the

Siemens

experiments in the

Eissler, The

same

Cyanide Process, London,

(about0*25

to

process should
direction ; but
1895.

GOLD.

357

358

BLECTRIC

it would
as

be difficult to

improvements
The

SMBLTXKO

of iron

use

upon

name

BKFININO.

AND

processes

could be considered

which

it.

by Andreoli, is,from

recommended

cathodes,as

incorrect,and this
standpoint,theoretically
technical
compensated
by any
advantage. It is proposed
the iron should
that the gold deposited upon
be removed
by dipping the metal into a batn of molten lead. As, however,
the alloyingof the gold with lead is still recommended, it is
pensed
difficult to understand
why the lead cathodes should be disthe electnM^hemical

for

is not

with.
Other

substitute

inventors

slightknowledge of

that would
the amount
An
electnM^hemical
In

specialattention.
from

outside,the zinc
are

coated with

arithmetic

cathode, although only


mercury
is necessary in order to estimate

be

requiredfor the purpose.


proposed by Betty is worthy of
process
this process, which
requiresno current
intended
effect the precipitato
turnings
tion

about

5 per cent

of lead

by

immersion

in

of the precipitation
In course
lead solution.
process the leadsmall zinc-lead couples,
in which
innumerable
coated zinc forms
the zinc,is so active that the cUlute cyanide
the positivepole,
solutions
are
rapidlyfreed from gold. The zinc precipitation
is
undoubtedly improved in this way, and the modified
process

for experimental work,


process is stronglyto be recommended
be liable to many
for small plants that may
interruptionsin
In
workings.
large works, however, which are in continuous

or

operation,this

with

the

Siemens

process.
The foregoingtable,suppliedby the office of the South

African

Republic in the Paris

general

method

scarcelycompete

Exhibition of lOOO,*^givesa good


treatment
of the Transvaal
gold ores

the
survey
Witwatersrand
of

can

PREPARATION

OF

FINE

alreadybeen pointed out that,by

It has
extraction

of

the

of

gold

district.

above

described,as

GOLD.

the methods

of copper
and
course
obtained free from silver and

also in the

the gold is seldom


refining,
and
also with the gold which
this is the case
is left
platinum ;
the residue in the partingof the alloysof the preciousmetals.
as
of separation
If the silver in the alloypredominates,the method
described in the Chapter on Silver would
naturallybe used;
in
the case
and
it is only necessary, at this point,to consider
which
the gold is rendered
impure by the presence of small
and
of
silver
platinum. The process used almost
quantities
of such gold was
some
exclusively,
years since,for the refining

silver

*Borcher8

Halle

a.

Die

S., 1901.

Elektrochemit

at^

der

Welt

AuasUUung,

Paris, 1900;

359

GOLD.

the

elaborated
Pettenkofer
by Pettenkofer.*
parting method
solution
which
the
in
other
in
words, a
tiqua regia,or,
chlorine
of nitric
of hydrochloric acid is set free by means
acid.
It is well known
with
on
that,
treatinggold
aqtui regia,
the gold with
whilst
into
solution,
platinum
present
any
pass
silver remains
insoluble
silver chloride.
The
is
as
gold
cipitated
prethe solution
of ferrous chloride,
from
and,
by means
from
the liquid,the platinum
alter
separatingthe precipitate
metals
of metallic
iron.
in the latter are
deposited by means
The
older
substitute
the
for
to
an
electrolytic
attempt
process
been
has
chemical
method
frequently made, as the author
used

pointed
full

out

the

in

has

first

of this

[German] edition

work

; but

only by Dr. E. Wohlwill,


electrolyticplant of the Norddeutsche
formerly manager
is well known
in the field of practical
whose
name
Affinerie^
research
in electro-metallnrgy.
success

attained

been

of the

WohlwUPs
in

the

of

the

have

Beflning

Eleotrolytio

experiments, and
led to

the

of

Wohlwill

Prooess."

has,

full account
very
considerations, which

ZetUchrififur Elektrochemiejfgiven
various

of

refiningas practisedat
electrolytic
with
This account
present.
advantage be quoted at length.
may
contained
Wohlwill
in a paper
first refers to errors
by Bock, J
who
was
formerly in the service of the Norddeutsche AJineriCf
pointing out, in opposition to Bock's assertion, that it is
impossible to effect the electro-chemical solution of gold in an
of neutral gold chloride.
electrolyte
*'

of

It

the

process

''
that such a
says,
from
acid
free
completely

solution

true,"he

is

AuClg

current, but

the

gas
it.

depositedat
The

the

is

"

gold

a
i.e,,

solution

decomposed by

escapes
solution
aqueous

acting upon
is formed
hydrogen gold chloride (AuClj HOI), which
evaporating a solution of gold in aqua regia to dryness on
This
bath.
solution
water
apparently decomposes under
same

of

the

out
with-

anode

of the

is true

"

on

of the

influence

into

current

chlorine, which

the gaseous
anodes
state, and
be
the cathode.
If the solution
in

oxygen,

mixed

of

chlorine,as

pure

with

interchangeof the

more
a

or

less
with

be

decomposed by

cyanide solutions
cannot

much

as

be

are

employed
gold

must

the

for

deposited at
small,

current

depositedin

place

the

oxygen
undissolved.

of water;

but

"

the
as
same
way
of
deposition pure gold,they
electrical parting process, in which

current,

in

an

dissolved from

Joum,, 1847,
Dmgler'spolylechn.

the

the anode

as

is

deposited

vol. civ.,pp. 118-131 and 198-204.


vol. iv., pp. 379, 402, 421.

ZeUtckrififikr
Elektrochemie,l897-"8,

X Berg- und

hiUtenmannUche

in

Thus, although
hydrogen gold chloride,

of

the cathode.

at

an

for the

used

be

the

product resultingfrom

the gold anode remains


every case
neutral goldchloride,or
of
solutions
may

is

the

chlorine,is

substitution

chlorine

or

the

separates at

gold, which
dilute

the

Zeitung, 1880,

p. 411.

360

SMELTING

ELBCTBIC

*'

This

anode

liberation

is, in

of gaseous

fact,opposed

BEFININO.

AND

chlorine

in contact

the

with

gold

expectationswhich

ably
might reasonaccustomed
to
are
grounded. We
regard all chlorine-producingmixtures, like chlorine itself,as
solvents
moistened
auriferous
for gold. We
with
extract
ore
should
chlorine
chlorine.
then,
Why,
separated by
gaseous
leave the gold unchanged)
means
electrolytic
which
''The
takes place during the decomposition
reaction
of hydrochloric acid between
prising,
gold electrodes is doubly sur-

considered

be

in

well

relation
that

to

to

the

behaviour

described.

above

It

is

hydrochloricacid between

platinum electrodes
completely decomposed into hydrogen and chlorine,and, as
the ])latinnmanode
is not
attacked
by the chlorine,both gases
be collected either separatelyor
together. If, however,
may
electrodes
be
substituted
for
gold
platinum, hydrogen is still
well known

is

evolved
of

the

at

cathode

yellowcolour,becoming

in the colourless
is

but

solution

evidentlypassinginto

chlorine

the

wider

at the

the

anode.

The

solution,and

it is not necessary
to employ
acid to effect this.
The

vanishes,and a streak
bottom, is observed

towards

laid

solution
to 1

The

c.c.

down

are

followed)attainable

anode

of

that

chloric
hydro-

of any evolution
of gas,
the
of gold at
anode, in
in

conditions
a

shortly to

hydrochloricacid

containing0*4 grm. of hydrochloricacid (corresponding


of hydrochloricacid of specific
gravity1-19)per litre.

addition

of alkali-metal

hydrochloricacid,and
potassium,or ammonium
the
density,to cause
without

of the

remarked

strong solution

very

absence

and, therefore,the complete solution


used, is (ifthe
proportionto the current
be

gold

it is to be

such

an

an

acts

exceedinglysmall
chloride

anode

addition, a

without

chloride

in the

quantityof

with
suffices,

gold to
mixture

same

low

way

as

sodiuni,
current-

pass into solution,where,


of chlorine
and
oxygen

Without

going beyond the


observation, the peculiarbehaviour of gold,
between
of discriminating
which
a
paHicles of
suggests
power
be
different sources,
chlorine
obtained from
might
explained
anode
with
in
that
contact
separated or
gold,
by assuming
will
solution
when
the
nascent
chlorine,
only pass into
in
suitable
form
to
materials
are
pounds
comproportions
present
of the
of
type AUOI4H, including such substances
and
the
like.
constitution
as
AuCl^Na,
AuCl^K,
analogous
in which
But
it may
that, in all cases
reasonablybe assumed
compounds of this kind exist in, or pass into, solution,the
gold exists exclusively,or at least mainly, in the form of
the complex anion
AuGl^, while the hydrogen or the alkali
metal
concerned
Hittorf,* indeed,
plays the part of cation.
the
in
made
this observation, many
of
electrolysis
ago,
years
chloride of gold and
his
In
the double
potassium.
judgment,
would

escape
region of actual

"

affectingit.

Poggtndorjfa AnncUen, 1859,

vol. cvt, p. 522.

362

BMELTINO

ELECTBIC

silver.
The

of

residue

salt used

gold

solid

1^

if it is allowed

fall

to

acid
hydrochloric

of

cent,

per

to

appears

drop by drop

in

the

explain the

suffice to

would

of silver nitrate

action

REFINING.

AND

discrepancy.
different
essentially
slightelevation into
each drop enters
as

be

from

In this case,
gold solution.
to form, which
a
yellow precipitateis observed
turbed,
disis not
solution
remains
unchanged for a short time if the
but soon
vanishes,giving place to white silver chloride,
is
This phenomenon
the more
readilyif the liquid is shaken.
if an
observable as long as the gold is present in excess
; and
filter
the
off
to
decompositionwill
precipitate,
attempt is made
the filter. It is impossibleto doubt that
be found
to set in on
contains gold,and it is at least possible
this unstable
precipitate
It is certain
it to be the compound AuCl^Ag.
to conceive
a

concentrated
solution

the

reaction

the

that, in

silver chloride

described,the

above

primary product^ but results rather, in all cases,


decompositionof the yellow precipitate a "eu^ which
of a complex ion and also the
the existence
to prove

formed

as

the

from

suffices

"

ions

from

In the

same

of chlorine

absence

acid.
hydrochloric
nitrate

produces
with

even

is not

at

once

which

behaviour

is

not

of

solutions

it is from

as

noteworthy that silver


a
yellow, precipitate,
neutral
gold chloride
If, therefore,

present.

silver nitrate

towards

it is

way

AuCl^

no

solution,free

the

reddish,

concentrated

in

(AUCI3)

'

ence
exist-

the

confirm

to

appears

the

the

instability
gold
of
the
solution
increasingdecomposition
lysis,
electrodilution during
follows on increased
anion AuOl^ which
Hittorf assumes
Hittorf.*
observed
in
as
by
already part
concentrated
take
in
that this decomposition does
not
place
solution; the gold would, therefore, pass into the chloride
ions.
Cansesolution
entirelyin the form of complex AuCL
guenUy, gold passes from the anode into the chloride soltUion only
the conditions
when
are
favourable to the formation of AuCl^
of the anion

of the

AuCl^

in the

compound and
correspond with the

solutions,

so

behaviour

the

silver

also

dilute

of the

ions A
"In

the

only, it

first

follows

solution

of

anode

gold

of

equation
chlorine
"

least

anode
Au

in the

exceeds

CI3

in

which,

the

consideration

explanation given
anode

remains

that

HCl

coincidence,

equallyunattacked

immediate

to

with

unite

hydrochloric acid,

the

would

p. 523.

of

of the behaviour
Ib

complete

the
place
neighbourhood
according to the

necessary,
of

the

when

take

AuCl^H,

absence

Poggeiidorfs Amialen, 1859,

t A

only

can

acid
quantity of hydrochloric
the

hypothesisthat

above

the

from

the

solution

hydrochloricacid

the

place,taking

not

in

platinum anode will show

Batisfactory

mixture

cause.

of chlorineand

The

that

the

platinum

hydrochloric

with chlorine in a solution free from hydro("doricacid;


acid, and in contact
of the anion PtCl^ being
the possibility
case
yet there is in the former
which
does not exist in the latter case.
formed, a possibility

363

GOLD.

eidier be set free or (in dilute solutions and with low currentIf
density)would liberate an equivalentquantity of oxygen.
smaller
of
be
a
proportion hydrochloricacid
present a part of
the

chlorine

absence

of

But
state.
since, in the
gaseous
the
of
chlorine
hydrochloricacid,
separated
weight
escapes

proportionalto the current-density


of the hydrochloricacid used as
be increased with
must
electrolyte
increasingcurrent-density,
if the continuous
solution
of the gold anode
be aimed
at.
that
the
concentration
of
acid
is
the hydrochloric
Assuming
the complete combination
sufficient to ensure
of the chlorine
liberated (in proportionto the current)during a short experiment
per unit

of cathode

in the

employed,the

under

the

density,the
suffice

selected

quantity

of

conditions
the

acid

of anode-area

present

would

and

current-

no

the

for

increased

is

area

concentration

or

either of the cun*ent


puri)ose in the event
of the cathode area
being diminished ; and
chlorine

longer
being
in such

the

of necessity
must
anode,
gaseous
escape at
wise
oorrespondiugproportionof the gold,which would otherhave
been dissolved
in proportion to the current, must
remain
Without
undissolved.
proceeding further,it is evident
that the means
is found of obviatingthe separationof chlorine,
which is one
of the difficulties met
with in working the process
acid
added
is
until
to the solution
continuously ^hydrochloric
all evolution
of gas ceases, even
the highercurrent-density
when
is applied. It is easy experimentallyto produce the interesting
phenomenon
enough to anyone
(surprising
unprepared for it)
of almost
immediately stopping the evolution of every trace of
in a solution from
which
chlorine
it is escaping freely
gaseous
by the simple addition of hydrochloricacid. From the practical
the
point of view, there may be recognisedin this observation
for
industnal
conditions
on
an
gold electrolysis
scale; for, by
in the concentration
a further increase
of the hydrochloric
acid,
it is possibleto increase also the current-density
which
the
at
anode is capableof dissolving
without
of gas.
any evolution
a

case

and

"

of the influence
''The consideration
formation of the AuCl^ ions will show

of
a

temperature

means

on

the

of still further

raisingthe current-density
permissible.Supposing that, in a
with
certain
a
given case
proportion of hydrochloricacid
has been reached,beyond
present, the limit of current-density
which
it is impossibleto go without
chlorine
being
gaseous
formed, it is still practicable,
by warming the solution, to
ensure
an
uninterruped solution of the gold anode without
the concentration
of the acid, even
when
altering
applying a
For every proportion
of hydrochloric
highercurrent-density.
acid,
the limitingcurrent-density
at which
complete solution of the
gold takes place is materiallyraised as the temperature increases.
the
of
By adopting,therefore,
advantage
electrolysis
at 60" to 70' C, it is possible
not only to use
considerable
very

364

ELECTRIC

with

currents

AND

REFIMING.

bydrochloricacid solutions, but


attain
to a markedly
than
is possibleif the concentration
current-density
acid be increased
far us possibleat the
as

weak
relatively
the

also, by combining

higher

SMELTING

maximum
of the

effects,to

two

ordinarytemperature.
"The
acid

above

discussion

behaviour

the

to

as

between
electrolyte

as

electrodes

gold

of
throws

hydrochloric
light also

which
is used for
electrolyte
ture
means
gold by electrolytic
namely, a mixacid
and
this
chloride.
In
of hydrochloric
hydrogen gold
dissolves
also the anode
mixture
only with the aid of the
acid
hydrochloric
present. So, too, the separationof gaseous
when
the current-density
is prevented
chlorine
is increased
over,
acid
hydrochloric
proportionately.Moreonly by adding more
has
heating the solution containingthe mixed electrolyte
the same
effect as in the case
acid alone.
It may,
of hydrochloric
the primary action must
for the present, be left open whether
of
be regarded as restricted in this case
also to the electrolysiB
is
demonstrated
the
But
acid.
it
by
hydrochloric
sufficiently
of gold solutions
acid and
difference
in behaviour
free from
others containinghydrochloric
acid,that the acid added in the
of the gold solution between
gold electrodes has a
electrolysis
different from that which
it has in other industrially
function essentially
which
successful electrolytic
are
apparently
processes
formation
in
which
there
unbroken
is
an
completelyanalogous,
free acid being present. It is
of metal ions at the anode without
behaviour

the

upon
the

of the

mixed

separationof

conceivable
effect of

"

the

that, in

adding

the

latter case, the


is to reduce

acid

only, or
the

the

principal,

resistance

of the

solution.

Although in decompositionsof this kind there is usuallyno


to regard the material
reason
depositedat the cathode as the
result of secondaryaction,yet a hypothesisof the kind is justifiable
in the case
of gold electrolysis,
whether
hydrochloricadd
is submitted
to the action of the current
alone,or togetherwith
A deficit of gold is always
its compound with gold chloride.
the solution undergoingelectrolysis
observed at the cathode when
little or no
contains
but is mixed
hydrochloricacid initially,
with chlorine,either directlyor
by diffusion from the anode,
**

and

this

deficit appears
to point to
acid
cathode
which
the
at
hydrochloric
with

the

H,

the

of these
afford sufficient

metal

occur

of

in accordance

"

Au

light of the ordinary view


at
capable of direct union even
to

must

formation

equation
AUCI4H

In

increased

an

two

substances

4Ha.

that

chlorine

low

temperatures,

in the solution

explanationof the reduction in


depositedbelow that required by theory.

and
would
the
But

gold are
the

existence
co-

appear

weightof
this

ex-

365

GOLD.

planationis
to

appears
sutfered
with

in accord

not

be

which

The

"It

illustrate this

normal

the

the

deficit

of

weight

loss

which

is also in contact
the results of
contains

"

proportionof -^

-^^

1 -2066.

that, in experiment (2),the evolution

be observed

should

than

same

chlorine.

that

the observation

considerabljgreater
time by the anode
The
following table

in the

experiments

with

of gas at the anode ceased for some


time
the current-density,
and accordingly
more

owing to a lowering of
tion.
gold passed into soluIn the other
experiments, however, gas was
given off
After experiment
without interruption
during the whole time.
cubic
of
acid were
centimetres
few
a
hydrochloric
(3)
strong
that
the
the
of
added
solution used, so
to
weight
gold passing
into solution

at the anode

cathode

accordinglyno

in

was

deficit

proportion to
observable.

was

the current, and


Then, in experiments

used in order to renew


(5)platinum anodes were
The markedly greater cathode
the separation
of chlorine.
deficit
in these two
experiments,as compared with experiments(1),(2),
and (3),is undoubtedly due to the greater quantity of hydrochloric

(4)and

acid

already been
only the

not

into

it from

the

in

used

in

chlorine
the

The

solution.

anode

solution

experiment (4),and
initially
present,

during the
to point

but

used

for

therefore
that which

(5) had

contained
diffused

progress of the
that in a

experiment.
solution
so
scarcelynecessary
stronglycharged with chlorine, and containing hydrochloric
acid in addition,gold will dissolve readilywithout
the assistance
of the current) even
though there is no correspondingdepositat
It

IB

the cathode
a

as

there is when

gold plateof the size used

lost 0*06

gramme*

the solution

in the

the current
is used.
cathode
in

for the

course

employed for the

out

same

of

an

hour

In

experiment (5)
immersed

when

experiment at

this way,

in

temperature

of73'C.
A small fraction of this loss (as will be explainedlater)is caused by a
but acid,gold solution
solvent action,even
of the completelychlorine-free,
the metallic gold.
on
*

366

ELECTRIC

It

*'

of

18

SMELTING

great interest^in

REFINING.

the

lytic
of electropractical
application
of
far
ascertain
how
separation gold,to

for the

processes

AND

the anode
be increased without
may
of
the
solution
of
under the combined
interruption
process
of increased concentration
of the hydrochloricacid
at
current-density

the

any
ditions
con-

and

higher temperature. It will sufBce,in this connection, to show


be attained in
can
requiredfor practical
purposes

that all that is


the

indicated.

manner

of 40

current

the

freelyin

amperes

solution,with

immersed,

surface

The

with

incipientevolution
and
at once
edges)was

on

140
of

of gaseous

Any

anode

an

about
cathode

(Wohlwill) has

writer

to act

of fine

sq.

chlorine

gold,hanging

[21-7sq. ins.]of

cm.

size

equal

caused

on

each

at the

(whichbegan
the

side.

addition

completelysuppressed by
after increasing
the strengthof
even
about
3 per cent,
the hydrochloricacid present, there was
only
the
bath
acid
in
of that
(correspondingto about 80 c.c. of
acid of sp. gr. 1*19 per litre).The average
currenthydrochloric
acid
hydrochloric

of

; but

40

densityused

in this

experiment was

2,857 amperes

twvtv

per

metre
but,since the densityat the
[265amps, per sq. ft.];
electrode
of
is
the
sensiblyhigher,the observation may be
edges

square
taken

of employing
proving the possibility

as

of at least

3,000 amperes

per square

current-density

[280amps,

metre

per sq.

ft.].

simple calculation to show that,under these conditions,a


thick,and weighing 4 kilogrammes
gold plate,4 mm.
[0*157in.]
[8*8lbs. av.],would completelydissolve in five hours under the
In actual practice,
of 308 amperes.
action of a current
however,
be
such high
not
to use
it would
for many
advisable,
reasons,
It is desirable
current-densities during the greater part of the time.
the
dissolve
anodes
in
other
to
as
completelyas possible,
or,
It is

words,

to

leave

as

small

subsequent treatment.
square
reduced

metre
to

is attained
133

square

residue

as

may

be

of
current-density
when

cm.

the

[206

area

3,000

of the

by
ins.]

sq.

undissolved
amperes
anode
has

the

action

for
per
been

of the

current.
to 1,000 amperes
Restrictingthe current-density
per square
metre
a
density which
[93 amps, per sq. ft.]for normal work
the complete solution of
could scarcelybe usable in most
cases
thick
and
4
4
of
a
weighing kilogrammes, by means
plate, mm.
would
of 308 amperes
current
a
require fifteen hours, or, of
the
of
number
of
kind could be dissolved
same
plates
course, any
in an equal period of time if treated in baths placed in series.
of using high currentr
*"As
bearing on the practicability
that relatively
densities at the anode, it should be remarked
be
the
without
cathode
densities
at
employed
prejudice
high
may
and without
and purity of the gold deposit^
to the cohesiveness
the
unduly increasingthe cost of the process by necessitating
of
baths
richer
in
Whilst
is
use
gold.
electrolytic
copper
**

"

"

367

GOLD.

obtained in

thoroughly compact and dense form by using such


as
convenientlybe employed in practice,
may
silver deposits(at least by the process
electrolytic
commonly
employed in refining)are in the form of weakly coherent
obtained
in the
crystals.Gold, however, is only exceptionally
dense form
acidified with hydrochloricacid ;
from
the solution
often
found
it
is
as
more
largelycrystalline
deposits,which
generallyadhere to the underlying and neighbouring surfaces
with sufficient tenacity to prevent their separating off as
a
a

current-densities

result either of their

own

substances,although

it is

growth
by

or

time

same

coherent

more

is raised.

solution

as

Increase

be

other

and
markedly crystalline
of
proportion gold in
currentdensity causes

at

the
of

and

with

contact

mere

them
difficult to detach
With
of
current
constant
a

if desired.
means
by mechanical
more
density,the depositbecomes
the

of

means

no

less

With

coherent.

the

the

solution

a
rougher
of gold per litre [3 per cent.],
a
containing30 grammes
good
with
coherent
be
obtained
at
the
cathode
currenta
depositcan
approaches that which is permissibleat
densitywhich initially
the anode.
During the progress of the depositionthe cathode
in volume, so that its area
increases,
plateincreases considerably
at the cathode
stant
while,conversely,the current-density
[withconcurrent! diminishes.
It is important to observe that,even
the growth of the gold
with relativelyhigh current-densities,
and
in
such
unlike
takes
a
deposit
place gradually
way that
silver and
lead deposits phites or needles
of the crystalline
metal do not tend to grow out into the solution,and so give rise
the gold hcUhs may
Hence
be arranged with
to short-circuits.
without
short
distance
between
the
the
even
electrodes,
only a
2his means
that it is possible
assistance of any separating
screen.
solution.
A
toith a modercUe
volume
tively
relathe
to work
of
costly
small plant,therefore,
suffices for the treatment
of a large
quantityof gold. As an example of this,it may be stated that
in the Hamburg works of the FrankfurterGold- und Silber-Scheidea floorspace
of only about 6 square metres
anstaltj
[64*6sq.ft,"]
in
which
it
tanks
taken
was
was
possibleto
up by electrolytic
iOO ozs,]of fine gold in twenJty-fowr
deposit75 Inhgrammes [2,

deposit to

"

"

hours,
"It

remains

now

separated from
described
fact that

is used.
almost

into solution

with

explained in what way the gold is


the
impurities when
electrolyteaboveThis
separation depends mainly on the
be

to

its

all the
the

other

constituents

gold,but, by

reason

of the

requiredto depositthe latter metal, it alone is


the current.
In regard to plcUinum,although
not

dissolve

when

used

by

itself

as

anode

pass

of the lower

voltage
precipitatedby
this

anode, even

dissolve
hydrochloricacid, it will, if alloyed,
wiU not be precipitated
wkh
it, even
from

vnth

metal

in hot
the

solutions

will

dilute

gold,but
rich

in

368

ELECTRIC

SMELTING

AND

REFINING.

the
platinum. On this account, it is possibleso to concentrate
materials
in
which
the
from
minutest
even
platinum,
only
quantitiesare present, that it may be obtained as a precipitate
This concentrain the form
of platinum-ammonium chloride.
tion
without

is effected

trouble

if the

solution

same

is used

repeatedlyfor the same


cycle of operations. When
relatively
the
is
alone
the
of
the
baths
and
use
same
treated,
gold
of platinum in the solution may
gradual accumulation
readilybe
continued
months.
So also,all the palladium preserU
for many
fine

the anodes

in

goes

into

becomes
graduafly

solution,and

concen-

tratedfwith the platinum.


leas
or
gold contains more
chloride upon the anode.
latter metal unll be deposited
as
the
in
silver chloride falls
too
large a proportion,
present
-removable
pended
bottom, or, better, into an easily
tray susthe
The
the
bottom
vessel.
anode
of
over
immediately

'*If,as
the
silver,
If not
to the
slimes

so

the

is

usually the

with
group, together
which
the originof

anode
Since

silver chloride

this

substance

periodof use;
out of solution

are

present

certain

more

proportion of

in

nevertheless,no

warmed,
the

the

will be said hereafter.

absolutelyinsoluble

is not

when
solutions,especially

dilute

the

insoluble metals
contain, besides silver chloride,

obtained

platinum
gold,as to

of

case,

solution

even

minute

in

very

quantitiesof
a
very short
of silver passes

after

trace
recognisable

depositof gold.
electro-deposited
gold therefore,if not
purity
absolute,is in every case extraordinarily
high. The ordinary
show
the
metal
not
infrequentlyas 1,000 ^tl"",
assay
processes
There
and only in quiteexceptionalcases
is
lower than 999*8.
doubt that these small differences in the purityof the gold
no
connected
with variations in the compositionof the solution
are
and
The
of the current-density
writer (Wohlwill)has
used.
been able to detect the influence of an unusually large proportion
of palladium. If the attainable approximation to absolute
purity is sufficient for practicalpurposes,*it is still desirable
the scientific standpoint that, just as electrolytic
from
copper
has been studied
by Hampe, and the gold of the Frankfurter
Scheideanstalt
Kriiss, the analysisof electrolytic
by Gerhard
into in a suitable place by a research
gold should be examined
with the greatest care
and with the closest investigation
made
of originof the metal.
into the conditions
**The

into the
of

the

*That
[Berg- und
certainlycould not be the case if Bock's statement
hiUtenmanniache
not
Zeitung, 1895, p. 37), that electrolytic
gold was
The Norddeutsche
suitable for coinage purposes, had been confirmed.
which
lytic
at that time
was
practicallythe only firm placingelectroAffintrity
their
the
ascertained
from
of
the
on
product
market,
purchasers
gold
of Bock's
that
article)
(by enquiry immediately after the appearance
known, by those most
nothing was
competent to form an opinion, of any
of electrolytic
or restricted suitability
unsuitability
gold for toe production
of any

alloywhatever.

370

ELECTRIC

REFINING.

AND

SMELTING

separation)be employed as the anode material, the proportion


below that which
is permissible
of gold might easilybe reduced
the course
of one
in
night'swork with strong currents, unless a
suitable excess
of fresh gold solution be added
in advance.
this
In making calculations
it
be rememfor
bered
must
purpose,
that the sum
of the substances
combining with chlorine at
the anode
of gold deposited
at the
is equivalentto the amount
cathode.
It is,therefore,
important to determine, beyond doubt,
the electro-chemical
equivalent of gold under the conditions
of gold chloride solutions acidified
obtainingin the electrolysis
with
acid
between
hydrochloric
gold electrodes. Assuming, as
is customary, that the gold is present in the solution
as
a
trivalent metal, it follows that either 1 atom
of silver (107*92),
"

("o-)"

of copper

atom

^^

of

*tom

gold (

o~~)"*^^^ich

"

are

the

with 1 atom
of chlorine,
quantitiesthat combine respectively
be depositedat the cathode,or be chloridised at the anode
by the same
quantity of electricity.Hence, the equivalentof
is
gold
given in all the books as the third part of the number
representingthe acceptedatomic weight of the metal. Adopting
would

this

number

and
which

according to

11 183

formed

of silver

2*450

[62*13
[18*30

"
"

1-323

if the current

decomposing
by

"
"

[20*42

"

described

depositedby a
weight of deposit

[37*81grains]gold,

gnus.

4*026
1*186

But

determination,

is

"

correspondingto

above

reliable

mgrms.
of time, the
in 1 second
be
in 1 hour would

of 1 ampere
by 1 ampere

current

Kohlrausch*s

also

the

gold

"

] silver.
] copper.
] chlorine.

solution

in

bath

the

be measured

of a good ampere
meter
means
measuring instrument, it will be found that, in every case,
the quantityof gold depositedwill be considerably
greater than
the calculation
1 ampere
2*450
of gold per hour
grammes
would
lead one
From
to
expect.
repeated experimeots in
the

or

==

which

copper

gold bath, the

voltmeter

in series with
up
first
at
arrived
at the ratio
[Wohlwill]

writer

Copper
whereas
1

the

2*066.

1 ampere

2*953
the

to

Gold

per
2-965

other
hour

words,
should

instead

and

equivalents-^
In

connected

was

"

be

2*49 to 2*50,

"

,-

correspond

to

the

ratio

the

weight of gold deposited by


be
according to this calculation
"

of 2*450

cannot
discrepancy

the

grammes.

assigned to

It is obvious

experimental error,

that
and

*The
number
is used throui^hout the following
197 '13 (0
16), which
based
Gerhard
Kriiss' researches
the atomic
calculations,
on
on
weight of
der CJiemie,vol. ccxxxviii.,pp. 30 and
gold {Liebig^eAnncUen
241), is
regarded as the best established at the present time.
=

371

GOLD.

certainlynot
fact,

the

to

that time,

inaccuracyof

the

voltmeter.

copper

depositof nearly 3

In

of

gold per
grammes
could
in each
hath
he reckoned
even
ampere
per hour
upon,
in industrial works, with the same
certaintyas the 1*18 grammes
of copper requiredby theory was
obtained
in electrolytic
copper
at

the electro-chemical
practice. According to this observation
of
lie
between
79*2
and
79*5 ; but these
must
equivalent
gold
bear
numbers
no
simple relation to the atomic weights A series
of weighingsnext showed
that the ratio 1 : 2*49 previously
found
the
is by no
of ten
baths
constant.
means
case
Indeed, in
and
in
series
the
to
it
connected
same
was
exposed
current,
up
baths
find
several
which
showed
the
to
or
exceptional
same,
nearly the same, weight of deposit. It appeared as though the
tions
Varia^Id had a different equivalentin almost every bath.
in the compositioneither of the solution
of the gold
or
used as anode or in the percentage of acid present, or, again,in
the

temperature,

quantity of the
otherwise

led

diverse

most

ampere

used.

to increase

Indeed

so

or

to

the

that

to

in

Even

be

his researches
arrived

at

the

under

most

in

was

proportion

found

varied

of that

conditions

expected according
Faraday'slaw,
to say that, if Faraday
scarcelybe too much

would
have

decrease

little evidence

constancy of weight of depositunder


would

alterations
hour.

conditions,the quantityof depositobtained

appeared scarcelyever
to

the

gold depositedper

constant

the current

to

to solutions

knowledge

of this

kind,

he would

of his law.

It cannot
multiplicityof the

that
had

it
stricted
re-

never

be doubted

irregularities
spite of this, the
afford only apparent exceptions to the fundamental
law discovered
by Faraday, and must in truth only confirm it.
observation
of the anode
*'An
phenomena throws light on
found.
the discrepancies
According to Faraday's law the loss
be equivalentto the
suffered by the anode in dissolvingmust
The
proof that this is exactly
weight of the cathode deposit.
rendered
difficult by the fact that in course
is in many
true
cases
solid
of electrolysis
size,become
particles,
generallyof minute
from
anodes
which
separatedin greater or less quantity even
If
these
oxidisable
are
are
particles
chemicallyhomogeneous.
with copper, especially
in acid soluand soluble,
is the case
tions,
as
obtain
it is almost
to
accurate
an
impossible
weighing.
be completelycollected
if the separatedparticles
can
But, even
be ascertained
and added to that
that their gross weight may
so
that, in
observed

of the undissolved
the

anode, it

separated at
particles

still remains

the anode

can

to

be

decided

rightlybe

whether

regarded as

anode constituents."
being originally
this question has practically
to
Wohl
will's negative answer
the
of the metallic copper
his
of
been
in
account
source
given
of copper solutions,
found in the anode slimes during the electrolysis
of silver in the correspondingslimes
and on the occurrence

372

BLKCTRIC

obtained in the
writes elsewhere

gold anode

AND

SMELTING

of
electrolysis
as

follows

in

BEFININO.

silver

(see p. 199). Wohlwill

regard to

the

behaviour

of the

:
"

of a
of the anode waste, which
in the case
be
those
anode
in
to
to
gold
analogous
respects
appear
many
noticeable
observable with a copper anode, are
the more
since
the quantityof the gold which
from
in the waste
is withdrawn
"

the

The

phenomena

solvent

influence

of the

ably
always consider-

is almost

current

in the case
greater than
current-densities
employed in

of copper.
practicein

With

the

average

gold-eeparating
processes,

one-tenth of
to about
weight so separatedamounts
and
this
the
in
same
cases
gold depositedduring
time,
many
If the explanationas to the
proportionis greatlyexceeded.
of gold
anode
slimes
of copper
is to be applied in the case
be assumed
it must
that a certain proportion of
electrolysis,
chloride accompanies the auric chloride at the anode, and
aureus
that the former compound at once
breaks up into auric chloride
and metallic gold. In other words, in addition
to the anions
with
trivalent
others
with
certain
number
of
gold atoms, a
monovalent
of gold will also pass into solution,and these
atoms
into
decompose again
AuCl^ with separationof de-ionised gold.
The
from
anode
waste
a
gold anode (or rather the principal
of
the
position
in that case, be a product of decomwould,
waste)
part
of the solution formed
at the anode, and
only a small
of
it
consist
unaltered
anode.
ould
of
o
f
the
m
particles
portion
The compositionof the slimes obtained from impure gold anodes
be regarded as confirming this view.
If the slimes were
may
line
of
of the unaltered
merely an assemblage
particles
very
of silver
anode, it would necessarily,
apart from any admixture
chloride and insoluble platinum metals,have the same
tion
composithe anode.
But this is never
the case.
After extracting
as
the silver chloride and allowing for the other difficultly
soluble
constituents
found
from
the
of
it
action
is
the current,
resulting
that the proportionof gold in the slimes is always considerably
This can
wise
higher than in the anode.
hardlybe explained otherthan by the commingling of pure gold (separated
at the
anode
of
the
same
as
a
during electrolysis
secondary product
action from
which
with
the silver chloride and the like result)
minute
of
On
this
there
the
anode.
must
portions
hypothesis
be a separationof pure gold at the anode
well as at the
as
the

the

cathode.
"As

evidence

product of

that

gold which
decompositionof aurous

separates at the anode is

the

chloride

formed

trode,
at that elec-

that aurous
chloride is present,in a gold
it may
be shown
acid
solution containinghydrochloric
sodium
or
chloride,at a
very

early stage

further,that
anode.

The

the

after the

and,
electrolysis,
from
the
unmistakably proceeds
of

commencement

sub-chloride

characteristic
distinguishing

of

aurous

chloride in

373

GOLD.

solution
and

of the trichloride is its

gradualdecompositioninto gold

chloride under
the influence of dilute hydrochloric
of the solution removed
Indeed, every cubic centimetre

auric

acid.

the bath

from
shows

time

some

separationof

property is observable
has

after the

outside

gold,even

the

twenty-fourhours

even

the

beginning of
or

electrolysis,

bath, and

this

after the

more

been

cut off,
or, in other words, as long as there is
composition
chloride in the solution.^
This deundecomposed aurous

current

any

takes

would

place,as

chieflyat
predicted,

be

the

with the
into contact
point at which the chloride first comes
anode.
acid
the
solution
that
is
at
to
hydrochloric
say,
of precipiUsually,however, exceedinglyfine glittering
tated
particles
gold may be seen throughout the whole solution some
time before any
appreciabledeposit can be recognisedon the
It is possible
surface
anode.
that during this periodthe smooth
of the cast plateschecks
the adhesion
of the depositedgold or
hinders its separation,
that at first the separation
"even
occurs
so
the
in
of the
action
after
the
solvent
a time,
only
liquid. Then,
"

destroysthe

current

time

gold by
the

of the surface,and at the same


of
is
formed for the fine particles
paste
the silver chloride which
of
surface
readilyclingsto the

kind

smoothness

of cement

or

anode, so that,from

portionof the

that moment
separates at the

onward, by far the largest


anode, and the presence of

gold
glitteringparticleswill no longer be observable in the liquid.
Nevertheless,to reproduce the phenomenon it is only necessary
with a new
to replacethe anode
plate.
'*

From

what

has been

said it will be

process has,in the manner


the
decomposition of the

neighbourhood
aurous

exists

way

described,assumed

anode

chloride

throughoutthe

cathode, where
valent

of the

seen

chloride

aurous

that

after the

even

its normal
in

the

course,

immediate

composed
by no means
complete. Undeions
monovalent
t
containing
gold
is

"

"

solution,and

therefore

reach

also

to

the

decomposed simultaneouslywith the trigold compound. It may thus be explainedin the simplest
how
it happens that the weight of gold depositedat the
it is

Mention
will be made
of
hereafter of the fact that smaller (quantities
chloride
remain
in hydrochloric
unaffected
a
cid
solutions,
even
may
here and afterwards
t The writer [Wohlwill], for the sake of brevity,
the expression "gold ions,"although the complex anion, AUGI4, is to
uses
in the case
of auric compounds, and the composition of the
be assumed
ion in the case
of aurous
compounds in this solution is not determined.
the
of
separation the gold as due, in each case, to secondary
Regarding
action
caused by the hydrogen primarily deposited,the action may
be
expressed by the two equations respectively
:
aurous

"

Au

H3

Au

HCl
3HC1.

in both cases, the solutions behave


in regard to the
cathode exactlyas if trivalent or monovalent
gold ions

Hence,
the

AuCl

AuCls

present.

separation at
were

actually

374

ELECTRIC

cathode

equivalent,and
quantity of chlorine

considerablyexceeds
The

is variable.

excess

REFINING.

AND

SMELTING

also

the

same

why

the

is combined

197*13
chloride

in auric

with

=6571

grammes,

"

chloride

with

197*13

equivalentto

are

copper.
should
aurous

one

of

another,

gold.
and

These

also

to

in

aurous

quantitiesof gold
31*80

grammes
6*198 of

of

current

of

1 part of copper, 2*066 of gold,and


gold
auric
from
chloride, and
separated
cupric sulphate,
in baths
chloride solutions
if electrolysed
respectively,
Hence

be

placed in
1 ampere

grammes

and

series.
should

Or,

put it in another

depositper

1 *186 grammes
2*450
"

7*350

to

"

hour

"

[18*30grains]Cu
]Au
[37*81
"

[113*43

way,

"

]Au

from
"

CUSO4
AuCl,
AuCL

"

gold ions in any solution exist with the gold partly


and partlymonovalent, it follows that the gold deposit
trivalent,
will correspond to a mixed
equivalent,the magnitude of which
kinds of ions
will depend upon the proportionin which
the two
be greater
mixed.
In every case, however, the weight must
are
than would
correspondto the equivalentof trivalent gold,which
is given in the books as the electro-chemical equivalentof gold.
It can
that if,for example, as menbe readilycalculated
tioned
now
of gold are
of copper and 2*49 grammes
above, 1 gramme
deposited by the same
exactly
current, there will be almost
1 monovalent
9 trivalent gold ions.
to every
the number
with the above
of
If, in accordance
explanation,
monovalent
ions reachingthe cathode be only a fraction of those
formed
from
at the anode, it follows
Faraday's law that the
solution equivalentof the gold at the anode
be different
must
from
the
(namely,greater than)
precipitation
equivalentat the
cathode.
the
In other words,the loss of
goldanode in weight must
exceed
the
increase
in
considerably
weight of the cathode, even
if no minute
should
become
mixed
of
the
anode
with
fragments
the anode slime resulting
from the decomposition of the aurous
chloride in the solution.
of the aurous
Moreover, since a i)ortion
chloride formed
is not decomposed either at the anode or at the
the
exceed
cathode,
preponderance in the loss of weight must
the total weight of anode slimes producedeither by decomposition
these
inferences
mechanical
Both
of
or
are
by
separation.
the
losses by
supported by experience. Instead of comparing
solution which can
with
d
etermined
be
difficulty accurately
only
detached
that become
of the solid particles
from
the
account
on
anode, the losses of weight of the anodes (which are approxibe compared, after thoroughly rinsing
mately a substitute)
may
them
free from slimes.
In this case, as with the cathode
deposit^
the greatest discrepancies
will be found within the limit set by
the maximum
variation
from
the equivalentof trivalent gold.
But

*'

if the

375

GOLD.

In

both

and
series,
agree

the results obtained

cases

therefore

themselves

among

is

placed in
onlj
absolute uniformityin the

fact,it

In

baths

several

the

by

if there

conditions.

acoompanying
influences

acted upon

with

current, will

same

is safe to

that

assume

the

above

referred to as determiningthe weight of the


the proportion between
the
deposit also determine principally
tri- and monovalent
and
ions
formed
the
at
therefore
anode,
gold
the

quantityof depositwhich

correspondsto

which

the two kinds of ions reach


the influences which
"Among

the altered ratio in

the cathode.

predominate in determining
gold ions enteringthe solution at
the anode, the current"density
is worthy of special
consideration
both theoretical and practical
on
grounds. The writer [Wohlobserved
had
in
that,other conditions
electrolysis
will]
copper
being constant, the increased loss of the anode, and therefore
the quantity of cuprous
is greater
sulphateformed temporarily,
be
in proportion as
the current^density
is less.
It was
to
be met
in gold
with
expected that a similar result would
The
form
in
by
electrolysis.
arranged
experiment was
simple
hanging platesof the impure gold ot approximately equal size
of
as
anodes, in several baths arranged in series,the number
anodes
The
anodes
such
then
were
varying in different vats.
the
either
of
action
the
for
to
an
current,
equal period
exposed
until they were
of time
or
completely dissolved, the results
was
being arrived at by weighing. A large copper voltmeter
the
of the average
determination
accurate
currentemployed for
densityemployed. A few of the results so obtained are quoted
below.
These
results were
obtcdned under
practicalworking
the

number

of monovalent

conditions,and, therefore,cannot
the

accuracy

relation

claim

to express

scientific

with

and
current-density

between

the

chemical
electro-

equivalentof gold in working with soluble gold anodes.


impossible,under the circumstances, either to prepare
an
plates of absolutelyidentical size or to see that there was
absolute
in
like
the
those
conditions
currentwhich,
uniformity
density,influence the alteration in weight ot the electrodes in
the actual
use.
They will, however, suffice to demonstrate
existence
of that dependence in a degree in which
it does not
It

was

appear

to

be

time,

same

found

in the

it will

serve

case

of any other element.


At the
has been
said above
what

confirm

to

concerningboth the equivalentof gold and the relation between


the loss of weight of the anode
and
the gain in weight of
the cathode.
^^

each
the
140
the

Experiment
with

five

1,

"

In

this

plates,and

area
superficial

of

the

experiment
three

part

baths,

sq. cm.
action

be

reduced

appeared
experiment varied
to

with

in
the

size.
area

same

the

baths
with

were

six

plate immersed

of every

[21*6sq. ins.]. The


in all
continued
was

six
each

current

baths

Hence,

was

until

the

of anode-surface

used,
plates,
being

used,
the

duration

and

anode
of the

exposed.

376

ELKCTRIG

SMELTING

BEFIMINO.

AND

''Weighings,after a period of 22| to 23^ hours, gave the


followingnumbers, which are expressedas averages in grammes
per hour

"

The

average

**The

copper
The

''

amperes.
the normal
would
No.

be

showed

an

depositthat would

be

voltmeter

100*7
the

No.

grammes;
minimum

"

but

the
114*0

was

as

follows

average

of 41*1

current

per hour, using


2*45 grms. per hour),
maximum
124-5 in bath
was

produced
=

(or 2*77

amp.

per

was
current-strength
of plates in each
number

used

per

hour)

4.

'Experiment 2.
Experiment 1, but
smaller.

is

equivalentfor gold (1 amp.

8, and

in bath

numbers

of the above

The

The

results

the
were

same

bath

as

in
was

"

123*6 in the originaL"


[This figureis given, evidentlyincorrectly,
as

Translator.]

378

ELECTRIC

SMELTING

AND

BEFINING.

are
longer,period of the work
sufficiently
great to render
of
almost
the
later
inappreciable
changes (both in the areas
reduce
which
tend to
surface exposed and in current-density),
the inequality.
In
the following experiments the same
"Experimenl 4.
this
in every
as
period was allowed for electrolysis
case, and
relative
the
sur"EU)es
hours
the
of
areas
periodwas
only seven
of the
not
at the end
exposed were
seriouslyaltered, even
in the
cast
the
experiment. Moreover,
plateswhich, though
were
so
same
mould, appeared to be somewhat
irregular,
that
baths
the
the
three
in
areas
containing
arranged
exposed
three plateseach were
whilst the platesin the other
different,
baths were
all of practically
the same
(medium) size as those
"

used in bath

No. 3.

The

results

were

as

follows

"

Baths

with

4 Plates.

Baths

5 Plates.

with

4.

Loss at the anode,

Deposit,

111-7
103-7

114-4

134-6

106-0

119-9

8-0

8-4

Difference,

''The

to

103*2

2*90 grammes

(bathNo.

7-9

14-7

the
and
amperes,
therefore
be 101*2 grammes.
of deposit,119-9
(bath No.
grammes

current
average
theoretical
deposit would

greatest weight

1271
109-2

1),

was

was

41*3

ampere-hour,whilst
equivalentto 2*49 grammes
per

the

normal
The
responded
6),cor-

lowest,

per ampere-

hour.
"

Experiment 5, In this experiment,the duration of which


four hours, only two plateswere
hung in each bath, and the
"

was
mean

was
current-density

therefore

raised

to

about

1,500 am-

379

GOLD.

peres per square


of 42*1 amperes,

[131amps,

metre

the results

were

per sq.

ft.].With

current

"

gold were
depositedper ampere per hour in the bath containingtwo plates,
whilst the lowest possiblenumber, correspondingto the normal
a
theoretical equivalent,
have
been 2*45.
would
Hence, when
of
number
small
is
high current-density used, only a very
monovalent
gold ions passes into the solution, and a still
"

smaller
"

had

this it will be

From

In

number

reaches

Experiment

to be

added

an

that

seen

2*48

of

grammes

the cathode.

quantityof hydrochloricacid
prevent the separationof chlorine.

increased

in order to

conducted with
experimentsdescribed above were
acid present per litre of gold
50 c.c. of strong hydrocliloric
solution (or 5 per cent),and at a temperature of 65'' to 70"*G.
At other
temperatures, or with other proportionsof acid, the
have been different,but, in this
series of figures
obtained
would
would
also operate in the same
case, changes in current-density

All the

sense
"

other

above.

as

In

addition

the

to

above

experiments, there

were

made

others also of long duration and controlled with the aid of


These
balance and the voltmeter.
experiments,like the
others,confirmed the observation that,accompanying an increase
many

the

in the loss of
there is always a diminution
current-density,
weight [perampere]both of the anode and of the deposit,and,
of monovalent
therefore,a correspondingreduction in the number
It
found,
was
as
compared with trivalent gold ions.
in the
however, that the existence of certain irregularities
compositionof the baths coupled in series,independentlyof the
of the proportion of acid, might suffice to
temperature and
As is further shown
the
by the
prevent
perceptionof this law.
figuresquoted above,the excess of the weight lost by the anode,
as
compared with that gained by the cathode, also diminishes
of the
In the case
is increased.
rapidlyas the current-density
was
largestsurface used in the experiments detailed,the excess

in

26^times

as

great

as

it

was

in the

case

of the

smallest

surface

of
in Experiment 5). The smaller,therefore, the number
(viz.,
the
the
the
into
solution
at
anode,
ions passing
monovalent
fewer will the ions be that are
decomposed into trivalent ions
the

380

either at the anode


anode

or

slimes,and
anode

the

8MBLTINO

ELECTRIC

will

REFINING.

Hence

in the solution.

therefore
be

AND

the

least when

the

formation

of

breaking away
fragments of
the highestcurrent-density
ia
and
anodeof
slimes
quantity
of

applied. This decrease in the


fragments which do not pass into solution reduces the amount
of material that requiresto be submitted
treatment.
to a second
Further
confirmed
the
that
below
have
expectation
experiments
which
found to be suitable for
the limits of current-density
are
the depositionof gold, the divergence of the electro-chemical
equivalentsfrom the theoretical normal figurefor trivalent gold
direction
is always in the same
namely, that the lower the
the
is
the
number
currentdensity
higher
representingthe
conditions.
equivalentunder the prevailing
Whilst
acidified with
in hot solutions
of gold chloride
hydrochloricacid the theoretical equivalentfor trivalent gold ia
nearlyattained with current-densities of over 1,500 amperes per
the equivalentapproaches
metre
[140amps, per sq. ft.],
square
that
monovalent
of
to
nearly
gold in similar solutions
very
acted upon
about
1 ampere
of
metre
by a current
per square
[0*09amp. per sq. ft.].As, therefore,in the one case the gold
almost
ions passing into the solution
are
trivalent,
exclusively
and
monovalent
ions are
in the other
in overwhelming
case
in the electrolysis
of
occur
excess, extraordinaryvariations
may
gold solutions containinghydrochloricacid with gold electrodes,
both of depositand of anode
in regard to the quantities
loss,
the
vats used are
even
though
placedin series and preciselythe
all. It will be
is therefore passingthrough them
current
same
"

**

understood

that

under
electrolysis

these

conditions

afifords a

remarkable

example, probably unique of its kind, that by


productionof the ions of the same
with Faraday's
element, but of different valency,in accordance
law, the inconstancyof the electro-chemical equivalentbecomes
of the simultaneous

reason

the rule.
'"

the

The

ditions
followingconand
from
description
in practice.
as
applicable
patent specifications

The

Wohlwiil
be
may

Process

in

Practice.

"

the above

accepted from

60* to 70* C,
and
the proportionof gold at from 25 to 30 grammes
pei: litre
free
of
The
3
to
acid,of
hydrochloric
[2*5
quantity
per cent.].
'*

The

temperature should be

maintained

at from

specific
gravity,to be added should range from 20 to 50 cc.,
accordingto the current-density.Since,owing to evaporation
and to consumption in other ways, the quantityof free acid may
of electrolysis,
become
it is necessary
greatlyreduced in course
If the bathintervals.
determine
the
at
.to
proportionpresent
of
temperature be correctlymaintained,however, a deficiency
of
acid
evolution
is
indicated
an
hydrochloric
by
gaseous
In this case, more
chlorine,recognisableby its smell.
chloric
hydro119

acid

must

be

added

until

the

odour

of

chlorine

has

381

GOLD.

it is first ascertained

disappeared,
provided that

that

no

siderable
con-

reduction

of temperature can
possiblyhave occurred.
fine gold
cathode-platesconsist of electro-deposited

"The

be of about the same


length,
may
Even
but of less width
the anodes.
when
high currentdensities are
than
employed, the electrodes need not be more

rolled into thin sheets.

Thej

than

[1*2ins.]
apart.

cm.

''The

vessels

used

as

tanks
electrolysis

earthenware, porcelain,or
the action

The

of hot dilute

other

material

be

may

capable

of

made

of

resisting

hydrochloricacid.

of hot solutions

provide the
tanks with one
of the well-known
arrangements for maintaining
the contained
level.
constant
The flasks employed
at
a
liquid
to supply the tanks
automaticallyare filled with the washthat have been used for washing the depositsor residues
waters
(suchas slimes). In the event of this supply failing but only
"

use

makes

it necessary

to

"

then

In this way it is easy to return


distilled water
is used.
to the baths those diluted
portionsof the gold solutions which
taken from them
in process of washing ; and in so doing the
are
diluted liquidsbecome
concentrated without
using any special
"

appliances,
by the gradualevaporationfrom the baths.
''If the
considerable
contain
gold under treatment
any
quantityof silver the anode will become covered with a coating
of silver chloride,which
is stronglyadherent, and at the same
The
time non-conductive.
of
resultingreduction in the area
the anode
evolution
rise
the
of
and
to
chlorine,
gives
gaseous
attacked, and the
consequentlythe anode will not be sufficiently
In
too low.
proportion of gold in the solution will become
tion
treatingalloysof this kind the stoppage of the process of solube prevented (ashas been proposed for other processes*)
can
by mechanicallyremoving this injuriouscoatingfrom the surface
of the anode
from time to time, the frequency of the treatment
the proportionof silver present and
with
with the
increasing
current
density. Any disturbance that might be caused by
the accumulation
of bismuth
oxychlorideis obviated in the
-

same

"If

way.
the

anode

alloy should

contain

lead

in any
metals, the

appreciable
solution
quantity,in addition to silver or other
be
mixed
with
it
to
will
hydrochloricacid
supposing
only
rapidlybecome saturated with lead chloride. From this moment
"

"

both the electrodes,the walls of the vessel,and the surface of


the bath will become
covered
with
crystalsof lead chloride.
The gold obtained
it is true, be
in the first operation may,
obtained free from lead by repeatedlyboilingit with distilled

water, and

tion
largeproportionof the lead contained in the soluwill separate out on
cooling; but it is undesirable to use
the solution thus rendered
impure by lead for further work.
a

"

German

Patent

36,610.

382

The

ELECTRIC

continuous

SMELTING

AND

REFINING.

and

of alloyscontaining
treatment
satisfactory
if
acid
be
added
to the solution.
sulphuric
may
such
In
it is best to use strong sulphuricacid in quantity
a case
about
equivalentto the hydrochloricacid present. The lead
forms
insoluble
then
almost
film of lead sulphate on
the
an
be

effected

which

either

lead

anode,

graduallybecomes

proportionof lead is
mechanical

replacedfrom

detached,

the

solution

time

to time.

in

with

combination

Since

or,

if the

like silver chloride

Evidentlythe sulphuricacid,which

means.

from

removed

large,is removed

the presence

by

becomes
be

lead,must

of

sulphuricacid
ordinaryprocess, it is generally
desirable to add a mixture
of hydrochloric
and sulphuric
acids to
This should always be
the gold chloride solution at the outset.
done in works
at which
goldcontaininglead has to be treated,
is only exceptional
even
though its treatment
described
The
above
is patented in Great Britain,
process
does

not

affect the conduct

of the

"

United
States,New South Wales, Western
Australia,South
Africa,Belgium, France, Germany, and Russia.
Large plants

the

operation at the time of writing in the NorddeuUdia


Gold- urid SUber-Scheideat Hamburg, the DetUschen
Affinerie
anatalt at Frankfurt, and the new
mint
parations
at Philadelphia. Prealso being made
for the introduction
of the process
are
in Saxony."
in the Royal Smelting Works
at Halsbriicke
Pure
of Gold.
Uses
gold is employed directlyin the production
of chemical
preparationsof gold,for the gildingof other
and for the productionof alloyswith copper, silver,
and
objects,
of
and
other metals.
The
gold
alloys
containingup to
copper
90 per cent, of the preciousmetal are used mainly for coinage*
purposes, but in addition to this they are very largelyemployed
for all kinds
of jewellery and
goldsmith'swork, both in the
condition and as a coatingfor other metals.
massive
are

in

"

CHAPTER

V.

CADMIUM.

AND

ZINC

ZINC.
of

Occorrenoe

natural

Zino

compounds

in

Nature.

of zinc

are

"

the

The

more

important of

oxide, free in

red

zlnc

with oxides of iron, maaganeae,


; mixed
firanklinite; a sulphide,zinc blende, ZnS;

ZnO
[or zincite],
aluminium

in

carbonate,calamine,ZnC03, and

zinc

bloom, a

basic

the
ore

and
the

carbonate

[The British standard


gold for currency is a 22-carat alloy; that is to
24 (or 91*6 per cent ) of gold. The
contains
it
22
in
parts
every
say,
*

residual
copper

for coinage is copper


; for jewellery it may
separatelyor togettier. Translator.]

alloyingmetal
or

silver

"

be

383

ZINC.

electric calamine, Za^SiO^ H^O,


silicates,

the

and

Zn.2Si04.Numerous
well

as

found in nature
with

calamine
and

mixtures

of

with

the

zinc

ores

willemite,
selves,
them-

among

of other

metals,are also
analogous ores
with pyritesand
galena;
; for example, blende
electric calamine, spathiciron ore, white lead ore,
as

others.
Zinc.
have
been

containing

Products

Waste

"

Intermediate

and

treated
products containing zinc
partly to
for
the
and
of
its
production
compounds.
produce zinc,
partly
furnacezinc-dust,flue-dust,
Among these may be enumerated
produced zinc carbonate (accretionsforming in blast furnaces
employed for the extraction of other metals from zinc-bearing
and lead
ores),zinc scrap, zinc ashes (from galvanising plant),
both
and
the
zinc
the
from
preciousmetals,
alloyscontaining
waste

"

"

of lead and

treatment

of

Properties

metal,

with

silver

ores.

Metal.

the

Zinc

"

is

bluish- white, lustrous

crystalline
(hexagonal)Ktructure, and

specific

gravity of 6*9 to 7*2. At ordinary temperatures it is brittle,


100" and 150" C. it becomes
and
but between
be
malleable,
may
into sheet or
wire.
At a higher
rolled,hammered, or drawn
temperature
it may
between

be

200" C.

^about

"

crushed

930" and

to

brittle that
so
again becomes
powder. It melts at 415", and boils
Its electrical conductivity
at ordinary

950" C.

0*27

is about

temperatures

it

"

that

of silver.

It has the power

of

being dissolved by most other metals ; and witli


dissolving
in
it
alloys all proportions.Lead, however, dissolves only
many
and zinc but little lead
little zinc (lessthan
1*5 per cent.),
a
2-5
than
(less
per cent).
Metallic zinc has a comparativelyhigh power
of resistance to
or

the

of

and other constituents


of the air.
It is
of oxygen
becomes
that in moist air it rapidly
covered with a greyish

action

true

film

of

basic carbonate
the

clingsfirmly to
protectedby
practically
boilingpoint,however,
carbonic

acid.

Water

this

but

sur"ce

of

it from
zinc

has

the

metal,

further

burns

but

coatingis

very dense, and


which
is, therefore,

oxidation.

readilyeither

little action
red

Above
in air

its
or

in

the metal at
upon
heat
it forms
zinc

a
ordinary temperatures, although
and hydrogen (seeLead Rejming), Zinc burns in chlorine
with sulphur;
to zinc chloride,but does not easilyunite directly
formed
a phosphorzinc may,
however, be readily
by introducing
the
of
melted
metal.
into
pieces phosphorus
On
of its stronglyelectro-positive
account
character,and the
of its salts,zinc is easilydissolved
of most
great solubility
by
dilute acids ; but the solution takes placethe more
the
slowlv,

at

oxide

used.
Nitric acid is in part convertea
the
metal
into
purer
The
action
electro-chemical
its
zinc.
ammonia
teristics
characby
upon
of the metal are shown
by the fact that it is capableof

separatingmost

of the

heavy

metals

from

their

salts,and

that it

384

KLBCTBIC

is soluble

8MELTIKQ

AND

REFINING.

ia solutions of the alkaline

hydroxides with evolution


of zinc
of hydrogen.
high electrolytic
solution-pressure
makes
it a good anode material for galvanicbatteries.
With
acids, zinc forms only one series of salts,which
are
oxide
derived from the oxide, ZnO ; with the alkalis,
zinc
(or
the
which
and
forms
salts
of
an
acid,
hydroxide)plays
part
may
be regardedas derived from the hydroxide,Zn(0H)2, the latter
being considered as a dibasic acid.
of the zinc compounds present as ores, furnace
The
nature
and waste
materials, together with the propertiesof
products,
zinc and its associated metals, are such that it is rarelypossible
The

to obtain

pure

A.

zinc.

EXTRACTION

BOASTIira

1.

AHfB

ZINC.

CRUDE

OF

BEDnCTIOir

PBOOESS.

Although, under the different working conditions, various


been
of procedure have
methods
adopted in carrying out this
used
which
for the extraction
is
of zinc
very commonly
process,
from its ores
(Silesian,
Belgian,Rhenish, and Englishmethods),
the same
chemical
all
basis.
founded
The
yet they are
upon
converted
are
as
ores
completely as
sulphide and carbouate
and
then reduced
oxide
i
nto
an
are
oxidisingroast,
by
possible
them
with
inferior coal or small coke,
and distilled by mixing
and collected
and heating in retorts,the zinc beingdistilled over
in condensers.

It is unnecessary
here to enter into the details
It may, however, be well to emphasise a fact,

of this process.
which
is not contested

by

even

the

zinc

manufacturers

selves,
them-

working conditions ^the small size and great


and the volatile and
reducingapparatus (retorts),
chemical and physicalpropertiesof the zinc
co-operate
that all the

of the
fragility
other

"

render

to

it the

most

wasteful

metallurgicalpractice,even

process
when
the

in the

whole

richest

ores

of
range
available

used.

are

The

Cowles

Zino

Prooess.

"

It

is well

known

that

the

heatingof a conductant charge used as a resistance has


results in many
for processes
cases
alreadygiven satisfactory
The
heating of
depending upon highly-endothermicreactions.
renders
electrical
from
within
pendent
indemore
means
us
a chargeby
the containingvessel is made
of the material of which
be the case
when
external
than can
firingis used, as soon as the
This
of very high temperatures becomes
necessary.
application
led
the
the
of
brothers
Cowles''*'
which
one
grounds
evidently
was
of heatingthe charge in the zilic
to experiment in the direction
retort by electrical means
(seeFig.214).
electrical

German

1885.

Patent

34,730,June

10, 1885.

[EnglishPatent

6,994,June

9,

386

BLKCTRIC

SMBLTINQ

AND

REFINING.

by A. Dorsemagen "^^ in this


experiments made
silicon
of obtaining zinc and
direction,proved the possibility
rich in silicic acid.
In the
of ores
carbide by the treatment
if the proportion of zinc is
of such ores, especially
treatment
not
high, a considerable quantity of heat is necessarily
very
stuff which
remains
expended in the heating of the gangue
The
silica
the
the
and
in
retorts.
completely unchanged
first of these

mixed

carbon

with

Fig.216.
lies not

reduced.
a

which

very
The

"

raised

it become

Dorsemagen'sziiic and
far

distant

from

production of

construction

of

pure

temperature

which

silicon carbide furnace.

that

furnace,and

to

at

silicon
entail

which

silica

would

can

be

certainly
complicationsin use

would

quire
re-

indicate that a combination


to
of this
appear
that
of
zinc
extraction
could
process
scarcelybe regarded
The
advisable.
as
formation
of silicon carbide
however,
may,
be effected in the simplest
and
doubtless
at a lower
apparatus,
with

"German

Patent

128,635,December

25, 1900.

387

ZINC.

The

temperature.

suggestion of Dorsemagen

of zinc with

the

carbide

by raisingthe temperature

carbon

was

found

in

effect

to

unite

of the

residue

into

of the

mixture

of

conversion

the

traction
ex-

silicon
ore

and

be

readily practicable. The


illustration
accompanying
(Fig.215) will suffice to show that
the apparatus is very
simple, and tliat,by maintaining the
of
on
simplicity construction,it may be adapted for use even
a
largescale. It requiresbut a simple calculation to show that
of zinc with
the production of
by combining the extraction
silicon carbide, commonly known
as
carborundum, there must
be a considerable
the
in
expenditure of heat as compared
saving
with
the processes conducted
the reduction
as
separately,
especially
acid
of
silicic
is
not
temperature
very greatlyhigher than
that

to

of zinc oxide.
of

Treatment

It

Blende-bearing

is

Pyrites for Zino

Ferroand
blende
in
pyritescontaining

possibleto treat
for the production of zinc and
ferro-silicon.'^
Ores of this kind are to be found containingover
20 per cent, of
zinc.
Tip to the present time only the sijdphur(so far as the
conditions
of transport allow)is utilised,
and that by converting
it into sulphuricacid.
While, however, the residue, or burnt
the
manufacture
from
other
of vitriol from
forms
of
pyrites,
find some
in blast-furnace
use
pyrites can
practicefor the
of
residue
the
from
this
production
pig iron,
corresponding
be utilised in the blast furnace
mineral
cannot
owing to the
of
zinc
other
contained
On
the
in
it.
hand,
high percentage
be extracted
the zinc cannot
it by the usual metallurgical
from
of the large proportion of iron present. Experiments
process by reason
which
been
have
made
in experimental plant, at
Duisburg and Fiirfurt,for extracting the zinc oxide in the
then
and
have
wet
means
working it up by electrolytic
way
successful issue, although
not
yet been brought to a practically
that
be
said
such
is entirelywithout
it cannot
a
yet
process
residues which
In the case
of pyrites,
not
are
hope of success.
of
extraction
zinc
and
at
too poor in zinc,a treatment
an
aiming
ferro-silicon in the electric furnace
is to be preferred,
especially
such
blast-furnace
where
of
water
sources
as
cheap
power,
power,
silicon.

"

similar

gases,

apparatus

are

as

treatment

of

carbide.

For

serve

they

available.

dec.,are

as

do

was

not

Both

the

those

used

itself and

the

by Dorsemagen

for

process

simple
highly siliceous zinc ores
experimental purposes,
as

used

in

the

contain
initially

last-named
sufficient

for
the

zinc

same

process.

silica,are

and

silicon

furnace
The
mixed

paratus
apthe
will

ores,

if

with

der
Aachen
Ardasa
aus
Denkschrift der k. t. Hochsehtde
Industrie-,
Oewerbt; und Kunstauastellung zu Dtieeeldor/im Jahre, 1902, Aaohec,
Institut fur MttaUhiUtenwesen
und
1902, 48 pp. ; and Borchers, Das neue
der k. t, Hochschvle
Elekirom^cUlurgie
an
zu
Aachen, Halle a. S., 1903,
*

13 pp.

388

ELBCTRIC

sand

SMELTING

ferro-silicon.

It need

for reduction
of

fused

is rendered
for the

2.

be

small

tapped

In

the

to

sulphide ores,

taken

the

ot

acids

cent,

of the

in the form
the zinc

furnace, while

process

working scale
readilythan is that
a

on

silicon

to time.

in the

account,
in which

METHODS.

which

solvents

been

have

ores

proposed

of zinc

case

the

of

insoluble.

are

group
of most

necessary
coke.
or

carbide,since the ferrowhich


is also formed, can
slag*

and

hydrogen sulphide

per

of charcoal

PBEOIPITATION

AND

addition

ginous
ferru-

25

the carbon

form

operation more

time

iron, with

of the reaction

The

quantity of

off from

LEACHING

other

in

production of zinc

silicon and
both

continuous

the

bottom

the condensers.

in

yield

to

said that

the end

at

the

regulusat

distils off into

sufficient

scarcelybe
provided in

is best

ferro-silicon is found
a

REFINING.

silioeous zinc ores, or, if deficient

or

fluxes, in quantity

The

AND

be

metals

of

the

nature

of

the

the
The

must

ores,

for

gangue,
which
be treated
cannot
percentage of zinc or of

(but especiallyof those


of their low
metallurgically
by reason
the nature
of the gangue) imposes very

gr"at limitations

use

however,

the

on

zinc

ores

of this solvent.

Zinc

be precipitated
from
its solutions or
may
salts by either chemical or electro-chemical
means,
with

one

need

be taken

exception to

mentioned

be

its fused

from
but

hereafter,only

obviously,
the

latter

largenumber of
treatment
ores
by leachingand precipitation
the immediate
aim
at
preparation of pure metal.
These
will be referred
for the
to in treatingof the methods
will only
of pure zinc ; and at this point a description
extraction
still
be given of processes
to be
far
so
as
which,
they appear
metal.
crude
under
yielda
practicable
existingconditions, must
To this category belong especially
the processes
involving the
it will suffice
anode
and
of
the
in electrolytic
ore
vessels,
use
as
Bias and
to explain the processes
of Luckow
and
Miest, since
historical
interest.
considerable
they possess some
Luckow
The
Process.
Iiuokow
specifies*that granular
zinc
zinc is to be obtained
of concentrated
the
electrolysis
by

inventions

into consideration.

for the

Most

of the

of zinc

"

salts,and
allowed

that the acid set free at the same


time at the anode is
the zinc ores, polarisation
to attack
being suppressed

According to the patent


the
used for the electrolytic
cells,
the
to
alternate sequence
parallel
and
cathodes
of the cell. The
zinc plates,
are
of
cloth
stretched
are
placed diaphragms
upon

and chemical
by mechanical
specification
long troughs are
polesbeing placedin them in
shorter

sides

beneath

them

frames

plates.

to

receive

Between

the metal
the zinc
"

German

means.

separates from

which

platesare
Patent

cells with

14,256, 1880.

open

the

cathode-

lattice-work

389

ZINC.

(orof basket-work)projectingsomewhat

sides

filled with

in the vat, and

roasted
of metal

is inserted

metallic

make
When

the

anode,

the

in order

to

conducting mains.

chloride

chlorine

zinc ores, or
A bar
alone.

above

from

this mixture

with

of zinc

solutions

carbon

into

contact

and

carbon

with

metallurgicalproducts,or

or

the solution

above

of carbon

mixture

with a
electrolysed
removed
is
pole
troduction
chemicallyby the in-

thus

are

liberated

this

at

of air,or
mechanicallyby a current
of sulphurous acid.
If,however, the anode consist of
and
of coke
a mixture
blende,the free chlorine attacks the latter
and effects the solution of the zinc.
A slightly
tion
acidulated soluthis
salt may
be used
of common
i
n
as
case
electrolyte

either

of zinc chlorides.

instead
Bias

Miest

and

proposed to

crush

to the
pass through a sieve of 5 meshes
into plates under
unite the particles

the

order

in

advantages as
with

obtain

be

to

anodes

it

which

methods

other

But

time.

to

linear
a

suitable

had

been

has,nevertheless,made

no

it would

until

then

inch,and

pressure
heated
and

They considered that their


compared with those in common

process.
and

then

plates were

blende

the

for

process

of 100

spheres;
atmo-

again
their

to

pressed,
com-

lytic
electro-

offered great

metallurgical
use,
that
to
proposed up
headway.

in this placeto enter into a detailed account


It is unnecessary
difficulties
of the
resultingfrom this method of work, after what

has been

in the

written

chapteron

copper

concerning

the

use

of

anodes.

sulphideores as
Up to a few years
had

treatment

ore

ago, before the electro- magnetic process of


reached its present state of development,the

product in the dressingof blendiferous galena ores


peculiardifficulties to mechanical separation
owing to the

intermediate
offered
intimate

of

nature

solvents

ferric

as

been

the

mixture

The

obtained.

sulphate,ferric

chloride,and

of

use

such

cupric chloride,

phide
of sulapplied of late in the treatment
of all kinds,appeared from the first to be unsuitable ;
ores
and therefore Dorsemagen, at the author's (Borchers')
suggestion,
and working in his laboratory,
undertook
experimentsaiming at
These experiof free chlorine.
attackingthis product by means
ments
results in regard to the
not
only gave very satisfactory
extraction
of the several metals
present, but proved also the
the
whole
of
of the sulphur present in the
possibility recovering
decomposed sulphides. The process was, in these experiments,
which

have

often

conducted
In

follows t
first startingthe
as

is mixed

with

:
"

process, the crushed


dilute solution of a

magnesium chloride,or

or
*

Bias and

the

like,and

(or dressed

ore

salt,such
is then

a
Miest, Esaai (^application
d^dectrolyee

la

xv.,

duct)
prosodium

treated

with

mitallurgie,
Paris,

1882.

iZeitschri/t/iir
angewandte Chemie, 1902, vol.

as

p. 637.

390

AND

8MBLTIHQ

KLBCTRIO

RKFIKIHG.

rotatingbarrel. The chlorine is most conveniently


through a hollow shaft,from the apparatas
It is best to keep the mass
slightly
emplojed for electrolysis.
30* to
of
from
the
warm
chlorination,a temperature
daring
for the purpose.
40* C. sufficing
Only a very slightpressure is
required to drive the chlorine into the slimes. It dissolves
readily in the solution and reacts with the sulphides. The
followingtable gives the quantitativeresult of treating 1,000
kilogrammes [1 ton]of a product from Broken Hill ores, which
magnetic
electroor
not
was
capableof further separation by mechanical
of chlorine
methods.
Only an exceedinglyslightexcess
was
employed :
chlorine ia

pasted into the barrel

"

For

the purpose
consisted
of

(Fig.216)

with

Fig, 216.
rollers.

"

In

construction

ders
experiments the chlorination cylinrotated
which
were
slowly
largeglass flasks,
of

these

aid of

the

small

Experimentalchlorination
actual

water

barrel

practice,chlorination

(as,for

example, lead-lined

turbine

used

and

wooden

by Dorsemagen.

cylindersof ordinary
iron

drums)would

be

employed (seeFig.217).
From
in

the

treating

results
mixed

recorded

above, it would

sulphides,the

lead

appear

as

though,

sulphide passed

into

391

ZINC.

solution

fore
therebefore the zinc compound.
Experiments were
tried in the direction of chlorinating
very slowly with only

the
lead

quantity of

exact

chlorine

necessary
the result did not accord

present,but

to

with

combine

with

the

this

assumption.
complete solution of
the lead and
the presence
of so largea proportionof zinc sulphide
in the residue were
explainedby the fact that the lead
sulphide,which is comparativelysoft,had been reduced during
the preliminarycrushing of the ore
smaller size of
to a much
had
the
harder
and
zinc
than
blende.
The chlorinadense
grain
A

closer examination

tion-residue
than

that the

showed

blende

this zinc

contained

The

the rest of the material.

more

cylinderto

Chlorination

"

condition

coarser

complete conversion

portionof the zinc blende


large-grained

Fig.217.

in

into chloride

of this

would

be used in practice.

excess
long time and a considerable
required a relatively
the metals
chlorine.
present in
But, taking into account
products separated after chlorination,it is evident that
complete conversion of this portion of the zinc blende

chloride

be

would

residue, which
under
works

unnecessary,
practicallyfree from

which

conditions
as

somewhat

is

rendering

the

would

not

material

be

have

for the

lead,
for

the
the
into

chlorination

contains

considered

unsuited

of

zinc

by the zinc
metallurgical

treatment.

It

may

be

above-described
made

mentioned
confirm

elsewhere,that the

Hill mixed

ore

is

point that the experiments


interestingobservation, already
largerpart of the silver in the Broken
this

at

the

present in

the zinc

blende.

392

ELECTRIC

SMELTING

AND

REFINING.

The

snlphur may be recovered from the chlorination residue


melting it out of the slimes under pressure, after the maimer
The
treating the soda residue in the Schaffner process.

by
of

slimes

obtained

after chlorination

of undissolved
both

remove

the residue

before

where

however,

but

chloride and

necessary
evaporation as far

slimes with

reheated

of the

some

to

On

best to

chloride

from

readilyeffected
a largerscale,

minimise

the

quent
subse-

possible,the author
might be dissolved by
solution previouslyobtained,
as

been

cooled

down

of the lead chloride

removal

was

ties
quanti-

of lead chloride

it had

after

separationand

lead

water.

be

it would

probably be

the
This

the aid of hot

of
process
that
residue
the
suggests

treatingthe

it will

treatingit farther.

scale with

considerable

contain

chloride,and

the dissolved

the small

on

lead

to

allow

of the

previouslyextracted

soluble in the hot than in the


[thiscompound being far more
The
of
liquidwetting the residue finally
liquid].
portion

cold

This
completelydisplacedby a little hot water.
be
used
in
naturally
subsequent operations,
again and again,until it should have attained the same
degreeof
concentration
the solutions obtained
as
by the chlorination itself.
after stirringthe slimes with water, the sulphur was
Finally,
melted
out under
a steam
pressure of two atmospheres,as in the
could

then

be

wash-water

would

of soda

treatment

residue.

alreadyexplained,a largeproportion of the lead chloride


has dissolved in the warm
liquidseparates out on cooling.
it
order
loss
In
of lead, is well to allow this separation
to avoid a
to take
place quietlyand completely,for the iron which will
the ore
also have passed into the solution from
be
must
next
The iron is present as chloride,and only requires
precipitated.
the addition
of a basic precipitate
in order to effect its separation.
Lime, soda, or the like,may, of course, be employed for
material containingzinc
the purpose, but it is better to use
a
obtained
a part
oxide, such as may readilybe
by dead-roasting
As

which

of the final residue.


There
from

the

available
is not

for

much

successful
the

available for the separationof the


ways
many
of them
are
lead,but by far the largestnumber

are

use

on

evidence

as

separationof the
mixed

become
After
offers

removing
no

metals

"

the

cases

not

there

one
as

the

another

being the

they have
satisfactory.

after
most

process which
liquidis rapidlyevaporatedwith the

silver from

difficulties

in these

experiments point to
(Borchers')
from

in the metallic state


the

even

yet of their being brought into fully

author's

The

use.

largescale,and

zinc

solutions

"

alreadyseparated,and so brought to dryness. As


of galvaniser's
in the treatment
waste, this can be accomplished
there
until
is
without
only a very small quantity of
difficulty
chlorides
then
left. The
water
are
nearly anhydrous mixed
fused and electrolysed.
lead chloride

394

SMELTING

ELECTRIC

zinc
electrolysing

chloride

AND

REFINING.

on
practicable

is thus

industrial

an

scale.
the
complete dehydrationby electrolysis,

After

which
lead and zinc chlorides give two alloys,
rest
little
zinc
other
lead, and
namely,
containinga
"

small

mixture

of

one

upon
lead with

the
a

This
being at the bottom.
result would, of course, have been anticipated
by anyone having
of zinc.
lead by means
a knowledge of the process of desilverising
the
form
in
the
of
to
Having regard simplicity
apparatus, it is

proportionof

obvious

that

no

zinc

the latter

"

attempt should

be made

to

separate these metals

The
latter should
tank.
tapping them from the electrolysis
the
metals
direct
into a
that
BO
run
arranged
separated
kettle,in which the metals are first separated
separately-heated
the deis separated from
mechanically,
just as the zinc scum
in
be

silverised

lead

in the

[Parkes]process

referred

to above.

The

familiar to those
product is sufficiently
lead
and silver. The
of
are
metallurgy
lead containingzinc is purifiedby means
of steam, whilst the
distillation.
which
contains
is
to
lead,
zinc,
subjected
The productsof the treatment
of blendiferous galena or of the
material
obtained
by dressingit are therefore as follows:
the
chlorination residue consisting of a zinc
(1) Sulphur; (2)
and capable of metaU
blende free from lead,but rich in silver,
lurgicaltreatment;
(3) silver; (4) lead; and (5) zinc. The
carried out so that it leaves practically
no
process is therefore
residue.
The quantityof material used up in the process is very
small,as it is only necessary to make
good the chlorine lost in
chloride or other suitable
working by an addition of sodium
further

treatment

who

of this

acquaintedwith

the

"

chloride.

containingheavy spar, which usuallyare not free from


compounds, may be treated by this process. If,however,
that are free from lead, it is probable
is requiredto treat ores

Ores
lead
it

that the electro-chemical


be

would

treatment

simplifiedif the

of the zinc chloride

obtained

solutions

were
electrolysed
;
aqueous
tinctly
althoughit is true that, in that case, the apparatus would be disless simple,
as
Hoepfher'sexperiments have proved. As
an

the zinc may


the
solution
evaporatipg

alternative

method,

be obtained

in the form

of

an

to dryness and
treatingthe
alloy,by
other
with
of
metals and
it
zinc
oxides
chloride,mixing
resulting
calcium carbide under the conditions described by von
Kiigelgen.'*^
The
of blendiferous
fear that, as in the case
galena,a large
proportionof the blende would remain in the residue containing
in
heavy spar, appears to be groundless,since if the blende were
would
suffice for
the form of largegrainsa mechanical
treatment
of the minerals
the separationof the ores ; whilst if the mixture

the zinc blende


very intimate
zinc dissolved without
difficulty
by
were

could
means

be

attacked

and

of chlorine.

Zeitschri/t
1901, vol. vii.,pp. 541, 651, 573.
fur EiektrocJiemie,

the

395

ZINC.

Xfothemann's
a

process

ores

of

dead-roasted

or

blendes

used

sulphate,are

is taken

"

alkali-metal

of neutral

or

and

Process.

Finallj,reference

Nothemann's,'*^aiming at

as

at the cathode.

Solutions

electrolyte.It is claimed

ensure

B.
1.

chloride

REPINING

that

if

care

and

the

will amount

to

cathode

ZINC.
OP

ALLOYS.

lurgical
of crude
zinc in metalpurification
works
is partly conducted
by a liquation process.
have
been
tried
on
a
Experiments
fairlylarge scale in the
of the crude metal, especially
in regard to
treatment
electrolytic
the silver alloys,
rich in zinc, obtained by the JElossler-Edelmann
for desilverising
hitherto
zinc, but
they have been
process
without
results.
the
One
of
longestin use has been
permanent
Friedrichshiitte
the
Tamowitz
in
at
a
Konigliche
plant at
obtained
Silesia. The compositionof the scum
in the desilverising
plant at these works varied within the followinglimits :
As

is well

PURE

to

zinc

of alkalis

salts,includingammonium

the
good contact between
the
the
o
f
extraction
zinc-bearingparticles
ore,
99 per cent, of the zinc originally
present.
to

be made

must

the redaction of oxide

known,

the

"

This
1

cm.

each.

accordingto Hasse's account, t was cast into anodes


alloy,
[0-4in.]thick,weighing 20 to 30 kilogrms.[44to 66 lbs.]
These

anodes, following the type of the old aiemens

crude

provided with side supports which rested


the
conducting bars laid along the edges of the tanks.
upon
of zinc sheet
The
which
also resembled
cathode-plateswere
those used in electrolytic
Each
cell contained
copper refining.
6 anodes
5 cathodes
of about
at a distance
suspended between
between
each
50 mm.
electrodes.
of
The
pair
electrolyte
[2ins.]
80 to
was
a solution of zinc sulphate. The
was
current-density

copper anodes,

90

amperes
*

German

were

per sq. metre


Patent

[7*4to

8*4 amps,

per sq.

118,291,October 19, 1898.


Berg-f HtUten-, und Salinenweeen

fZeUaehri/tfur dtu
PrtUMen, 1897, p. 322.

ft.]for
in

which

Konigreich

396
KM.F.

an

8MBLTIM0

ELECTBIC

that

of 1*25

30 amperes

by using

is

of spongy
of over

current-densities

depositedby

employment
working with
preferred on

insoluble

100

amperes
overlooks
the

states

current

of

is

only

when

or

sq. metre
the
fact that
when
necessary

such

per

densities

are

on
a
grounds as in electroplating
large
wliich
the
of electrolytic
experiments

other

scale.

In

author

has
[Borchers]

the

anodes,

and opposes
the
per sq. ft.]
zinc is only to be avoided

he
per sq. ft.];but
of high current-densities

[9*3 amps,

Hasse

necessary.

[2*8amps,

per sq. metre


the formation

that

REFINING.

was

quite unexceptionablezinc

view

volts

1*45

to

AKD

course

conducted

laboratoryunder

the most
of
frequentopportunities

with

insoluble anodes

in

his

of work, he has had


observing that the formation of spongy
conditions

varied

could
in working, at the cathodes
by irregularities
the
anode
be checked by
at once
connectingup of a zinc
0["posite
750
of pine wood
tanks were
the faultyplace. The electrolytic
24
600
wide
700
mm.
mm.
mm.
27|
deep [30 x
by
long by

zinc,caused

ins.l lined

with

sheet

lined with

further

prevent injuryto

the lead sheet

bath, but

front side the liningof boards


from

centimetres

the

[0*08in.]thick.

mm.

pine boarding,which

thin

in the

the electrodes

lead

wall

This

only to
suspending

process of
also to check currents.
was
placedat a distance

of

during the

caused

thus

the

lining left

to pass through the space


The
tank
at the bottom.

the

vat, and

the

free at the bottom


[6 ins.]
accumulated
in this space.

of the

In

continuous

formed,

tank,

and

was

served,not

so

On
of

solution

the
few
was

that it entered

space of
the anode

15

cm.

slimes

The

eight tanks were


arranged in
batteries placed terrace-"shion
two
(at descending levels)to
the
of
circulation
the
the
At
facilitate
liquidthrough them.
lower end of each battery there was
placeda set of steps for the
these
The
trickled over
the
solution.
of
electrolyte
purification
and gentle stream
left
after it had
steps in a steady uniform
the

tanks.

with

the

improved
and

air

this way

was

and

brought about,

such

introduction

of

by

even

the

the lowest

of the steps were


of zinc
amount

as

very intimate contact


have
could not
been

air-blast. The uppermost


shaped like flat basins in
an

oxide, and zinc sheet scrap


themselvea
on
was
Hence, the small quantities
steps
of injurious
metals which
enter the zinc sulphatesolution during
which

was

laid

certain

the

its passage
through the depositingtanks would thus be separated,
since the liquid was
the
and
always carefullyled over

steps, it

was

maintained

arrangement
whole

appears,
A
process.

obtained
In view

until

these

sufficiently
Simple as
pure.
the
conduct
of
important for
result
was
continuously satisfactory
it is

steps

of the author's

were

this
the
not

introduced.

statement

has proved to be
this arrangement
there appear to be objections
to the

gainsaidthat
satisfactory.Nevertheless,
of the apparatus
disposition
it cannot

be

397

ZINC.

which

point
at

one

converted

ferric

if

zinc,as

time, the formation


least be rendered
this
the

is

with

well

as

of the

be
be

may

Yet

The

from

same

compound

must

the

account

above

at

It would

better

appear

that

the

zinc

that

full tunity
topmost steps alone, so
opporfor the completion of the oxidation
of the

given

anodes

remained

to four

baths

days

after

from

in the

four

baths.

days, the

six

to

The

slimes

of from

were

cathodes

from

removed

from

eight
days. The
slimes contained
in increased
ents
proportion all the constituzinc
in
the
with
certain
a
accompanying
alloy,together

anode

period

oxide

of zinc

amount

materials

All

removed,
may

^that,

so

remained.
be

present that
The

reckoned

in

the

had

constituents

the

analysesgiven

11-64

1519

Ck)pper,

50*95

29*89

earlier

DetUsche
papers,

Gold-

date
und

describingthe

appeared

that

30 and

had

accounts

been

SUber-acheideanstaU
of the

treatment

zinc chloride

solutions

of

zinc,

"

silver

60 per cent.
contributed
various

to

zinc

thus

were

(2)

considerably,the

between

first

follows

as

Lead,
varied

the

removal

64-92

....

the

principally

copper

above

from

sulphuricacid.

(1)
37-41

proportions,however,
in singledeterminations
an

and

slimes, after

Silver

At

in

were

in this acid

lead

end,

away

of dilute

means

composition of the
from

broken

soluble

were

fourteen

to

zinc which

and

disintegratedplates. The latter


from the slimes by
place removed

it

at the

to react

ferric
precipitable

compound.

ferrous

The

that,
air,the iron present as

and

air, is allowed

difficult.

more

zinc scrap.
the
on

should

the

fluous,
super-

known

here, if the steps at which


unquestionably the case
the opportunity of reacting most
energeticallyare

covered

three

of zinc oxide

being

It is well

has

air

scn^

instance.

is
only capable of precipitationwith difficulty,
and
becomes
therefore
hydroxide
precipi-'

into
But

table.

reagents used

of the

present

action

salt,and

ferrous

other

or

in the

combined

the

by

to

least

by

the

technical
From

scum.

of

ing
rang-

these

specificgravity
and that they were
electrolyte,
purifiedfrom time
time
to
zinc
basic
chloride
The
by adding
(ZnCl 3ZnO).
cathodes consisted of circular zinc platesmounted
on
a
vertically
That
horizontal rotatable
shaft.
unsatisfactoryexperimental
very
obtained
results were
in the originalprocess
for desilof zinc is shown
by means
verifiing
by the fact that the zinc
1-27 served

1*2 to

as

up to 77 per cent, of lead.^


There
is no need
to go minutely into certain older processes
Hermann
t and Watt
| for the electrolytic
proposed by
refining
scum

contained

Dingier^8 polytechn, Jourtuil, 1887, vol. cclxiii.,


p. 93; Festschriftzur
lOOj"hr, JvbUduTMftier dtr kdnigl.FriedejishiUte, Berlin,
t German

Patent

J English

Patent

24,682 of 1883, and


6,294, 1887.

33,107 of 1885.

398

BLECTBIC

of crude

SMELTING

zinc,since they do

by

paper
observations
zinc

that he had

depositsunder

solution
Kiliani

Kiliani

and

of

which

of

Experiments

Mylius

to the requirements
practically
purification.
appeared in 1883 described

the characteristics of electrolytic


conditions

current-densities.

for his

and

on

various

experiments
practical
importance.
The

zinc

made

REFINING.

contribute

not

of electro-chemical
A

AND

have

Mylius

The

conditions

not, however,
and

in

chosen

of

by

led to results of

by
exceptional
the practice
of zinc
at
quote
length,at

Fromm.

t which

Fromm

of concentration

"

paper

1895, is of

appeared
concerning both the theory and
It is desiraole to
refiningby electrolysis.
the separationof zinc in the spongy
on
least,their observations
of
condition,and the means
prescribedby them for the removal
this difficulty.
of spongy
The
zinc depositshas not jet been determined.
cause
Nahnsen
considers
that
attributed
be
must
to
X
they
formed
the oxides which
are
by the decompositionof the water,
whilst others " believe in the existence of a hypothetical
hydride
of zinc, ZnH,, which
produces a molecular alteration of the zinc.
As we
(Mylius and Fromm) are at present engaged in a special
investigation
|jof porous metallic deposits,we are prevented
from
entering farther at this time into the question of the

interest

as

'*

formation

mechanical
that

out

of zinc

its formation
and

that

oxygen,
is proved without

is

sponge

we

however, point

may,

accompanied by

absorption of
always contains oxygen or basic salt. This
doubt
by the followingobservations :
an

it

"

without
"(1) The spongy zinc will not dissolve in mercury
behind
residue
of
basic
oxide
a
or
salt,amounting
slight
leaving
usuallyto considerablyless than 1 per cent.
'^(2)The production of the sponge is induced by oxidising
agents. Thus a 10 per cent, solution of neutral zinc sulphate,
0*01 per cent, of hydrogen peroxide,shows
which
contains
a
of sponge
density of 1 ampere

formation

again,if the

solution

even

after

two

minutes

with

current-

per sq. dm. [0 0645 amp. per sq. in.]. Or


contain
0*1 per cent* of zinc nitrate in

placeof the hydrogen peroxide,a greyish-black


depositof zinc,
Or
containingoxide, will be formed after about one minute.1I
if a sheet-zinc cathode be spottedwith oil of turpentine containing
greyish-blackflakes,which are the first signs of
oxygen,
tion
a
re
sponginess, formed at these places. The zinc sulphatesoluin
these
hour
for an
used
employed
experiments,when
1883, p. 251.
Berg- und hiUtenmdnnische Zeitun^,
*

i ZeiUchriftfuranorganischeCfhemie,1896, vol. ix.,p. 144.


tBerg- und hiiUenmdnnische Zeitung,1891, p. 393.
(German Patent 66,592).
" Siemens " Halske
d, deutachen, chem, OeselUchaft,
vol.
IICf, Mylius and Fromm, BerickU

xxvii., p. 630.
IT The

precipitatecontains

nitrate and requiresfurther

investigation.

399

ZINC.

and

alone

without

oxidisingagents, gave

smooth

deposit

white

thronehout.
zinc is produced only when
spongy
favourable
of zinc oxide.
to the formation

are

turbid

cathode

action, however,
of the

surface

The

"(4)

proved

"c.

arsenite),
a

minute,

and

to be

at

contains

In

contained

10

The

zinc
such

an

Nahnsen

becomes

grey

time

same

oxidation

has

solution

of

distinct

of the

of the

already
readily

most

spongy

impuritiesas

the

by

oxidation

per
of arsenic
cent,
per
observed
zinc was
to

of the water

the expense
It should

produce
action.

cent,

0*004

porous
at the

seen.

the

that

is determined

zinc

spongy
which

electro-chemical

many
the solution

which

of

foreignmetals
times

antimony,

zinc upon
grey spongy
of electrolysis
with
a

five minutes

liquid.*

through

when

was

per sq. dm. [0 0645 amp. per sq. in.]. The


at the level of the upper
only observable

was

formation

of

presence
metal

was

after

of 1 ampere

current

10 per cent,
made
what
someintentionally

oxide, gave
by precipitated

sheet-zinc

sulphate,which

of zinc

solution

conditions

the

The

"(3)

copper, arsenic,
zinc sulphate,

(as

ammonium

form

after

evolution

of

one

hydrogen
place

zinc,therefore,took

of the solution.

be

here explained that the grey zinc sponge


tains
conof which
has been
crystallisation
prevented by
of the co-operation
the absorptionof oxygen
; and the possibility
be altogether
excluded.
of hydrogen need not therefore
In auy
it
the
view
is
that
such
to
however,
impossible
case,
accept
substances
as
chlorine,iodine, hypochlorous acid,and the like
of the grey zinc by decomposing a hydride
formation
the
prevent
''

zinc,the

would
otherwise
of zinc,t which
be harmful
be ascribed
solelyto the fact that they are
Our

observations

zinc
upon spongy
the views of Nahnsen.

with

experiments be correct, spongy

The

acid,

or

purposes

basic
of

available;

appears

be

of our
interpretation
be
can
never
separatedfrom
fact,it is never
produced if

zinc

of

ment
agree-

If the

shall
the

It is well
electrolysis.

and

in exact

have

an

acid reaction.

:eirhether
a zinc sulphate solution
to

is to

acid-formingagents.

therefore

are

of
"Ui%d solutions ; and as a matter
be taken that the zinc solution
care
determination

; their action

the indicators

is

neutral,

greatest importance

known
which

that

litmus

for

is not

ing
capableof showamong
the presence
of free acid in zinc sulphate,
red
Congo
occupies
the premier position. This colouringmatter, when
in aqueous
phate
or
solution,is not altered either by the normal
by the basic sulof zinc,but is coloured
blue by free acid.j:The
reaction
are

*
At the placewhere
the zinc,water, and air meet, hydrogen peroxide
would always be formed.
t Siemens " Halske, loc, cit,
X The use of congo papers is to be recommended
; they can
easilybe
of the Congo red solution.
prepared by allowing filterpaper to absorb some
The colour of these papers changes like that of litmus paper
but in an

inverse

sense.

400

ELECTRIC

AND

SMELTING

ifl siifficieDtly
sharp for most
being observable only in the

REFINING.

purposes,
estimation

of sensitiyenefls

want

minute

of very

qaanti
however, will not
colouring-matter,
indicate whether
zinc sulphate solution is normal
or
a
basic;
this pointa titration experiment is necessary.
and to determine
found
"We
in our
experiments that in 10 to 50 per cent
solutions at 18^ 0., 10 grms. of zinc sulphaterequired4 ac
of
soda solution to producea distinct turbidity
in half
a centi-normal
with
The
salt was
minute.
a
repeatedlyre-crystallised
great
acidified
and
first
from
at
wards
aftera
solution,
slightly
care,
very
ties of

acid.

free

from
towards
further

This

alcohol.

and

water

soda

centi-normal

behaviour

The

showed

solution

and its reaction


re-crystallisation,

characteristic of the

as

normal

soda solution

may
salt.

no

of

the

salt

change

after

therefore

be

garded
re-

The

quantityof
dependent upon both

the

necessary is,of course, very


temperature and the degreeof concentration.

the

followingvolumes

of soda solution

for every
turbidity.The

Thus,
10 grms.

we

used
of zinc

sulphate,in order to produce


weights of zinc
oxide correspondingto the soda used in each experiment are
given in adjacentcolumns; the quantitiesof soda used (and
equivalentzinc oxide)are calculated in the last two columns as
per 10

"

The

of the solution.

C.C.

first appearance

of the
with
a

very

; and

oxide

for

may

turbidityindicates

has

centi-normal

the

become
soda

more

that the solution

saturated
is therefore

than

solution

ascertainingthe neutralityof a
mination
determining its acidityor basicity. The deterof cubic
be made
by deducting the number

convenient

solution,or

of the

sulphateof zinc
means

for

Percentageby weight.

403

BLBGTBIC

the

obviated, bat

be

SMELTING

white

AND

and

REFINING.

well-crystallised
deposit that

hydrogen bubbles remain


clingingfor a long time to the zinc. An early limit is thus set
The presence
to the thickeningof the layerof depositedmetal.
the
solution
acid
tends to promote
of impuritiesist
of the free
would

result

would

the anode,

rough,

since

effect that is to be avoided.


to obtain a solid and
regulinedepositof zinc

an

order

''In

be

a glasscell
of refining,
compartments by diaphragms of

the process

zinc
purified

into

cast

was

the

used, divided

was

into

cloth ; for the


of either round
or

form

cm.
[0*4in.]thick ; for the cathodes sheet zinc
correspondingwith the anodes in size and shape. The

solution in the central compartment


of mechanical

by

means

in

contact

the

with

of the

oxidisation

whole

zinc

in

square
used

cathode

that it was

surface
the

was

kept constantlyagitated
thoroughlymixed

was

so
stirrers,

three
anodes

silk

plates1

of the

bath

is

cathode.

Since

be

generationof

acid in the bath

neutralised

itsell

For

separate small platinum anode


purpose
introduced into the cathode compartment,
a

connected

with

second

slightevolution

surface;

of oxygen
wire from
the

the

this second

batterywas

cathode, after
illustrated
matter

to

in

the

constant, its
practically
continuous
a
by

effects could

was

in

the

this
was

and

battery,so that
placeat its
negative pole of
took

connected

to the zinc

diagrammatically

manner

It

Fig.218.

regulate the

was

thus

an

easy

current-strengthin

subsidiarycircuit in such a way that


^OM ti^hTw: ""i^"''"""ld be generated at exactly the
and
that the acidityof the
diary electrodes required rate,
thus
be maintained
s
hould
in zinc deposition,electrolyte
stant.
conof 0*01
Thus, for example, a current
would
produce 0*43 grm. [6*6grains]of sulphuricacid
ampere
in twenty-four hours, and
this would
suffice for the neutralisation
*^"

rt

o,o

*!""

of 0*36
all
the

grm.

of
possibility

[5*5grains]of

zinc

renderingthe cathode

oxide.

zinc

Or,

to

avoid

impure by platinum,

of the second

circuit may
be omitted, and the necessary
of
acid
be
added
to the bath from time
to time
quantity
may
(at about 12-hour intervals).The quantity thus required for
total electrode surface
of about
600
a
[93 sq. ina.]
sq. cm.
would
0-2 grm.
amount
to about
[3*08grains]of sulphuric
acid every
be
twenty-four hours; and this quantity would
use

distributed
The

through

anodes,

from

about
which

1*5

litres

bubbles

[2*5 pints]of
of

solution.

seen
hydrogen were
removed
from
the bath
occasionallyto rise,were
once
every
day in order that the impuritiesclingingto them might be
brushed
After they had been
replaced the electrolysis
away.
proceeded as before. Any particles
that might become
detached

403

ZINC.

visible evolution

No

anode

in the

retained

were

of

by the diaphragms.
permittedat the cathode,
observed
were
they were

compartments

hydrogen

was

and

if any
isolated bubbles
of gas
removed
the
electrode
plate. The
by raising

distance between

the

to

electrodes

in

amounted

experiments
at least
current-densitywas

the

our

several

metres,
centi-

1 ampere
per sq. dm.
of
cathode
the
and
surface,
[0065 per sq. in.]
potentialgradient
between
and
the
anodes
cathodes
amounted
0'3 to
to from
0-6 volt.
*'

It is advisable

advantage

that

introduced

into

"The

the

back.

the

on

This

the
a

can

coated
2

be

may

used
corresponded to a
ampere
of zinc per sq. dm. [28*9grainsper
twenty-four hours, so that a layer about 0*4 mm.

any
with

the

deposited in

was

for
ordinarily

from
The

solid

of porous
zinc.
white
of zinc
coat

which

thickness.

in.]in

however,the

At

the

The

day.

formation

[0 08

mm.

that

will.

at

29 grms.

in.]in thickness
10*016
ysis could be continued
without

cathode,

of the

electrodes

be increased

current-densityof

in.]in

the

of

sides

zinc may
mence
easilycomhas also the additional

arrangement

number

bath

separationof about
sq.

depositzinc on both
separationof grey

to

because,otherwise,

electro-

to three

two

cathodes

exceeded

never

the

of

edges

days

became

plates,

was
that, as the
depositwas
formed, in
operationproceeded,rough patchesand growths were
which graduallysmall nests of spongy
zinc were
found, and this
the sign that the cathode must
be replaced."
was

The
Work
F. Forster and

solutions with

experimenters

thicker,and

of

O.

GUnther

zinc anodes
have

chloride solutions.
the

and

Forster

on
are

obtained

They

here

it

Gimther.

of

researches

The

"

of zinc chloride
electrolysis
These
of
close
attention.
worthy
the best results with weakly acid
the

write

follows

as

the

on

conditions

of

normal

in

:
electrolysis
"

The

solution

works

best when

it is from

^V

-izo^

regard to free hydrochloricacid; but it is not spoiledif the


proportionof free acid present either sinks to from y^ to i^^
In the latter case,
normal, or rises a little above ^ normal.
bubbles

of

hydrogen
cathode,although more
solutions. As

these

appear

in

considerable

sparinglyin
bubbles

adhere

the
for

some

spot the depositedzinc presents a somewhat


This difficulty,
which
presents itself in a
with

case

number

at

less acid

of the
time

to the

scarred

the

same

appearance.

degree even
nearly or entirely
ing
bath, by maintain-

smaller

more
weakly acid solutions,may be
avoided,without reducing the acidityof the
a small
proportionof chlorine in the acid solution of zinc
chloride in the manner
The
shunt-current
explained above.

nsed

for the

current

should
be about 0*1 to 0*2
purpose
in the authors' experiments to
sufficing

0*2 grm.
per litre of free chlorine

in the

liquid.

ampere

keep

This

; this
at most

means

did

404

SMELTING

ELECTRIC

AND

REFINING.

actuallysuppress the formation of hydrogen bubbles at the


and
cathode,but it reduced their number
eyidentlyprevented
of
for
time to one
the
them
from clinging
spot on
any length
of uniformity in
surface of the cathode, and so causing a want
and in the distribution
of the electrolyte
the current-density
The metallic depositsobtained
the surface of the cathode.
over
acidified zinc chloride
solutions containingchlorine
from
were
and
few
showed
and
traces
of
with
contact
even
slight
very
very
gas-bubbles.
Using a cathode of 160 sq. cm. [24"8sq. ins.]area, and a
not

current-densityof

1*8 to 19
[16-7to 18
amperes
per sq. dm.
380
o
f
grms. [13^ ozs.] a very tine silver-grey
amps, per sq. ft.],
In
uniform
zinc were
depositedby the process just described.

experiment 225
of
current-density

second

with

[8 ozs.]of

grms.
0*6 to

lO

zinc

obtained

were

per sq. dm.

ampere

Further

[5-6to

to
experiments were
amps,
per sq. ft.].
the results obtained
in the above experiments
ascertain whether

9-3

with

zinc anodes

pure

could

place if, in the


employed as anode.

be

employed
refiningof zinc, a

take

chloride

made

The

test

made

was

would

less pure
metal
were
2*5 litres [| gall.]

with

solution

previously used, containing the


The anodes,
given above.
consisted of commercial
zinc,were
looselyenveloped in
had a gross superficial
cloth. The square cathodes
filtering

of the

zinc

proportionsof
which
linen
area

of 300

and

the

free acid

sq.

chlorine

and

[46^ sq. ins.]


; the

cm.

current-density
was,

current

therefore,1-8

and the pressure


[16'7 amps, per sq. ft.],
could
or
more
way 0-5 kilogrm.[I'llbs.]

operation in

one

to foretell what

edges

cathodes,and

of the

showed

zinc

removed

excellent

an

on

these

branching growths, which


mechanical

by

means,

in order

amperes
0*9 volt.

readilybe

dense

and

even

was

5*5 amperes,
per sq. dm.

was

In

obtained

condition.

On

this
in
the

platesthemselves, the
however, readily
were,
to

avoid

the

formation

of short-circuits.
The

cathode

zinc

examined

purity only in respect


found
of arsenic, but
to be
was
absolutely free from that
The
possibly,therefore,be used for
impurity.
may
process
from
free
the preparationof zinc
arsenic to be employed in the
was

as

to

of the latter element.

detection

kept in mind that the introduction of air


into the bath may
possiblybe substituted for the use of chlorine
in dislodgingthe hydrogen bubbles
from
the cathode.
The
desired end may certainlybe attained in that way, and in that
Finally,it

case

the

there

in which
action

The

be

be

no

need

of any

device

other

electrode zinc would, however, be

for
so

stirring

strongly

given quantity of free acid in the bath would be


more
rapidlythan in the earlier experiments,
only neutral zinc chloride was obtained, produced from

that

neutralised
the

would

liquid.

oxidised

must

much

of chlorine

on

the

electrodes.

On

this account

the

405

ZINC.

careful supervisionwhen
process requiresespecially
into the bath, and therefore in the opinion of the

shunt-current
is to be preferred.
chloridising
A
of the numerous
review
proposalsaiming at the electrowith
anodes
exhibits the influence
zinc
insoluble
of
deposition
of many,
less conflicting,
views
of
or
to the cause
more
as
so-called spongy
zinc being produced,and also as to the nature
of the product and the means
of combating the depositionof a
material
which is technically
worthless.
The observations
which
have
be divided
been published concerning this objectmay
for
use

the

of

air is blown

authors, the

most

part into
the

One of these
groups.
authors
Mylius, Fromm,

two

groups,

which

is

Forster, and

O.

represented by
Giinther
alreadyreferred to, and which is based upon the best
in producing a dense depositof
evidence, attribute the difficulty
zinc to the deposition
of zinc oxide,or of basic zinc salts between
the crystalsof the metal.
The
other group,
the contrary,
on
ascribes the sponginessto the formation
of zinc hydride at the
cathode.
No
unexceptionableproof, however, of the latter
ing
hypothesishas hitherto been advanced, although certain oxidisthe
which
has
of
been
to
use
proposed
agents,
prevent the
formation
of zinc hydride according to the theory, have
been
shown
favourable
influence on the densityof the
to exert
a very
zinc.
electro-deposited
Forster
O. Giinther, in their work
above
and
quoted, put
forward
the first view in statingthat spongy
zinc must
always
be formed if hydrogen ions as well as zinc ions are dischargedat
the cathode, in neutral or weakly basic solutions of zinc,in such
numbers
that any considerable
concentration
of hydroxy 1 ions
and
take
in
this
if
at
so
place
large a
point,
consequence
of
basic zinc salts are
formed
that they deposit on
quantity
and so interfere with crystallisation.
the zinc crystals
Mylius,
Froiiim,Forster,and

O. Gutither

have

described

ways

and

means

for

preventing these objectionablephenomena ; but special


importance should be given to one point,namely, the movement

of the
paper

solution.
on

the

Forster

and

O.

Giinther,

of zinc chloride
electrolysis

at

the

end

of their

solutions,point to

the

is agitated
rapid consumption of free acid when the electrolyte
the
of
this
and
show
the
on
air,
by
ground
advantage
injection
within
the cathode
of producing a small quantity of chlorine
chamber.
This chloridising
action or the dischargeof SO^ ions,
able
recommended
by Mylius and Fromm, which, to a very considerextent, lessens the simplicityof the apparatus used, may
readilybe dispensedwith if the solution be agitatedin the right
The
primary objectsought in keeping the solution in
way.
alteration of concentration
motion
is to prevent any prejudicial
in the immediate
neighbourhoodof the cathode, as the depletion
of the electrolyte
in regard to zinc ions at the cathode, produces
favourable
of spongy
conditions
to the formation
deposits. It is

406

SMELTING

ELECTRIC

AND

necessary, therefore,first to ascertain


solution suitable for each individual
the

which

solution

is

flowing

at

REFINING.

the

flow of the

rapidityof
The

in

direction

process.
the cathodes

is, however,

Although the author


but
hydride hypothesis,
importance to
he urges
the necessityof removing the bubbles of hydrogen,
in these cases
the zinc deposited from
in which
since (especially
the anodes)a dischargeof
the solution cannot
be replacedfrom
of
hydrogen ions, accompanied by a diminishingconcentration
by

no

means

zinc

less and

of

zinc

less avoidable.

In

electro-metallurgical
specimens there

suspended as
electrolyteflowed
so

was

current

the

solution,is

collection of
which

indifference.

little

attaches

the

of

matter

cathode

the

in

bath

it from

over

author's

the
is

zinc

that

plate
brisk

downwards.

above

fluid zinc had

Its upper surface looks as if the viscous


gradually
like
of rainthose
drops
solidified while flowingin numerous
streams,
window
Viewed
below
these
d
own
from
a
trickling
pane.

drops are seen


explanationof

be

to

hollow, highly perforatedshells.


is evident.

this

The

bubbles

If

phenomenon
hydrogen
they would remain longerattached to its
than under
surface if the solution were
flowingdownwards
any
other circumstances.
The zinc undergoingdeposition
naturally

form

the cathode

on

banks

like a
up
accumulation
of

roof

the

over

bubbles,

and

favours

so

the

largerquantitiesof hydrogen. The unevenincrease,as do also the placesat which a


be
of
the
if the solution
to rest
even
liquid comes
portion
briskly. Hence, there is always an increasing
agitatedmore
of centres
number
of disturbance, although the main
portion
of the electrolyte
in accordance
with the statements
acts
given
above.
On this account, when
with stationary
zinc is electrolysed
should be kept in brisk flow from
electrodes,the electrolyte
of the
below
In
this
the direction of the motion
upwards.
way
of the surface

nesses

"

hydrogen bubbles
platesremains

is of

smooth

the

assistance,and
for

longer time

A
motion
oppositedirection.
or
oscillatory rotatory,materiallyaids

tn the

surface

than

of the

of the

when

zinc

flow is

the

cathodes, whether
removal

in the automatic

of hydrogen bubbles.

regards the diflerences in the action of the various


oxidisingagents proposed for use by the adherents of the zinc
of
to the work
hydride theory,attention may again be drawn
F. Forster
O. Giinther, who
and
have
the
following
given
explanation: "In so far as the oxidisingagents act as depolarisers, they assist the dischargeof hydrogen ions; but they
will only favour the productionof spongy
zinc if the hydrogen
returned
their
into the solution
action
does not sensibly
by
As

"

the concentration
increase
of the hydrogen ions
the
hydrogen returning into the solution

here.

condition

the

ious

at

the

cathode,

remaining

at

that

will

point

form
and

water
so

check

with
the

in

wise,
Other-

the

ionic

hydroxy!

formation

of

407

ziNO.

the

Among the oxidisingagents of the first class are


sponge.
nitrate,the former producing
hydrogen peroxideand ammonium
cathode
the
with
water
hydrogen, whilst the NO3 ions of the
others form

latter and
and

Mylins

of the

found

Fromm

this

sulphuricacid

normal

zinc, but

spongy

on

halogens,!and, as
has
already been
to check

ceases

hydrogen

the

tend

so

deci-

in

the ammonia
than

more

balances

oxidisingagents
formation

the

of
the

prevent it, are


contrary
found, ammonium
persulphate. It
the
chlorine
of
out
that,
former,
pointed
to

formation

of sponge

there

when

are

no

free

alreadygrouped ammonium
persulphatewith
trolysis.
halogensbecause they originatein the same
way during electheir
In each case
ions
two
charges
give up
negative

the

and

has

unite

molecules

to form

ci +

NH4SO4

ammonium
and

in this

of iodine

the anode

at

ci

in

=CL5

NH^SO^

(NHJjSA-

"

also resembles

the

of neutral
electrolysis
of OH

continuance

Mg

Ni

free
zinc

ions

(NH4)2S04 + MgS04
KI
+ Nil,.

in the solution.

hydrogen,two

nascent

once

form

water

with

SO4 or

OH

ions

great depolarieiiig
power

example, by

the

fact

that

halogensin its behaviour during the


sulphatesolutions in inhibitingthe

"The

"

" has also shown that a neutral solution of


persulphatemay dissolve metals,forming sulphates,
in a manner
analogous to a solution
respect behave
iodide
:
potassium
(NHJ,"A
KI,

with

Marshall

Hugh

"

at

that

have

we

the

the formation

found

ions in the solution.

"Nemstt

It

the cathode

present initially.*Neutral
kind, which do not promote

second

do

not

of acid

excess

the

of

does

solution,obviouslybecause
at

the

activityin weakly acid

of

nitrate

its reduction

resultingfrom
the

kind

ammonium

to

the cathode.

at

they reallypromoted
and Giinther)
have
(Forster

hydrogen peroxide loses


solutions, whilst

contribute

hydroxy 1 ions

that

We

of zinc sponge.

ions which

ammonium

in concentration

increase

of

2H

If the
-

SjOg ion

reacts

2S0^ ions

present.

result.

In

These

practicethe

the

for
NOj group is also shown
is
formed
the
cathode
at
hydroxide
copper
solutions are electrolysed
with
high currentbe quantitatively
deposited from animoniacal
they contain NO3.

neutral
when
copper nitrate
densities. Nickel also cannot
solutions of the metal when
t Siemens k Halske, see p. 413.
t Berichte des devtsch. chem. GeaelUch.,vol. xxx.,
%Joum. Soc, Chem, Ind., 1897, vol. xvi., p. 396.

"

p. 1561.

408

REFINING.

AND

SMELTING

ELECTRIC

(Forsterand GUntber) have found that when a perfectly


neutral solution of ammonium
persulphateis added to a similar
solution of zinc sulphate(containing
250 grms. of the latter salt
with a current-density
and the mixture
is electrolysed
per litre),
authors

clear
smooth
a
per sq. ft.],
per sq. dm. [9*3amps,
of
obtained
without
zinc
of
trace
a
was
sponge, even
grey deposit
and
1 per cent, of the persulphate
the solution contained
when
had been exposed for a full hour to the action of the current.
of 1 ampere

the other

On

neutral

hand, a

strength,but with an
with
the
electrolysed
of
deposit spongy zinc

2"

zinc

sulphatesolution

of 0*025

addition

of the

HjOg, when

cent.

per

showed
current-density

same

distinct

after ten minutes."

at the cathode

LEACHING

same

FBECIFITATION.

AND

fications,
L^trange,*in several patent speciand
tions
condithe
methods
ail
terms
general
of work
of zinc-bearing
of a process for the treatment
be observed
for the
must
substances,excepting those which
of
The
coherent
zinc
production
plates.
patent specification
that are
details of work
prescribesmany
quite impracticable
;
here had not
and the process might have been Jeft 4innoticed
the accounts
books
publishedin various technical journalsand textThe

Iietrange

Frooess.

describes

led to
It cannot

be

calamine

and

"

in

the belief that

it

in actual

was

in zinc works.

use

disputed that L6trangehas made practicalexperiments


in the electrolysis
of zinc on a largescale at his works in
St. D^nis, but it is certain that if he obtained
any practical
of his
the
details
not
result,it was
by followingaccurately
is
blende
this
**Zinc
patented process. According to
patent,
roasted
low a temperature, that very little sulphur is
at so
of the sulphidebeing converted
into sulphate.
most
removed,
The
is
dissolved
in water, and
sulphate
decomposed by the
electric current
(a process which appears to be very simple on
the
a
nd
to dissolve
sulphuricacid thus set free serves
paper !),
zinc oxide.

For

through a system of masonry


another
one
by pipes,and
material.

oxide, it
then

As

soon

is disconnected

again introduced

saturated

with

lower

the

the

In

this reservoir

foreignmetals

German
Patent 21,776. Austrian
Patent 3,211, July 22, 1881.]

with

the

zinc-bearing
deprived of its zinc
and is
series,is re-charged,

last of the
to

to fiow

connected

is

series.

the

is

which

placed at

zinc solution

according to known
Priv. of Nov.

solution

The

reservoir,from

vessel,which
electrolysis

level.

purified(!)from

as

are

from

are

filled with

first vessel

zinc is conducted

usuallyled to the

"

the

as

it is caused

this purpose

basins,which

12, 1881

Ac.

it is
what
some-

be
may
methods.

[English

410

"L8CTRIC

8MKLTINO

AND

REFIHING.

to alter his
experiments,however, have led Nahnsen
of his later views
opinionson this subject; and the statement
taken
be
from
in
a
subsequent [British]
specification,*
may
which
he writes that
and
alkali
the double
sulphatesot zinc
metals, proposed by Herrmann, permit the use of lower currenthad been referred
densities than do the simple zinc salts,which

Farther

'"

to in the earlier

however,

said

SO4 groups)
at

the

of

of the

finds

the cathode

conductance

its way
is reduced

double

that

salt

has

by

singlesalts

these

anion, and
the anode,

to

of the double

of the

solubility.Again, in

constituent

The

to be less than

of their inferior
forms

patent.

so

double

salts is,

by

reason

salts the zinc

(accompaniedby

while

secondary action.

two

deposited
peculiarity
unsatisfactory
in
electrolysis

the zinc
This

practiceled to very
regularworking of the
the baths almost impossible.
When
anode
of
soluble
is employed for the purpose
a
separatingor refiningmetals, a solid salt is formed at the anode
the passage
at a very low density of current, and, finally,
even
is interrupted. When
of the current
using a solution of simple
30'
of
zinc
concentration
at
of
a
Beaum6, and a current
sulphate
having at the anode a densityof 418 amperes
per sq. yard [46-4
takes
5
or
ft.,
amps, per sq.
amps, per sq. dm.],no crystallisation
of
solution
place,but when employing a concentrated
sulphate of
results,which

render

in

the

"

zinc and

ammonia

the

formation

of zinc is

alreadyobserved

with

of 63 amperes
a current
per sq. yard [7 amps,
per sq. ft.,or 0 75
of this chemical
process is,that
amp. per sq. dm.]. The reason
in the last-mentioned
salt two equivalentsof sulphateof zinc go
to

the anode.
"

into
with

When

sulphateof zinc alone it is decomposed


electrolysing
Zn and SO^, the latter forming sulphuricacid by combining
and giving off one
the water
of oxygen
phuric
atom
; this sulacid being specifically
lighterthan sulphate of zinc rises
"German

Patent

71,155.

[EnglishPatent 2,913, Feb. 15, 1392.]

411

ZINC.

the

to

surface.

potash and

of

double

salt,for instance sulphateof


ordinary circumstances, decomposed

alkaline

zinc,is,under

into K
by electrolysis
insoluble
an
employing

when
ZnSO^ SO^, so that even
of
an
agglomeration sulphate of

and

anode

free acid is
whereby the nascent
the
in
tration
concenslightestchanges
which
of the electrolyte,
on
changes largelydepends
the quality of the zinc belonging to the anion
the cation,
or
influence
this process, and the practical
result of the latter is,
that part of the nascent
acid rises to the surface,but by far the
Even
the best
the
of
sinks to the bottom.
same
greater portion
circulation is at length insufficient
regulated and best conducted
A remedy may
be found
to prevent the stated inconvenience.
by employing very diluted solutions,but there the conductivity
is so much
decreased
that no sensible advantage is secured.
I have
position
ascertained
"Now
by experiments that the decomzinc is
salts of sulphate of alkali and
of the double
influenced by the temperature in the same
as
measure
by a
dilution of the electrolyte.Between
104** and 122'' F. [40"and
50* C] the point is reached
the decomposition of the
at which
double salt into the simple salt is completed. In practiceI
prefer to employ a temperature of 122" to 140" F. [50" to
60" C], and
I obtain
position
thereby with perfectsecuritya decomwhen
manner
as
taking place in the same
simple salts
is formed

zinc

drawn

used

are

the

at

the

bottom.

; and

all the

to

same

The

in the

acid, as

nascent

latter

case,

rises

of a double
Notwithstanding
the
in
electro-chemical
being completely wanting
sense,
the relation between
the density of the current
at the cathode
and the depositof zinc has remained
the same,
and it is thereby
shown
of
the
that
it
is
the
of
not
electrolyte
clearly
quality
the

to

surface.

the

character

salt

being a

solution

of

for the

double

salt which

is the

first condition

employment
density,but only the
of the zinc by the
partial or complete secondary reduction
alkali.''
primary
The electrolyte
should be so diluted that it contains from 45 to
90 grammes
of zinc sulphate(ZnSO^ THgO) per litre,
according
will then be so enriched
to the current-density.This solution
in alkali sulphate that it will dissolve
the
at
temperature
generallyused, or at about 10" C. lower still. The electrolyte
contains
45 to 90 grammes
of zinc sulphate and
300 to 150
of alkali sulphate,according to the current-density,
grammes
of currents

of

low

and

is used

60" C.

at about

Using condensing engines,


by this process
expenditure of

to

extract

from

calorimetric value

of the

at

of

temperature

100 amperes

per

sq.

to

92"
metre

Nahnsen
ton

3^

tons

fuel.

In

C,

and

[9'3

that
he is able
says
zinc from
its ore
at an

of

coal, according

of
with

amps,

to

the

experiment, conducted

one

per

current-densityof
the deposit
sq. ft.],

412
of zinc

was

formed

at

not

the

Nahnsen's

experiments which
may
fact may
is formed

be

he

brought

into

anode

the

at

has

remain

to

bubbles

of

steam

were

in the
electrolysis
described
in his patent specification
as
they are expressedabove. But the
prominence that persulphateof zinc

concerning the

views

REFINING.

though

even

spongy,
cathode.

be allowed

AND

SMELTING

ELECTRIC

when

of

action

500

densityreaches
ft.].

the

current-

[46*4amps, per sq.


amperes
per sq. metre
the current
Frooess."Coehn*
Coehn's
seeks,by interrupting
from
evolution
of
time
to time, to prevent the
hydrogen ()),
which

gives rise

to

currenlndensities

are

sq. metre,

per
solid

deposit if

minute.

the

interruptedmay
between

current
a

mechanical

the

be

two

sets

Coles'

^46*4amps,
His

per

the

sq.

the

be effected

may

is

current

of the

alternation

continual

the

to

by

of

means

depositionof

the

an

starts
deposits,

of 500

current

but
ft.],

solid

at

amperes
per sq. metre
he
intervals of eight minutes

over,
considerably. Morethe
in
zinc dust in suspension
electrolyte.
with zinc (*"
intended
for electro-plating
galvanising
be impossibleto
is quite evident
that it would

is
it

zinc dust

the

but

ore;

additional

the

current

into the vats

very

the

that

Process.

rapid variations

be

may

So, also,Eschellmann^ recommends

possiblein the current passingthrough


the separationof the gas bubbles

as

cathode.

The

current, and

the

baths

must

never,

potentialdifference

always be well
employed.

must

of zinc sponge

reducingagent.

to hasten

baths,in order
the

"

it affords

noteworthy, because

formation

of
application

Eschellmann's

without

the

of zinc from

extraction

in the

suggestionis

evidence

prevented by

from

which

times

maintains

process
and
^'),

the

50

consideringthat
Cowper-Co]e8,t

"

density of the

introduce

as

during
a

of baths

Frooess.

favours
current
irregular
the electrolysis
with
a

he

about

switch.

Cowper-

increases

low

a densityof 50 amperes
sulphate should give a more

time

wasted,

not

when

with

broken

be

current

order that

In

Thus,
of zinc

solution

cathodes

the

depositsat

spongy
used.

above

zero,

be

however,
between
with

even

the
the

left
trodes
elec-

lowest

current-densities

In the attempt to prevent the formation


zinc there
of spongy
have been specified
of chemical
for the purpose
a number
agents,
the

of
efficacy

tested

before

Forster
the

and

which

not

appear

in all

differences

between

the

effects

oxidisingsubstances

have

been

of

these

reagents, bnt

recommended.

Patent

75,482, 1893.
79,447, 1894.
[Cf, English Patents
1893; and 7,145, April 10. and 19,797, Oct. 17, 1894.]
Patent
X GermiMi
124,622, Dec. 28, 1897.
("erman

t German

to

cases

work
of
they were
proposed. The exhaustive
GUnther," quoted above, explainsclearlyenough

especiallyof the
*

does

Patent

8 See p. 405.

21,760, Nov.

14,

413

ZINC.

Siemens

Halske's

"

Processes.

Siemens

"

dc

Halske,

as

proposed the addition of hypochlorites,


and
other analogous haloid compounds, with the
hjpobromites,
object of destroyingthe hypotheticalzinc hydride which was
of spongy
zinc.
This
credited with
causing the formation
that
firm, in their English Patent 13,434 of 1895, recommended
be kept in brisk motion
should
the electrolytes
of
means
by
In a later patent*^they use
aluminium
air blast.
an
sulphate
solution in leachingoxidised zinc ores
or
metallurgical
products.
During the process of solution zinc sulphateand basic aluminium
sulphateis recovered
sulphate are formed, and neutral aluminium
This process
double
salt
in
of
the
from
course
electrolysis.
again
under
the influence of a groundless
appears to have been originated
dread of free acid produced during electrolysis.
already indicated,have

Pertschf recommends

the

of mixed

use

chlorides

and

oxalates,

|
reducing agents, in electrolytes.Lindemann
zinc sulphidein the electrolyte
to suspend precipitated
proposes
These processes lead up to a group in which
during electrolysis.
therefore

and

the

of

is

attempt

utilise the anode

to

has

with

connection

vat

be

may

"

not

speciallynoted

very

harmless

it

which

to

proposalsin
which

the

into the electrolyte


procedure that has

Luckow,

however,

of

sulphurous acid,inasmuch
of converting into
means

use
as

of

later date.

at a

chlorine

the

substance

several

anodeH, among

method

"

in this

fortunate

made

patent,"

sulphurousacid

of

current

proposedto employ

he

harmless, but actually


his

in

of insoluble

use

frequentlyre-discovered

been
was

the

of

introduction

to render

reactions.

Process.

attention

only

not

Luckow,
already been drawn,

Luokow's

as

made,

that

is evolved

at

the

anodes

being electrolysed.It must


be
not
deoxidisingagent
forgottenthat the use of Luckow's
at an
the acidityof the electrolyte
rate.
increases
enormous
be
the
chloride
used
the
the
solution
or
Thus, whether
sulphate,
whether, therefore,the group Clg or SO^ be liberated from the
depositedzinc, the use of SOg to render these anions harmless
will always be attended
by the formation of a quantityof free
which
double
that
is
to the
corresponding theoretically
acid,
when

ziac

solutions of zinc chloride

thus
precipitated,

SO4
Clj

If,therefore, the
of zinc

ore,

as

+
+

"

SO,
SO2

2HjO
2HjO

+
+

in
specified

2HjS04

2HC1

H2SO4.

acid is to be neutralised

liberated

Luckow's

after the first neutralisation


*
German
t German
X German
" German

are

two

molecules

of zinc

Patent

88,202,Jan. 1, 1896; and EnglishPatent

Patent

66,185.
81,640, 1804.
14,256 (see p.

Patent
Patent

by

patent,it is evident

means

that

salt will be

1,575,1896.

414

8MBLTINQ

ELECTRIC

cont4i^ined in the

decomposed.
necessary

liquidfor

Hence

to find

in

some

one

that had

means

is doubled
dissolve

it would

time

become

(the
than

operation)other
compounds. But, at the
each

at

zinc

previouslybeen

the acid
neutralising

of

of solutions

use

REFINING.

short

very

other

proportionof which
that of allowingit to
time, the direct

every

AND

which

been

have

same

neutralised

by

is not permissiblein practice,


owing to the
thus
introduced
them.
that
into
are
quantity of impurities
of the

means

ores

A.lthoughLuckow's
the largescale,it

on

reactions,an idea which


received,consideration.

anode
has

matte

Fromm

not

the

account

been

adopted

utilisation

deserves,and

in

some

of the

instances

proposed to apply to the treatment


process that they have used for copper
and
The
work
of Mylius and
sulphide copper ores.
that a dense
has, however, shown
deposit of zinc

Siemens
of zinc

patented,has

process, as
takes into

"

Halske***^ have

blende

the

be obtained

cannot

same

when

iron

salts

are

lyte.
present in the electro-

objectionappliesto the process of Oassel and


at obtaininga serviceable
depositof zinc
the cathode
from solutions of zinc sulphate,
compartment being
contained within porous walls and the anodes being of iron.
On
the same
Ashoroft's
ProoeBS.
grounds it is obvious
that no practical
future could have
been foreseen for a process
the patent specification
of which
of Aslicroft's,^
appeared almost
simultaneouslywith the publicationof Mylius and Fromm's
This was
in two
results.
pointed out by the author (Borchers)
which
appeared respectivelyin December, 1895," and
papers
the followingstages :
in
1896.
early
|| The process embraces
(1) Oxidising roast of the ores to convert the zinc sulphide
and oxide.
into basic sulphate,
roasted material by means
of solutions of
of
the
(2) Leaching
which
chlorides
ferric salts, with
or
sulphates of the alkali
ferric salt then
The
metals or of magnesium might be mixed.
The

same

Kjellin,twhich

aimed

"

"

reacts

with

the zinc oxide


3ZnO

as

follows

FejCl" + 3HaO

"

3ZnCL,

FeoCOH)^.

Simultaneously any lead chloride which forms


sulphatespresent to produce lead sulphate.
of the solutions obtained in
(3) Electrolysis
three

tanks

with

iron anodes

2ZnCl,
and

in the third vessel

ZnCL,
*

German

t German
t U.S.A.

with
+

reacts

i^wo out

with

the

of every

"

Fe^

2FeCl9 + Zn,,

insoluble

2FeCla

anodes

FcaCl^ +

:
"

Zn.

Patent

42,243. See also Copper.


Patent 67,303,and EnglishPatent 21,193,1892.
Patente 546,873, Sept. 24, 1895; 595,513, Dec
14, 1897; and

602,295,April 12, 1898.


" ZeUschriftJiir
EUelUrochtmie,1896, vol. ii.,p. 376.
IIJahrhuchfur Elektroehemie,1896, vol. ii.,
p. 163.

415

ZINC.

the

After

had

been

tried in

experimentalplantat
formed
Gray's
Sulphide Corporation,a company
for the purpose,
a
1,500 H.P. plant to work it at
put down
Cockle
Creek
South
Wales.
A portiononly of the large
in New
into use by March, 1897,
experimental plant had actuallycome
in

process

an

"s8ex, the

and, allowing

for intervals
in order

in the

work,

been

liad then

some

huge expenditure,what
1895
simply from an
examination
of the patent specification.
It might have
been
possibleto verify his predictionwith an expenditure of onehundredth
part of the work and capitalactuallyapplied.
his
Since the negative result with
Process.
PhcBnix
The

months
the

in use,

confirm, at

to

(Borcbers)had

author

foretold

in

"

process, Ashcroft
of the Phoenix
accounts

has

former

taken

out
"^

many
which

patents.

The

first

Swinburne
in
a
was
process,
his
than
those
of
earlier
do
better
not
CO- patentee,
give
promise
In
is chloridised in a bath of fused
this
the
ore
process.
process
the reaction
zinc chloride ; when
by lead,the lead by zinc

is

the

8ilver

is

tated
precipithe iron by
electrolytically,
of air,and the zinc by electrolysis,
the zinc chloride being
means
maintained
in the fused anhydrous condition
throughout.
the
before
recent
a
Faraday Society,!entitled
[In
paper
with
Swinburne
Chlorine Smeliing
Electrolysis^
gives a further
of his process, as elaborated conjointly
account
by himself and
after
with
an
Ashcroft,
experimental plant set up on a
testing
such
that obtained
from
the
as
working scale. A mixed
ore,
Hill
Broken
and
district,containing lead, zinc, iron, silver,
sulphur,possiblywith other constituents,is treated with chlorine
transformer
of iron lined with fireclay,
made
in a
capable of
About
1 cwt. of the fused
holding,say, 10 tons of material.
from
chloride and floating
a
previouscharge being left in
gangue
the transformer,ore or slimes in the dry condition
are
charged
remain
the
in
melted
in little by little above, and
suspended
is then
blown
in at the
charge already present. Chlorine
carbon
under
bottom
a
tuyere. Decomposition
pressure through
takes place,sulphur distils off and
of the ore-sulphides
lected
is color

"

'*

in

being

euded,

suitable

fused, mix

remains

feed of

receiver,metallic

with

unchaifged,and
ore

and

chlorine

fullycharged,when

chlorides

are

the

formed, and,

charge already present ;


is suspended in the molten
is continued

until

the

the
mass.

gangue
The

transformer

is

the

off into another


vessel for
liquidis run
with
the exception of about
further treatment,
1 cwt., which
remains
to start the next
charge. The proportionof chlorine to
be
must
adjusted according to chemical
sulphide
equivalents,
Vidt ABhcroft's Paper before the Institution of Mining and Metallurgy,
June
19, 1901; [Trans, Inet, M. and if., 1901, vol. ix., p. 378].
Ztitung,1901, vol. Lx., p. 466; and English
Berg- u, hiUtenmanniwhe
Patents 14,278, 1899, and 17,611 and 17,612, 1902.
and Metallurgiet,
t The MectrO'Chemiet
1903, vol. iii.,
p. 68.
*

416

ELECTRIC

and
of

the
the

charge,

chlorides

supply of

of

rate

fluid

SBfELTINO

which

both

to

is

REFINING.

the temperature
sufficiently
high to keep the

be

must

and

sulphur, while

AND

governed by

the

prevent

formation

it is not

of

chloride

of

high enough
with the sulphur. The
over
distilling
be perfectly
must
dry ; this being the case, it may be pumped
iron
through
pipes,which would be attacked if moisture were
allow

to

of any
of the
chlorine
used

chlorides

mixed

The

present.

chlorides

are

the

into

run

water

pressed,whereby
gangue
are
separatedfor subsequent treatment.
and

of the

most

lead

chlorides

is treated, first with spongy


with
lead and silver ; then

copper
zinc to

throw

to

filter-

and

silver

The

down
the

remove

and

filtrate

the residual
copper

next,

peroxidation,with zinc oxide to precipitatethe iron as


with more
zinc oxide and further
ferric hydroxide ; and, lastly,
chlorination
to depositthe manganese
solution
as peroxide. The
from
the
each
at
ata^e,theremaining
being separated
precipitate
liquidshould contain nothing but zinc chloride. The solution
and
the residue
is evaporatedto dryness carefully,
is fused.
fused compound is first electrolysed
The
in open vats to break
be formed.
The zinc chloride is
up any oxychloridethat may
iron
in
tanks
lined
then
with
electrolysed
firebrick,using
afler

and

anodes

carbon

keep

necessary
of current

voltage is

therefore

and

largercell

be

the

cell

the

by an excess
The
electrolysis.

using 3,000

of heat

economy

of the

temperature

is maintained

pressure

in

amperes,

employing

being reduced

to

3 volts

The
latter figure
capableof taking 10,000 amperes.
that could conveniently
reckoned as being the largestcurrent
The
worked
under
at
vats
are
applied
slightly
present.

for
is

allow

would

4 volts for

that

The

cathode.

actuallyrequiredfor

about

it is calculated

zinc

charge molten

that

above

fused

the

to

tank

reduced

leakage
charge

means

chlorine.
estimate

so

pressure,
The

in the

"

the

is inwards, and
pressure
any
of air instead of an
escape of
evolved
is used for blowing another

slightadmission
chlorine

transformer,

of cost, based

in the paper.

that

on

so

the

that

the

is

cyclic. An
preliminaryexperiments,is given
process

Translator.]

have
returned
idea of
to Luckow's
Lange
acid
the
anode.
acid
at
With
to sulphuric
oxidisingsulphurous
is roasted, and
the gaseous
zinc blende
this object in view
product is led into the mixture of roasted ore and water, thereby
to be treated for zinc and sulphuricacid.
yieldingthe electrolyte
Coehn f has proposed the use of lead oxide accumulator
plates
of oxygen
in the electrolysis
salts,such as zinc sulphate. These
and could then be employed
peroxidised,
plateswould become
in
the
of
acid
for
production electricity lead peroxide sulphuric

and

Kosmann*

"

"

carbon

batteries.
*

German

t German

Patent
Patent

67,761.

79,237,1893.

418

BLBCTBIO

50

SMELTING

[0*2in.]per minate,

mm.

anode

sinks

completelyto

of the favourable

reason

the

AND

REFINING.

lead

peroxide formed

at

the

this cause, and by


of chlorate
quantities

From

the bottom.

influence of small

zinc, diaphragms have been found to be


electro-deposited
which
is
obviouslya great advantage in the process.
unnecessary,
The
separationof the lead peroxidein loose form, especially
under the conditions determined
by Rontschewsky, has much in
the
favour
with
its
reference to its further applications,
as
author
has alreadyshown.
The
separationof the peroxide in
would
be
form
ploying
plate
undoubtedly
preferableif the idea of emthe stored-upenergy
for the production of electricity
could be made
For
all other purposes, however, the
practicable.
form of powder is more
convenient, since the present consumers
do, and the future consumers
will,requireit in that condition.
It is,of course, understood
that this does not apply to consumers
who
utilise the peroxide made
works
in their own
simply as a
on

the

carrier

In this
of oxygen.
in almost all cases

the

case

and

lead

is retained

the

in

lead

peroxide is regeneratedby
of producing lead
processes.
would
these
be
of
to
consumers
use
peroxide
only if they abo
undertook
The
to treat the zinc sulphatesolutions.
only other
lead
manufacturers
of luciferthe
of
consumers
peroxide are
be satisfied. A new
matches, and their requirementswould soon
outlet,however, might be found in the preparationof red lead,
and similar lead pigments rich in oxygen.
lead-orange,
Bed
lead,as is well known, may be regarded as a compound
of the basic lead oxide with
the acid peroxide,
its synthesis
beingindicated by the equation:
works,

well-known

Such

method

"

2PbO

author

The

PbOj

s=

Pb804.

not, however, succeeded

has

in

obtaining it by
peroxide in the proheating
portions
450"
of the above
C, as directed by the
equation to
chemical
At this temperature a badly-coloured,
and
test basis.
obtained.
therefore technically
useless,
product was
Further, it
is common
knowledge in connection with reverberatory-famace
mixture

that

work

obtained

by

oxidation
have

the

of

lithargeand

finest colour

lead

is obtained

the

when

lead

is

the very gradualcoolingfrom a dull red heat of the


of lead.
Experiments made by Dorsemagen

product

the temperature of formation


peroxide is considerablylower

of red lead

provedthat

lithargeand
above, and

red

is about

250** 0.

very

than

fine red

from

that

^ven

compound

^vould

lead oxide and peroxide


difficulty
by treating
of
the
latter
as
compared with the above
(using slight
mixed
equation),intimately
by grinding them together in the
be obtained without

excess

wet

condition.

The

temperature

highestlimit for red lead


of

the

mixture

of

last named

production,for when

lithargeand

lead

is undoubted.1

j the

largerquantities
heated
peroxide were
in

419

ZINC.

sealed

tubes,

the

layers,which

outer

indications of alteration

red,showed

at

first

beautifully

were

in colour at the walls

of the

the
This
glasstube.
process is unquestionablysimpler than
wella
nd
at
a
used,
and,
oxidising
roastingprocess
present
given
designedapparatus, the finer shades of colour could probably be
obtained
with greater certainty.
by its means

Hoepfner's

Prooess.

previouslydealt
often

with

the

described, and

in

others

ignored,is

The

"

work
some

because

not

fact

that

the

author

Hoepfner, which

of

not

been

has

so

over-estimated, whilst

cases

he

has

has

which

failed

in

appreciatethe

to

of the
some
Hoepfner
problems in electro-metallurgy.On the contrary,
he hopes to bringtogether,
in a form useful to the reader of this
has occupied Hoepfner for a
which
of the work
book, accounts
of
time.
long period
The
utilisation of burnt
pyritescontainingzinc is one of the
problems to which Hoepfner, recognisingits importance, has
Hence
his name
himself.
is indissolublyconnected
devoted
with the electro-metallurgy
of zinc. If he has had comparatively
with

tireless energy
difiScult
most

little

in

success

actuallybeen

this direction

circumstances

have

contributed

which
be

[Borchers]

author

to

as
collaborators,

Dr.

he

has
processes
works),it will be understood

He

has

Eschellmann

does

not,

in
justified

done
and

of

Hoepfner

even

this.

to

attacked

(only one

practicein

in

put

that

has

in

of his

are

Thanks

to Dr.

E.

Gunther,

who

appear
fault

Giinther,on
author, deserve

the

were

his

contrary,

credit

obtained
for

to the
to

ments.
publishedstate-

E.

has taken

recognised

not

however,

to the
personallyknown
remarkable
degree for the results which were
electrolytic
plant at Furfurt on the Lahn
indeed, so long as these two
gentlemen

who

has

ascribingthe

several

Dr.

his

in

with

long time
managing

the trouble

the
"

it.

to prepare

[Borchers]for publicationan account


give to the author
of his experiencesin this work, the readers
will now
be in a
positionto form an opinionas to Hoepfner'sintentions,and as
far they have been carried out.
In spiteof Hoepfner's
to how
failed to show
has not
full recognitionof his
attack, Giinther
of this by no
services in the solution
means
simple problem.
and

He

to

writes

as

follows

:
"

Hoepfner has, for seventeen


years, devoted a large proportion
of his energies to the solution of the problem of the
of aqueous
solutions
of zinc.
He
has taken
out
electrolysis
well
like
about
and
number
of
ten
as
a
German, as
English
of zinc alone.
extraction
American, patents for the electrolytic
variations in the several processes recommended
The
by him are
mostly to be found in the differences in the zinc-bearingraw
materials
of operatingnecessitated
employed, and to the method
suitable electrolytes. Hence,
thereby in order to prepare
has
methods
various
of treatment
for poor
Hoepfner
proposed
"

420

ELECTRIC

zinc
for

SMBLTUia

ores,*for poor zinc and


mixed
oreBy" for calamine

It is needless

here

obtaininga solution
alkali-

and

almost
of zinc

earth-alkali

or

ores,!for zinc snlphideores, |


the like.
zinc blende,||and

lead

to describe the individual


proposalsin detail.
other inventors,
remark
that Hoepfner, unlike
most

It will suffice to
has
worked
the

REFINING.

AND

the

exclusivelyin

of

direction

chloride,mixed with the chlorides of


metals, as electrolyte.The further

generallyin the
because
same
Hoepfner preferszinc chloride as electrolyte,
way.
of
chlorine
obtains
The
he then
as
a
by-product.
recovery
zinc
by-productsis, however, a necessity,because otherwise
anodes
could
be
at
with
insoluble
never
electrolysis
profitable,
the cost of power
is not below the average.ir
least when
has found
The only process which
on
a technical
application
that
the
German
Patents
described in
85,812
a
large scale is
oxide
Calamine
the
zinc
and 86,153.
or
as
ores, containing
is then

of this solution

treatment

conducted

"

leached, under

carbonate, are
solution
the

of calcium
The

time.

same

equationsthen

take

hot

with
pressure,
dioxide
chloride, carbon
shown
reactions
qhemical

concentrated

being
in the

led

in

at

following

place:
"

ZnO

ZnCO,

+009
CaClj

ZnOO,
ZnO, + CaCO,.

=
=

be crushed
'*The ore
must
very fine before leaching. The
the application
of this process
additional patent 86,153 extends

sulphidezinc

to
'

zinc carbonate

zinc

It

ores.

which
(blende)

ore

condition,a

also be

^ZnCO")can
solution

contains
of

the

that
specification
produced by treatingroasted
in

is claimed

free zinc

oxide, in

powdered

magnesium chloride (MgOl^),or

No.
for

85,812. Finally,zinc
This
electrolysis.'

used
a

(ZnClj). In

this way

zinc

oxide
a
is obtained ; the zinc hydroxide which
separates out is treated
with carbon dioxide and so converted
into zinc carbonate.
The
is
accordance
latter
with
German
further treated in
Patent,
chloride

in

England.

little doubtful

The

whether

basic

chloride
or

process,

solution

and

is obtained
one

of zinc

similar

to

this is used

it, has

complex, and
process is somewhat
the extraction of zinc from the

been
it is
ore

is

quitecomplete.
chloride

"Zinc

by
zinc.

Lenne,
are

two

be obtained
may
suitable treatment

It is well
in

known

that

ikr

more

of burnt

veniently
simply and conpyritescontaining

am
Meggen, near AJtenhunden
There
of
are
largedeposits pyrites.
Sicilia and Sigena^on the oppositesides of the

at

Westphalia,there

mines

:
*

Germaa
t German
t Qerman

Patents
Patent
Patent
" EnglishPatent
Patent
liGerman
IT German
Patent

85,812 and 86,153.


62,946.
86,543.

8,328,1805.
87,398.

91,513.

421

ZIKC.

of which

Jjenne,
been

the

in

former
since

operation
pyrites have been made

is the

1880.

by Fresenius,as

hy others

also

North-west
Per

37-49
4-23
4473
0-66
0-20

SO,,
McO,
CO,

CaO,
Afl,

SiO, + AI5O3,

Pb,
Cu,
Mn,
Ni,

10-80

42-26
0-74
050
1-20
0-96
0-09
8-21

015

119

Trace

0-03
013

0-32

"

Minute
trace
Trace

....

Minute

trace

Trace
"i

005

0-15
99-98

99-78

''The

Meggen

pyrites,by

of the

reason

sulphur present^ is of great value


and
sulphuricacids. The
however,

prevents
furnace.

The
from

them

They

they

a
occupy
residues
formed

and

valuable

of

to

hydrochloricacid,
to

to

leach
remove

separate the

liquid either
temperature corresponding to
aware

iron

as
on

roasting,

nuisance

ores

in

the waste

the

heaps
recognisedthat

soon

methods

them.

the

is not
[Giinther]

left after
often

are

for the

material

to

these

extraction

introduced

were

blast
where

for

to

the

of
the
and

The

f proposed

chloride,then

by cooling

use

raw

several

zinc from

works
metallurgical

of sulphurous

manufacture

comparativelylargeproportionof zinc

being

iron, and

large proportion of

residues

are, therefore,thrown
It was
large space.

of the

present, and

for the

only worthless, but

not

are

manufacturer.

writer

Working.

0-87
0-07
1108

BaO.
O,

sodium

"

cent.

0-20

...

PA.

removal

0-01

Ag, Au,

zinc

this

33-39

"

Organic matter,

the

has

latter

analyses of

South-east Working.
Per cent.

Fe,
Zn,
S,

the

older,whilst

Exhaustive

Konigshiittemining
the burnt
pyriteswith
ing
product with water contain-

roast

the solution
if
from
copper
sodium
sulphate in the solution
tb
normally or artificially
the grade of concentration.

whether

the

company

the
The

initiated

experiments on these lines,and, if so, with what results. The


principleof treatingthe residues is,however, bere indicated,as
and
it was
later carried into effect,
the question of what
were
the practical
results.
'*W.

Stahl
*

has
(Niederfischbach)

made

series

Berg- und hiiitenmdnnisc?ie Zeitung^1896, p.


t/6id., 1884, p. 475.

351.

of careful

422

ELBCTBIC

SMELTING

AND

experiments* in this direction.


of the followingcomposition:

He

BEFINING.

employed pyritesresidues

"

IL

Percent.

Zn,
Fe.
Mn,

Ni^
CoJ
Cu,
8.

80,,
CaO,

MgO,

A1,0,.

Percent.

7-75

41-52

0-36

48-46
0-24

10*65
45-24
0-41

Trace

Trace

Trace

Trace

0-02

0-O2

4-23

4-56

6-59

7-51

412

6-86

0-82

015

025

Trace

Trace

6-49

4-90

10-55

10-86

9-95

18-72

18-94

16-21

100 00

100 00

Percent

10-69

Oil

III.

Reeidue,
0 (by difference),

3-82

The

"

and

zinc is contained

partly in

10*69

per

submitted
an

zinc

sulphide

oxidised state; for example, in Ore I. the


of zinc conaisted of 8*51 per cent, of zinc as

2*18

per

crushed

the

addition

residue,partlyas

the

cent

sulphide and

in the

100-00

of from

in

the

material

to

cent,

18 to 23

per

form
a

cent,

sulphate. Stab I
chloridisingroast with
of waste
salt,according
of

proportion of zinc,either with or without an addition


of pyrites. The
roasting lasted six hours, and the material
stirred during the latter half of the time.
The
results
was
Stahl
obtained
not
are
altogetherencouraging. After
by
acidulated
he obtained
residue
water
a
working with weakly

to

the

which

contained
of zinc.

in the

best

Stahl

case

2*16, and

to the

in

conclusion

the

worst

3*93

that,conducted

came
per cent,
the process was
examination
in this way,
not profitable.An
that zinc chloride
of the product of the roastingfurnace showed

of the zinc sulphide


during the process surrounded some
from
further
and
it
decomposition. In order
protected
present,
to secure
a more
thoroughremoval of zinc a further roastingis
similar
in a manner
conducted
to that originally
necessary,
residues
with
obtained
were
applied. In this way extraction
of sulphide. A
0-53 and 0*56 per cent, of zinc in the form
results
in regard
satisfactory
sulphatising
roastinggave no more

formed

to zinc extraction.
^*

to

be
Hoepfner cannot, therefore,
have
attempted the extraction

residues, and
*

therefore

the

credited

with

of the

zinc

being the first


in the pyrites

the

residues

utilisation

Berg- urid hiUtetimdnniwhe

of

ZtUung^ 1894,

p. 1.

them-

425

ZINC.

seWeM, but

played an important part in the practical


problem. It is largelythrough his work that
the first more
less unsatisfactory
in time superresults were
or
seded
far
others
more
satisfactory.
by
"In
with
the object of
addition to the experiments made
producing a cheap zinc chloride solution,Hoepfner, as far back
the beginning of the year
as
1890, had instituted others to
electrothe possibility
of decomposing the chloride
determine
tried
These
latter
several
in
places,
lytically.
experiments were
As
notably at Eiserfeld,near
Siegen, and at Giessen.
they
position,
proved to Hoepfner that it was
possibleto obtain such a decomenabled
he was
to erect
a
larger experimentalplant
a
on
an
manufacturing scale. The site selected was
existing
Fiirfurt
which
in
water
at
on
was
available,
factory,
power
the
Lahn.
first it was
intended
At
an
only to put down
obtained
which
in
chloride
zinc
solutions,
electrolytic
plant
could be treated after further purification,
from
other sources,
Various
led to the wish
if necessary.
to promishaps soon
duce
solution

he

has

of the

zinc chloride solutions


in the same
necessary
Accordingly, in the years 1894-95, a roasting and
the

plant

erected,and

was

consumed

it

to

treated;

and

should

above
it

up

"The

consists

of

of

solution

lime
to

chambers.

leach
"

The

fresh

with

water.

chloride, with

sodium

the

and

Zinc

separates

being then

form

works

latter

available

follows:

of

salt,

and

cathodes

passed
nearlyfree

of

zinc
last

to

chlorine

the chloride

to

from

of

zinc,serves

mixture.

contained
14

the

to

on

an

average

zinc,but occasionally
specimens were

the

was

The

"

common

transferred

are

ou

portionof the roasted

sulphide,of which

be

to

the

The

the

at

solution,when

largerproportionup

present in

the

as

addition

chlorides

latter

10 to 12 per cent, of
with

of

resultingliquid
of sodium
sulphate,sodium
various
impurities. After
other
impurities,the pure

of solutions

pyritesresidues

which

is conducted

is leached

The

material

products

the

and

pyrites residue

raw

chlorine,of

that

so

of lime.

sulphuric acid

anodes, the

the

with

zinc

zinc

the

leaching

extended

was

first,the
as

roasted

tanks.
electrolytic
at the

and

cyclicaland

are

mixture

chloride, and
removing the

the
that

into chloride

product

the

and

was

plant

contemplated
intended

is

process
residues
pyrites

whole

From

was

zinc
electrolytic

be

be worked

to

H.F.

300

referred

the

works.

and

oxide,

The
16 per cent.
zinc sulphate,and

from
found
zinc
zinc

preponderates greatly
only from 1*5 to 2 per cent, is present as oxide and
of
of the zinc is in the form
sulphate,whilst the remainder
This
the
to
sulphide.
proportion varies,however, according
time
during which the residues have been lying exposed to
A
second
atmospheric influences.
roasting is necessary if it
is required to obtain
of the
the whole
rate, most
or, at any

that

named

so

424

8MBLT1NO

BIiBCTBIC

zinc

present

in

to

obtain

it is desired

in which

form

the

salt is suitable.

common

between

yaries
with

30

quantity

residues
conducted

and
of

be

must

60

REFINING.

AND

it is soluble

zinc

as

The

size of

before

grain

of

the

residues

in diameter,
ins.]

to 2*36

material

crushed

chloride,roastingwith

zinc

[1 18

mm.

finer

Since

in water.

Hence

intermixed.

roasting,a

the

is
process which
construction
: the

of the usual
crushing-rollers
funnel
ore
through a
upon two cylindersrotatingtowards
The
each other.
productfrom the rollers is raised by a chain
of buckets
and depositedon
a
siftingscreen, which allows the
and
the largerpiecesto
fine material
returns
to pass through
in

falls

the rollers.
1*5 to

The

[0*06to

mm.

dealingwith

from

of about

quantity

of

This

weight

chloride

still warm,

is mixed

of from

with

the necessary
crushing,in order that

before

substances
be ensured.
two
may
5 per cent, of raw
pyrites. The total
is from 18 to 20 per cent, of the weight of

with

with

it is extracted

residue after

Fe,
SiOU,

diameter

crushing-roller
capable of
hours requiresan
diture
expen-

in ten
ore

The
mixture
so
prepared is now
pyritesresidues.
of
furnaces
ordinaryconstruction,afler which,
roasting

placedin
while

to

of the

mixture

of salt used

burnt

crushed

in.].A

008

20 to 25 tons
H.P.
The

salt is mixed

the

The

12

sodium

intimate

an

is thus

material

leachingcontained

and

water

dilute solutiona.

"

AljOs,.
*'

The

sodium

produced was
manganese
and calcium

sulphatecontained in
removed
by concentration
extracted

next

were

precipitated
by
contained

on

cooling;

in the

ZnCl, (9*5 Zn

10*4 CI per oent.)

NaCl

135

of chloride

or

former

average

"

from

of lime

metals
electro-negative
The solution so purified

20 per cent.

form

thus

iron and

of chloride

described

of zinc dust.

means

solutions

22

together with
always in the
form

an

and

the aid

with

by the method
Finally,the more

carbonate

edition of this work.


were

the crude

0*05

(87 Na
to

of calcium

0*1

per

CI

cent,

sulphate,and

sulphate. Only

traces

"

of
some
were

sulphuric acid,
calcium

found

in the

of other

constituents.
'*

The

solution

treatment

with

zinc

alkaline,owing

to

dust
the

has

the effect of

absorptionof

zinc

making

the

oxide, the

alkalinity
ranging from 0 06 to over 0 1 per cent. The solution
conducted
is now
through iron pipes to large iron tanks,which
itself or directly
either
the vat-room
in
are
adjacentto it.
ranged
with danger to
The use of iron tubes and tanks is not attended
the zinc solutions on account
of the alkalinity
of the latter. The

426

KLBCTBIC

SMBLTIHG

quantityof hydrochloricacid
contained
with

elevated
tanks
"

constructed

The

in

supports restingupon
decreased
bath

from

stood

Passages of
the

the

Sufficient

cm.

lower
[4ins.]

about

80

cm.

[2 fL 8

far

which

as

was

coated

been

never

four

in

in such

carried

the

than
width

for

left between

to

man

each

precedingone.

weie

of about

provided

on

pillars

that

way

of

rows

electrically

were
were

passages
left between
the baths

first with

to
slightsloi"e
might escape on
a

the baths
"The

batha, which

heightsof these

similar

were

also

was

60
have

vats

in
ins.]

These

50

cm.

transversely.
move
freely

the Ijaths.
In this way provisionwas
made
for access
The flooringunder
possibleto all sides of every tank.

the tanks
It had

room

which

back

10

width

take

fashion, and

the

for

into

mixing.

pillars. The
to

ready

is

pumps
baths.

the

arranged

were

about

in
[1 ft. 8 ins.]

as

front

for

individual

lengthwise,and

rows,

beneath

iron

into

another, but

The

series.

by

used

used simultaneously. The tanks


fifteen each, placed in terrace
connected

earthenware

designedto

was

after

one

prepared

so

it flows

like those

room
electrolysis

all erected

were

raised

which

from

now

solution

is therefore

receivers

are

The

pole.

It
electrolysis.

BEFININO.

added to the pure solution


tanks, and the mixture ia stirred

is

in the double-walled

wooden

AND

could

side

one

to the

concrete

that

so

floor

and

then

the bulk

by leakageor

with

asphalt.

of the solution
otherwise

from

be recovered.

first baths

by Hoepfner consisted of separate threecornered


and with a thick
frames, joined up like filter-preeses,
The
o
f
plateplacedon the two ends.
triplets strong clamps on
these ends were
bound
of iron
togetherlongitudinally
by means
bars.
The iron bars had a screw
thread,so that by tighteningor
the
frames
could
the
be pressedtogethermore
nuts
or
loosening
less firmly. A layerof asbestos or other suitable material was
laid
At
the same
time there were
the frames.
placed between
between
was

and

the frames

used

the membranes

by

which

divided

the whole

up into separate cells. In this way


7 cathode frames were
providedin each bath.

of the cathode

and

anode

frames

chamber

8 anode
The

frames

third side

representedby a top strip


two
sides.
stripsserved,on the
one
hand, to carry the membranes, and, on the other hand, they
of the anode
cell gasgave the opportunityof making the cover
used as anodes at first,
and
wards
aftertight. Retort carbons were
The
sheets
carbons.
of
iron
cathodes
were
prepared
large
of zinc ; more
will be said later as to their specialarrangeor
ment.
The electrolyte
is the same
cathode
for both anode
and
the
but
circulated
order
solutions
to
two
are
cells,
separatelyin
the
saturated
which
anode
becomes
solution,
gradually
]"revent
with the cathode.
with chlorine,from coming into direct contact
For example, the solution enters
the outermost
anode compartment,
the long side,at the bottom, then, traversing the cell.
on
dovetailed

into the other

was

These

427

ZINC.

passes
This

over

possiblebj

bored

channels
cathode

concerned.

side

beneath

anode

compartment,

of

the
*"

to

in

similar

cell,and
The

compartments.

effected

of the

circulation

within

the frames

obtain

access

then

was

sought

circulation

to

channel

was,

tubes.

This

it

the next

into

above

one

of

passes
the one

cells,from

oppositeside

the

at

the last

from

to
finally

escape
in the cathode

circulation

under

cells is

obviate

this

it

as

impossibleto

was

stoppages

It

occurred.

difficulty
by conducting

outside

extent

greater

that

this arrangement.
U-shaped channels

the

control
so

passages,

to

with

inevitablyoccur
through

solution
not

was

the

to

and
form

way.

would
Irregularities

The

anode

side above, then


on
pass out thence

into the next

the

the solution

In this way

the several

lengthwise

frames

has

channel

compartment.
one

anode

two

the other

to

bottom

the

the

the frame.*

within

and

transverse

This

zig-zagfashion through

anode

the next

into

two

in
respectively

frame

double-bend
in

the other side

on

is made

therefore,replaced by
arrangement, however,

baths.

the

cross

U-shaped glass
a
remedy

external
did

The

the

afford

not

difficult to

keep it water-tight.The apparatus was


better
which
was
faultyowing to its complicatedconstruction
suited for laboratorywork
than for manufacturing operations.
A damage to any portionof the bath, such as the tearingof a
the whole
membrane, a leakage, or any other failure,made
apparatus so ineffective as to necessitate its being taken to
labour, as also a loss of solution
pieces. This involved much
as

was

considerable

and

of this kind
It

of

example

not

were

be

may

and

wear

well

apparatus

in the

first German
the

constructed
edition

translation

Disturbances

material.

infrequent.'*
to
give here, with

an

the year 1891.


To quote from

of bath

tear

the

of this

in Electric

[1stedition, p. 310],the apparatus

illustrations,an

this

on

system,

scribed
de-

as

work, published in

Smeltingand

^'consists

of

ing
Refinnumber

of frames, R, which
held togetherby means
of a screw-press
are
working in a horizontal plane,and which thus forms a single

vat, divided
paper

up

other

or

is
description
vertical

into

shown

suitable
in

by
partitions. A

compartments

narrow

Figs. 219
the

section

line

and
AB

220,

"

120

this

give,first,

which

and

ment
parchof

frame

then

(Fig. 219), and

along
horizontal section through C D (Fig.220).
The wooden
planks,S, S, ?t, form the side
of the tanks, and are 70 to 80 mm.
thick by

of

sheets

bottom
mm.

wide

walls

[2}

tie

width

of which

is

equal

"German

to

Patent

the

thickness

63,133, Feb.

of the
22, U89.

wooden

lath.

428

ELECTRIC

By placingO

and

SMELTING

little out

AND

RBFININO.

of the middle

Fig.219.~Section.

line of the frame,


be left for
may
space
admission
of even
^^^
electrodes.

thick

end

each

strip,M,
a

thread

manner

in such

cut

that

frames
One

the

held
screws

of these
of such

is made

the

be

may

togetherby
G.

rod with

metal

round

At

of the copper
is fastened a

rods

length

be cut
a slot may
in the end projecting
that

beyond
thread

to take

shaped

Fig. 221."

End

elevation.

of zinc
Apparatus for electrolysis

which

is attached

to

the

conducting wire.

the
metal

Fig. 222."

screw

wedgekey, W,

Plan.

solutions.

The

other

end of the

429

ZINC.

provided with

wire

is

with

one

four

apertures, and

together,unite

to

lengthwise in

the

% and
passages,
similar passages

X^

similar

of the electrodes

cell

x,

The

cells.

through

the
P

the channels
; and
the
with
connection

X^

and

anode

round

the

These

diameter.

and

three

rods

to

the

(Fig. 222), and

the

shows

bands, H.

sides

of the

The

frames,

supports, resting

as

100

about

are

carried

are

into

220

Fig.
metal

only as handles, but

bars, P, which

iron

and

I, and flows away


through
in
for a similar purpose
serve

from
on

between

compartment.

screwed

are

not

serve

contains

is introduced
electrolyte

channel

K, suspended
cathode-plate,

they

frame

of communication

means

that

is made

contact

Each

all the frames


are
these, when
joined up
four channels, I, I^,X and
X^, running
bath.
From
the ducts, 1 and
X, narrower
lead into the cathode compartments, whilst

form

cast-handles, N,

which

bath.

form

the anode

and

cathode

wedge by

in the next

[4 ins.]in

mm.

through

the

fastened

in

so
on

frame

of the

by
and
pressed together by the screw
hand-wheel, r, and the pressure plate,Z, which also rests on P.
Fig.221 shows an end view of the pressure plate,Q.
''It should be unnecessary
to explain that the electrolyte
may,
if desired,be circulated
through the various anode, or cathode,
of
successively,instead
simultaneously, the
compartments
in the wooden
frames
channels
being then, of course, cut to
Numerous
modifications
correspond with the new arrangement.
been patented,but nearly all the details
of this apparatus have
Q

press,
The
frames

in most

themselves

The
filter-press.
less

by

after the

of tho

apparatus

model

and
sugar-refinery

descriptionof

of recommendation

way

it

screws.

are

devised

are

cases

osmosis

are

above

the
than

as

of the
the

well-known
forms

newer

of

apparatus is given,
illustration

an

of the

principle."
To return
follows :

to

Giinther's

this

communication,

continues

as

"

Almost

"

all the above

described difficulties

introducingseparatelyinserted
such

use

who

the

was

then

cells

consisted

anode
closed

is,the

owner

of two

cells. The
the

writer
of works

ends

anode

cells.

with

were

overcome

believes,due
[Giinther]
in Giessen.*

The

separate parts, the tanks

tanks

by
suggestionto

were

The

built

up

of broad

to

G.

bath
and

Throm,

apparatus

the enclosed

wooden

frames

wooden

plates,and, like filter-presses,


clamps on the ends and
made
in the shape
were
by
of an
side.
the
on
equilateraltriangleopen
Leakage
upper
between
the frames
and between
the frames and
the end-plates
The
bottom
of the
was
prevented by a packing of asbestos.
tank
the
of
the
made
at
tight by pouring
trianglewas
apex
at

held

firmlytogether by strong wooden


The
iron rods on
the sides.
frames

day

This is the arrangement met


cells {Bcrchere).

with

in

primitivebatteries using porous

430

ELECTRIC

it a
upon
frames was
of

mixture

painted

resistingthe
of

the

object of

The

solutions.

prism

and

with

over

using, with

form

of hard

with

one

REFINING.

AND

SMELTING

pitch. The inside of the


of pitch the first time
rendering the wood
capableof
soft

mixture

whole

long edge

tank

had, therefore, the

turned

downwards, and

431

ZINC.

with

the

side

right-angledside subtending this angle upwards, this

beingopen.

wide

and

The

inside

[75

one

(to

into

come

direct

pitch-pine. This wood,


because
the

it

of zinc
resist the

not

indeed

which

chloride

contrary, these

and

is

has

that

chloride
the

wood

destroyed,so

few

became

scrapedoff
used

to

the surface.

protect the surface

solutions,the

action

was

the

of the

but

pitch-pine
On

wood

the
very

for zinc chloride solution.

The

cellular tissue of the


the tanks had been in use

millimetres
Like

resisting

it

Fig. 225.
section.
longitudinal

Part

of soaps.
that a^r

months, layers,some

of

solutions.

resin

section.

the formation

cells
which

because

shown

attacked

stronglywith

the anode

specialpower

solutions, and

tank
Hoepiner'selectrolytic

mm.

above
ins.]

the

Fig. 224.
Transverse

1,900

[84J

mm.

tank.

parts
of
solutions,were
highly resinous,was preferred
with

of zinc

solutions

[9^ ins.]

mm

for each

all the wooden

have

to

action

2,150

the frames

Both

slightlypervious. Experience
does

of

contact

considered

was

action

225).
and
later),

described

would

width

and

240

used

therefore, about

were,

length,with

(Figs.223, 224,

frames, each

wide, were
[5^ ins.]

mm.

measurements

ins.]in
be

wooden

Seven

140

in

the resin

is also

more

being strongest

thickness,could

be

in the wood, the pitch


less attacked
by the

or

when

the

proportionof soft
proportionof soft
be
hard
dispensedwith, as
pitch cannot, however,
pitchalone is
of 80 parts of hard with 20 of soft pitch
brittle. A mixture
too
be the most
found
suitable.
to
Exhaustive
was
ultimately
kinds
of wood, includingpitch-pine
experiments with various
oak, fir,willow, maple, copper beech, and white beech showed
tried,white beech was most durable
that, under the conditions

pitchused

and

in the mixture

had^ the greatest

solutions.

is tarry.

power

of

certain

resistance

to

zinc

chloride

432

ELscrrBic

"The

anode

tanks
cells.

free space
cells are,
two

smiltimo

intended

are

Between

which
anode

shown

Figs.223

in

enclosed

sides

short

two

the cathodes
smaller

The

are

The

of wooden

box

and
side

and

bottom

ar

cells is

bottom
broad

the

the

cells forms

consists of

and

top

rectangular,whilst

and

of these

complete cell
the

cathode

tank

of the anode

the

is a de6nite
The

of the

construction

trapezoidalin shape.

is

sides

s|)ace.
22d.

to

walls

each

The

sides, of which

six

on

by

and
electrolyte

cells there

compartment.

the

cells,whilst

completely enclosed

the

contain

to

the cathode

forms

hkfining.

adjacentanode

two

therefore,bounded

nearest

and

the

"cing

the

two

joined together.
iiriuly
provided with grooves on both sides (where
which
are
they face the cathodes),to take the membranes
wedged into them by tongues of wood gripped firmly to the
boai^ by ramovable
wooden
clamps. At the top, the boards
sides
the
smaller
are
forming
slightlytapered and provided
with an
inner and an
iron strip. The
outer
upper edge of the
membrane
these stripsand
is introduced
between
firmlyheld
there by means
of a groove and tongue. The stripsare gripped
the
described
boards
against
by wooden clamps in the manner
above.
in Fig.225, the outer
As shown
stripprojectsbeyond
These

are

boards

the

inner

the

two

both

one

and

below

above.

fillets togetherwith

forming

constitute

boards

are

outer

boards

made

small

the

channel

pitch to
will not

top of the cell,

ends
upper
small
wooden

two

the

inserting the

after

which,

filled up with tar and


All jointswhich
gas.

the

and

sides

the

At

of the

boards

anodes,

is

prevent the escape of chlorine


in the solution are
be immersed

mixture.
of the above
whole
rendered
The
tight by means
enclosed
anode cell is now
of
which
the
a
vessel,
completely
of wood, the cover
of pitch
bottom
and small end walls are

mixture,
of

mostly
cell

and

as

wherever

the

side

broad
To

walls

(exposed

the

to

cathodes)

the

of .the
greater stability
and
are
whole, screwed
employed
stays
supports
possible. Any iron parts in these supports are most
membrane.

insulated
carefully

with

ensure

celluloid,india-rubber, pitch,or

the

like.
"Oarbon
carbon
the

was

obtained

middle

sufficient

of

always used for the anodes.


the gas works
direct from
was
the

year

durabilitywere
to

as

cost.

1890, however, prepared

produced, and
They

carbon

quantity from

first retort
employed. In

At

scrap;
purer and

were

no

dearer

of

carbons

satisfied

obtainable

were

they

these

in

all

quirements
re-

sufficient

than

retort

also
they were
of electricity.They possessedthe further
better conductors
into any form that might
that
they could be moulded
advantage
but

were

necessary
necessitated

or

carbon,

be

with.

wished
the

for.
of

more

The

retort
use
by
Figs.223, 224, and

durable, and

troublesome
carbon
225

show

after-treatment

is thus
the

pensed
entirelydis-

arrangement

of

434

REFINIXr..

AND

SMELTING

ELECTRIC

the like),
to form one
so
or
as
(by cementing,riveting,
largeplate. Two of these largeplates,with a layerof asbestos,
powdered carbon (1),or tl)e
paper, tissue, clay,sand, gelatine,

fashion

like between, can


also be used as a membrane.
**
These
mica diaphragms have found no use

tory
except for labora-

In
are
only too obvious.
experiments. Their drawbacks
the
offer
resistance
to
the
of
they
spite
great
perforations,
chemical
current.
they withstand
Although in themselves
it
attacks well enough, this advantage is removed
soon
as
as
of them
becomes
into one
to join several
largeplate,
necessary
unatt^ckable
the problem then arises of findinga sufficiently
as
doubtful
material
for rivetingor cementing. It is,moreover,
such
whether
plates,especiallywith other materials between
action sufficiently
could
mechanical
withstand
to render
them,
their use advantageous on a largescale.
The
second
experiment did not give the desired result,but,
based on a noteworthy idea. As
in the writer's opinion,it was
be able to resist both
the
diaphragm must
already explained,
oxidisingand reducing influences,and also the attack of weak
"

acids

and

zinc

example,

chloride
these

meet

whether

requirements,reserving
absolutely indifferent

zinc chloride.

attack

would, for

the

remain

it would

continued

acid

Silicic

solutions.

question

to

long-

The

made

now
by
attempt was
impregnate muslin or jute with silicic acid that the latter,
entering into and surrounding the fibres of the fabric,should
protect it againstthe attack of the gases, Ac, above referred to.

to

so

For

this purpose
the material was
dilute
cold solutions
of water

glass

This

or

the

process
fabric was

acid.
a

immersed

repeated three

was

washed

four

after
carefully

alternately

in very

and

hydrochloricacid.
times, taking care that

each

with

treatment

the

used as diaphragms in
prepared in this way were
four
months, and proving
large bath, remaining in use for
Cloths

themselves
time.

in

But

friable and
from

came

fell to
Dr.

might
cloth

to

have

was,

incomplete and
it under

The

powder.

G. Eschellmann.

however,

appears,
results
of the

fabric
way inferior to the nitrated
of this period they became
the end

no

at

the

in

suggestionof these experiments


It
not continued.
They were

writer
obtained

been

during th^t
absolutely

[Giinther]that
m

time.

The

these

experiments, never
superficial
; probably it would
and at a higher temperature.

still better

impregnation
otherwise

be well

to

than
efiect

It

might also
impregnationto
and
specialtreatment, by removing greasy matter
dressing.
After the anode
been
carbons
have
suspended in the cell,
the diaphragms are attached
to the longersides by the arrangement
The
cell is closed with the
provided for the purpose.
be found

pressure

desirable to submit

the

cloths

before

"

exception
between

of the

uppermost

the tops of the

side,where

carbons.

This

small

space

space
is closed

remains
as

fer as

435

ZINC.

is

practicable
by

25

for

tube

be withdrawn

is left

and

on

opening of

An

side,and

one

enable

closed

closed

in the

The
'^

Glass

pipe

in order

is made

to

into

wider

placed

horizontal

the

by

with

tar and

diameter.

same

tube

allow

to

cells,of

the

is

of any

flow away

rows

diameter

water

vapour,
lower end.
of the

is

cross

the

30 baths.

of 200

tube

The

two

united

are

the

The
same

for each

by

is connected
chlorine

diameter, leading to the

same

after

[6 ins.]

their ends

at

diameter, to which
[7fins.]

mm.

pipe, of

main

eight
deliver

little inclined

the

at

means

The

tube
higher end
joined to a vertical pipe
diameter
leadinginto a long horizontal tube of 150 mm.
diameter.
of these long tubes are
Two
provided,one
two

cross

pitch.

tank

[3|ins.]internal

mm.

transverse

in order

of the

the

80

collect and

condensation,to

formed

T-pieceis attached, by

eight anode

the

transversely. This

the

from

To

of about

tube

cell is

first part of the chlorine


insulation ; the continuation
of

of about

a rubber
tube, a tube
tubes,correspondingto

T-piece

for the

secure

of lead.

of

of

anode

gas-tight.

is used

caoutchouc

or

outlet tube
this

closed

is therefore

top

channel

cell is filled up

of the

an

of gas to
of the cell for the purpose

space

described,the

manner

side walls

filletsand

with

samples

for the chlorine consists


testing. The escape-pipe
caoutchouc.
As
the top of the
as
soon
glass or

of

about

the other

on

is afterwards

pinch-cock,to

the chlorine

from

wood.

stripsof

glass tube, which

thin

india-rubber
of

thin

[1 in.]diameter

mm.

hole

small

chambers.
"

Zinc

have
its
for

or

discs

iron

diameter

of

1,400

presupposes
separating the
iron

from

the

discs

the

hammer.

that

this treatment

it could

tried

and
with

course,

that

the

These
it must

brittle.

not

casting and

became

bent

firmlyto

blows

with

greatlyunder
and

had

to

be

With

these

it was,

of

deposited zinc, provided


zinc.
of electrolytic
cathodes
in
proved very satisfactory use, although
be forgottenthat the cost of producing them
by
have
discs
small
is
The
zinc
not
one.
a
rolling
remove

it
stability

to

make

each

violent

suffered

effect,for

so

is unwise
end

the

themselves

were

of

At

by

discs

cathodes.

as

to

thickness
a
initially
'^

iron

they

case

in its

became
using again, but they also soon
On
these
grounds, experiments were

discs

zinc

removed

found

been

facilitate the

frequentlyadhered

be

only

cheaper,but

emery-cloth,
graphite. It often

failed

measure

very

; in every

unnecessary
cathodes

zinc

this

to

discs

with

rubbing

of oil and

coat

Obviously,the

straightened before
cracked

thin

These

is
has

means

order

In

it.

discs, after

provided
happened, however, that
the electro-deposited
zinc
with

were

convenient

zinc

cathodes.

for the

[55 ins.].Iron

mm.

that

use

separation, the

used

are

of the bath

mm.

made

[0*08in.],but

for the

sake

of

it less.
a

bearing is provided,on

the

upper

436

ELECTRIC

SMELTING

supportingbeam, carrying
rotatingshaft.
maintained
by
them.

between

all

keep

The
The

the

rings

dia[2ins.]meter.

mm.

vertically

adjacent discs is
flanges,
placed
held by rings which
tubes are
firmly j)ressedtogether. This
wide

sleeves,with

discs

the cathodes

to be rotated.
arrangement permits
working parts are accuratelyfitted. The shaft

bearings,one

red-brass
the

of

source

wooden

beams

bearing

on

glazed

by
end

one

under

the

ton]

of zinc.

tank-room

various

without

cathodes

able

to

whilst

by

cathodes

any
that the

and

of tar

coat

bath,

the

does

pitcii.

between

admission
The

cathodes

in that

and

time

to

attachment

and

removal
below

tanks
electrolysis
the

top

the

on

compelled to
prescribedcourse.

taking

ensure

of tlie

solution

is well

throughout.

circulation

at

the

It is

side

rotation

mixed

only

cathodes.

at

of
the

the whole

traverse

The

one

on

other

and

of

of the

fairly

possiblein this
The

solution

is

under
the anode
cells,
pass freelyby the side of and
the enclosingdiaphragm partially
or
completelyprevents

passingthrough the
flow of solution

The

the

words,

about

at

of the
draws

the

be
zinc may
its solution

of

always be
a

given

so

time

whole

arranged
replaced

is

In

other

this way, be
The
of
zinc.
tion
substitupercentage
individual
arranged that either each

same
so

from

series

common

is fed from

reservoir,or
the

only the
liquid

reservoir,the

first to the second, thence to the third,and so


it is finallv diacharored from
The
the last of the series.

passing from
until

cell itself.

by the fresh solution introduced.


in the bath
must
electrolyte
always,in

the

first bath

out

anode

to the bath must


of the liquidin

time

same

maintained

on

The

plant.
at

that the zinc taken

bath

the

1,000 kilogrms.[16 cwts. to


the whole
running over
travellingcrane

concentration

it from
**

of

severallyconnected

are

by

driving
places,

necessary
chain-wheels

The

the

it

the

at

in the

assists in the

ensures

uniform
to

from

teeth.

the cathodes.

and

800

from

escapes
It is in this way

oppositeend.

in

sleeves

long sides,and

way

insulated

protectedby
moisture
gains

no

parts of the cathode


solution enters
the

"The

bath

Beyond

five weeks

to

deposit of

of the

iron

four

from

receive

that

taken

flangesof

the

the

blocks.

is effected.

driving

from

revolutions

12

to

solution,are

is also

remain

the

enter

the

the

with

connect

iron

bath, as
Care

shaft

bath

of the

in. two

per minute.
cathode
of
the
apparatus which lie over
parts
middle
of
discs that
also the
the cathode
portion
10

from
The

not

and

chain- wheels

separate

turns

insulated

fortyiron

series of baths.

chains, whereby

make
"

small

whole

the

driving shaft
iron

shaft, but
with

The

to

serves

earthenware

the

of

also

bearings are

chain-wheel

shaft,provided with
runs

The

current.

caoutchouc, is

which

of

this

on

between

space

outermost

and

of 50

mounted

are

necessary
tubes or

iron

shaft

iron

an

cathodes

several

The

REFINING.

AND

the

437

ZINC.

methods
of

accomplishing these

of

small

the

By
parallelworking, each
extent.

first

ends

two

method,

bath

receives

different,to

are

which

be termed

may

no

that

its solution

independently,
own
supply
dischargepipes. The composition
baths
and
of all the
is practically
the same,
the baths
themselves
under
work
almost
identical
conditions.
By the
second
method
(connectingin series),
only the first bath of the
series receives
fresh solution, the others are
always fed from
the
bath
immediately ])receding.In this case, one supply and
with
connections
between
one
discharge pipe are necessary,
The
tanks.
successive
composition of the solution differs in
different
the
first
tank
baths,
working with concentrated, the
first sight there
last with
be
dilute, electrolytes. At
may
and

and

requiresits

doubt

some

have

first laid down

solution.
in

Each

both

was

the first and

between

system
was

The

difference

; both

Fiirfurt

supplying the
arranged terraceof

[4 ins.]lower

cm.

better

drawbacks.

baths

10

being

Hence, there

one.

their

for the series

tank

is the

systems

of fifteen

group

series,every

f59receding
ins.]
which

of these

advantages and

their

plant was
wise

which

to

as

in

than

the

level of 1*5

m.

last bath

of the series of fifteen,


in about
The
tion
solu40 m.

gradientof 1*5 m.
was
through a rubber pipe from each tank to
and
the next, always enteringa tank at the bottom
leaving at
The
circulation
is
the top.
good so far as it goes, but the
system has the disadvantage that, after the first,the baths are
those
It has been
preceding them.
always dependent upon
above
that acid is neutralised
stated
(0*05 grm. per ampereand
it is impossible to introduce
hour) during electrolysis;
of acid that will suffice
into the electrolytes
initiallyan excess
represents

conducted

the

for

even

baths

bath

last

would

be

of the

series, for in that case


Hence, in this case, the

acid.

too

first

the

necessary

quantity of acid,controlled
the

to

and

second

whole

by analyses,must
always be added
The
chief objectionto the
following baths.
is, that

arrangement
in

conditions
time

much

as

deposited
the

zinc

first bath

with

flowing into
as

the

theoreticallybe
since

the

up, and
anode

process

in

the

solution

cathode

to

in

per

but

takes
anodes

practice they

of their

cent,

given
is

as

period. Hence,

The

them

impure
like, and soon

0*2

any

first tank

same

continued.

electrolytebecomes
the

the

similar
dis-

is
concentrated, and, what
solutions.
The
electrolyte

deposited upon

the

and
manganese,
chlorine
gas, up
"The

is

quite

electrolyte.In
into

very

insoluble, but

chlorine

causes

series

under

work

very
pure,
is technicallypure,

bath

the

baths
the

introduced
with

works

important,

more

regard
is

whole

the

in

the
to

mineral
from

and

electrolytecontains

are

gradually breaks
constituents.

the

becomes

purities
up imshould
not

so,

them
The

addition

of iron,
saturated
with

over.

less than

0*01 per

cent,

of

438

BLECrrKIC

chlorine.

It is true

the anodes
but

is not

REFINING.

AND

SMELTING

removable

that with

seriouslyaffected

so

the Bolution at

anodes
that

as

the

at

cathodes,

it is

of the two
impossible to prevent a partialmixture
taken
in
bath
substances
one
foreign
go in part
up
purities
the cathode
solution of the next, and the quantityof imsteadilyincreases,whilst the proportionof zinc decreases

liquids. The
into

bath

from

bath.

to

contain

up
2 per cent,
10 per cent

zinc and

of

this it will be

might

even

however,

in the last tanks may


of
iron, and from 1*5 to
more,
in the first contains
from 9 to

solution

than

more

the

first for

supplying

first five

The

on

the

questioned whether
advantageouslyused

the

series

be
the

to

for each

pipe

common

good

tanks

satisfactory,it
these experiments,
later exerted

often
[Giinther]

writer

might

also be

not

circumstances.

after
used

gave

or

described

Fiirfurt
abandoned
at
However, it was
and
the
time,
parallelsystem was
the chief difficulty
to distribute
case
was

therefore

less

favourable

short

of solution

has

six

connection

otherwise

favourless able
The
reasons.

tanks

first of

the
to

result, and
under

or

last few

be spongy
zinc.
In
misadventures
certain

under

difierent
the

to

From

of iron.

trace

work

two

solution

passable zinc, the

influence

an

not

successful.

least

at

than
of

system

proved

not
or

the

the last baths

that

seen

conditions
series

Thus

0*1 per cent., or


of zinc, whilst that
to

comparatively

In this

instead.

the necessary
quantity
To conduct
the separate baths.
supply
a special
bath, or 60 pipes in all,is not altogetherpracticable.
least
therefore
at
be
used
must
supply pipe

torily,
problem has not yet been solved quite satisfaclast
the
at
sufficiently
was
although
adopted
arrangement
good for the time being. In the senes
system of supply tbe
be caused
solution may
but in the parallel
to flow continuously,
the
this
it
is impossible,
if
is wished
to use
a portionof
system
in

The

part

in

solution
"

the

After

In this

common.

intermediate

case

to feed into

it is necessary

sn

chamber.

we

have

become

bath, it only remains

the separate partsof


tion
that the most
careful insula-

acquaintedwith
to

remark

Blocks or plates
practicalkind is necessary.
tbe
ebonite
as
serve
glazed earthenware, porcelain,
glass,or
The whole
tank rests on strong glassplates,
insulatingmedia.
of any conducting connection
that there is no chance
between
so
of the

most

of

it and
another

its supports. The main conductors


and from earth, and the conductors

tanks

and

small

plates. It
leakage to

it must

on

the

supportingbeams

and
great difficulty
"

The

caused

that it is almost
at

very
completelyfrom

considerable

is started
electrolysis

from one
of tbe

the frames

on

to rest

be that, in spite of these


may
earth occurred, especially
in wet

be remembered

large plant

are

insulated

are

on

ware
earthen-

a
precautions,

weather, but

impossible,
except with
cost, to

insulate

such

earth.

by connecting up

the first "ye

or

439

ZINC.

six baths

of

primarily. In order to reduce the pressuie


shunt-wound
machine) to that necessary in
generator (a
this case, a water-resistance
is introduced
The
into the circuit.
series

of the

should

current

sq.

be

1,000 amperes

[9*3 amps,

metre

between

3*3 and

'*The

per bath

sq. ft.J.

per
3-8 volts.

and

The

100

bath

amperes

pressure

per
varies

flowing into the bath contains 9'5 to 10 per


of zinc, and
the proportion of zinc must
sink below
not
At 1 -5 per cent, the depositis grey and
cent.
dull, it is

cent,

2 per

solution

not

yet spongy,

the

bath
do

tests

or

however.

The

controlled

are

percentages of zinc and

titrations

by

made

twice

acid

day.

in

These

tory
much
time, and may be made in the laboraoccupy
the
The
workman
himself.
of
by
proportion acid is

not
even

be
never
per cent, of hydrochloricacid : it should
0*05 per cent., nor
rise above
0*25 per cent, of that

usually0'15
less than
acid.

solution

The

"

it is freed
the
"

leaving the
chlorine

baths

and

that it may

carbonate,so

sodium
to

from

flows

acid

into

collector where

of zinc-dust

by means
safelyconveyed

be

in iron

and

pipes

leachinghouse.
disturbances
the many
which
occur
be made
of teeth
to the formation

Among
must

edges of the cathodes.


projectionsare formed
black

become

and

Even

or

work,

ence
refer-

on

the

days work, tooth-like


periphery,and these gradually
whole
cathode
to become
rough and
after

few

the

on

the

cause

in

needles

the action proceeding from the circumference


dull in appearance,
Patent
inwards.
By the process patented by the German
of these projectionsis prevented by
No. 91,513 the formation

causing

the

cathode

wooden

laths

surface

to

be

rubbed

outside

the

horizontally.This

bath

by

a
placed
arrangement
without
the
laths
desired goal.
attaining
great expenditure of
with
the
such as
The
of
a
non-conductor,
periphery
painting
also
failed
for.
and
to
the
efl'ectwished
At
tar,
produce
pitch
made
the suggestion of Dr. Eschellmann
to
an
attempt was
this
the
available
anode
area
growth by lessening
prevent
opposed to the cathode surface at the edges. For this purpose
shields were
wooden
placed in front of a part of the anodes, so
side as shown
covered
in
that the diaphragms were
at one
the
The
surface
cathode
at
224.
peripheryoverlapped by
Fig.

This

about

could

be left in the

zinc

In

arrangement

obtained

was

white
**

cm.

baths

in

turned

causes

out

well.

The

cathodes

the
five to six weeks ; and
and
often in a silverbeautiful,dense,
for from

condition.

spiteof

connection

many

with

such
difficulties,

as

undertaking,it

must
was

be encountered
found

in

at
possible,

a
any
25
30
baths
unbroken
in
of
maintain
time
to
year, to
When
the
time.
for
months
at
a
electrolysis
proceeded
operation

new

favourable

as

it

should,

the

zinc

separatedat

the

negative

electrodes

in

440

SMELTING

ELECTRIC

deposits. The

lustrous

white

and

cent,

deposited

five weeks.

to

disconnected

by

out

dense

not

was

therefore

apparatus

Although
suited

lifted

was

the

zinc

for mechanical

melted

from

was

ment
treat-

together.

detached

used, the depositwas

been

to

a
s)"ace of from
elapsed the bath was

had

be

to

per

within

the cathode

of

it

It had

had

cathodes

bath

travellingcrane.

structure

direct.

to

this time

whole

of the

means

good

of

After
the

and

reached
95
efficiency
1,000 kilogrms. [16 cwts.

each

in

REFINING,

current

800

From

over.

ton] were

four

AND

If iron

the

discs

chisel ; this was


with
of a
usuallyeffected
well, or less easily,
accordingto whether the process had worked
If zinc cathodes
had been
entirelyor moderatelysatisfactorily.
the aid

employed
The

**

hammer

the cathodes

fusion

and

has

process

of shears.

up by means
the additional
cut

were

effect of

freeingthe

in,
impuritiesmechanicallyattached to, or enclosed withsubstances
the
of
was
small,
only
quantity impurity
concerned
being chlorine and oxygen in the form of zinc chloride
and hydroxide respectively.The
loss in melting,assuming the
from 1*5 to 2 per
been regularlyconducted, was
process to have
be run
cent.
togetherat all,but becomes
Spongy zinc cannot
from

zinc

The

it

converted

completely

simple
used

the

to

exposure

effected in

into

refiningof
metallurgicalway."
From

there

was

to

no

be

FUrfurt

trouble

lack

zinc obtained

communication
of earnest

by

by
and

and

with

commensurate

in construction

thought.

It

GUnther

Cheshire*;

"

be
may
those
to

purely

it is clear

that

endeavour

to

were

It is,therefore,
obtained

remarkable

more

yet have

Co., at

on

expenditure

enormous

is,therefore,the
should

heat

distillation in the

enlightened

the

of

zinc

work.
Hoepfner process in practical
regrettedexceedingly that no results

a
plant working this process
of Brunner, Mond
the works

in

similar

of the

the

introduce
in

above

the

generation

fusion

The

air.

furnaces
reverberatory

for the

with

oxide

of

that

been

kept going at
Winnington, Northwich,

the process, if
for the apparatus and
carried out
has stated,
Giinther
as

they are so
can
by no
The fact that the English plant
leads to the assumption that, in all
maintained
in use
was
substantial
probability,
improvements had been effected in the
there
applied;
process as
Yet
other i)atents for the preparationof chloride
solutions
For example,Kellner t has patented
have since been taken out.
ing
a
process by which the zinc is dissolved as bisulphiteby attackmaterial
zinc
oxide
with
sulphurous acid, this
containing
salt being converted
into
sulphate by injectingair, and the
designed and
be regarded as simple.
means

p.

Jahrbitch

dor

EUktrochemie, 1900, vol. vii.,p, 387;

and

1901, vol. viii.,

536.

t English Patent
1901.

7,028,April 14,

1900.

U.S.A.

Patent

690,295,Dec. 31,

442

ELECTRIC

works, consistingof
oxide, sal ammoniac,
is

as

best

AND

SMELTING

metallic

REFINING.

zinc, hard

(ferrozinc),zinc

zinc

mechanical

and

most
are
impurities,
dissolved in ordinaryhydrochloricacid until the
Lead-lined
wooden
vats
nearly as possiblesaturated.

to

for the

use

of solution.

process

the

with

These,

veniently
con-

acid
are

sary
neces-

and
drawing
pumping
are
solutions,and for the subsequent handling of the residues,
so
arranged that a systematicextraction may be effected on the
principleof allowingthe fresh solution to attack the most nearly
extracted
material
first. Even
ing
during the last stagesof saturatoxides
the solutions
the
and
of
metals
metallic
a
portion
which
at first pass into the solution are
by the
re-precipitated
of
and
Since
zinc
oxide.
zinc
neutralisation
a
complete
agency
of zinc chloride solutions
by the waste
products of galvanising
would
be somewhat
towards
the end, the last
slow, especially
of acid may
traces
convenientlybe neutralised by adding a little
soda or powdered limestone.
The
iron
contained
in the waste
for

apparatus

oif and

the

solvent

which

the zinc is,for the most


part,
passes into solution with
will
the
the
in
form
of
in
ferrous
and
not,
salt,
liquid
present

therefore,be completelyprecipitated
by the neutralising
reagent
the
iron
in
solution
now
must
Hence,
employed.
remaining
any

peroxidised. Oxidation
by air, as proposed in a patent
Sdzof the Actien-GeselUchafi
vormals
specification
Egeatorff'B
werke*
attained
time.
end
desired
Tiie
is
requirestoo long a
more
rapidlyby using chloride of lime. Obviously,care must
be taken to neutralise
the solution
during the progress of the
in the following equation,
peroxidationof the iron, as shown
be

which

the reaction

expresses

"

4FeCl2 -I- Ca(0Cl)2 -I- 4Ca(OH)2


When
the

the

oxide,

becomes

eFeCla

-I-

-I- iNa^COa
+

salts

Process.

-I- 5CaCU

is very small
adding soda,zinc

of

chromate,
the iron

-I-

I2H"0

i2NaCl

-I-

as

the

which

from

hydroxide:"

6Fe(OH)8

2Cr(0H),

4CO3.

Pflegerf recommends
(ZnCl.^ 3ZnO, or ZnSO^
4ZnO),

Ffleger's
zinc

solution

with
precipitated

2Na.,Cr04

4Fe(0H)s

rapidlyon

place most

carbonate, and

chromium

iron present in the solution

quantity of
takes
precipitation
or

2HaO

the

"

use

obtained

of basic

by

solving
dis-

of
precipitation
out
This method
is satisfactory
if,as pointed
foreign metals.
above, any ferrous compounds present have
previouslybeen
be completely precipinot
this,iron would
tated.
peroxidised
; failing
The solution,purified
as
above, is passed through a filter
is then
either at once
or after
ready for electrolysis,
press, and
zinc oxide

in the

neutral

evaporation to dryness, if chlorides


to

be worked

in the
"

anhydrous

German

t U.S.A.

Patent
P.itent

salts,for the

are

under

treatment

condition.

23,712.
495,637, April 18, 1893.

and

are

445

ZINC.

this

tion
preparationand purificain
for electrolysis
are
far as the most
so
agreement
important points are concerned.
Much
be
used
must
in the purification
of aqueous
care
greater
solutions which
are
to be electrolysed
such, than when a fused
as
such
zinc
be
is
chloride, to
salt,
electrolysed.From what
as, say,
has been said concerning the neutrali.sation of zinc solutions, it
will be understood
that in dehydrating them, even
if all impurities
have been precipitated,
of zinc chloride with
a mixture
Up

to

point

the

of the solutions

salts

double
obtained

much

for the

zinc-sodium

of

instead

disadvantage from
double

methods

of zinc salts destined

salts, and

or

chloride

zinc-calcium

of pure
This
zinc chloride.
the electrolytic
standpoint;
zinc

is, however,

be
no

the contrary,
on
double
salts,are

chloride

containing
completely dehydrated than are solutions

more

will

of pure

zinc chloride.
dilute

If very
upon, the

solutions

of zinc

chloride

be

operated
dehydration is effected in three stages "preliminary
evaporation,evaporationto dryness,and fusion of the salt. The
preliminaryevaporation of these dilute solutions may be effected
in a plant similar to that almost
exclusivelyused before for the
first concentration
of sulphuricacid
namely, in flat leaden pans
terrace-wise
a heating flue with
a
arranged
corresponding
upon
conveniently
upward slope. Evaporation to dryness is most
lead-lined
in
cast-iron
vessels,hemispherical in
accomplished
shape,about 800 to 1,000 mm.
[31*5to 39-4 ins.]in diameter,
and 400 to 500 mm.
19*7
to
deep. These vessels may
[15*7
ins.]
with the preliminary concentrating
economicallybe so combined
are

to

"

afterwards
led
the former
are
pans that the heated
gases from
It is not possible,
under the latter.
however, to thus obtain a

complete dehydration of

the

considerable

of

chlorides.
solution
has

if it contain
zinc chloride, even
earth-alkali-metal
alkali-metal
or

proportion
near
approach to dehydration may

is concentrated

in the

kettles

leaden
of 230"

be made,

until

240** C.

the

if the

mixture

to
boilingpoint
carry the
dehydration further would
endanger the lead-liningof the
300" C, it
lead
fuse below
does not
vessels,since, although

attained

becomes
Lorenz

very
has

soft at

temperature
endeavoured, by means
a

of 250"

To

C.

laboratoryexperiments,
the purest zinc possible
be
obtained
from
zinc chloride
can
dehydrated as far as is
practicable by heating. He employed small porcelainor glass
vessels,which were
permissiblein view of the low melting point,
not
only of the zinc chloride and its double salts,but of the
metal
itself. In these experiments he first proved that even
molten
zinc chloride contains
a considerable
proportionof water.
It is improbable that this observation
will be called in question
by anyone who has had experiencein the production of the salt.

to ascertain

Zinc

the

conditions

chloride, in this

sxs

under

in

many

of

which

other

respects, behaves

very

444

ELECTRIC

SMELTING

REFINING.

AND

magnesium and of the earth-alkali


metals, and no electro-chemist is likelyto attempt experiments
the electrolysis
chlorides
without
of such
on
having carefully
studied
the pioneer work
accomplished in this direction by
and contemporaries. Their researches
and his students
Dunsen
what
si)own
have
what
be observed, and
precautions must
trouble
these
chlorides
from
their
taken, to convert
crystalline
hydrated condition to that of anhydrous neutral salts. Bunsen
described
known
to him
very fullyall the details of the methods
for accomplishing this.
But
the first experiments which
we
much

like the

make

in this direction

that

chlorides

of

teach

us

that, even

double

when

salts

composition
comparatively easilydehydrated without serious defor
are
evaporated (such,
example, as camallite),
and when
all precautionsare
most
observed, a
conscientiously
certain
after
of water
will be retained by the salts even
amount
prolonged heatingat a dull red heat. The water is probably in
the form
basic chloride.
of hydroxide or
When
dehydrated
from their crystalline
chlorides,obtained
salts,are electrolysed,
the first products of electrolysis
are
hydrogen and oxygen.
These
alone
off
for a few minutes, the time
come
depending
and
been
which
had
the
the
in
effected,
dehydration
upon
way
chlorine
then
time
and
chloric
hydroby
they are
accompanied for a
acid vapour.
The last traces of hydrogen are observable,
the surface of the melt
often after an
on
hour, by the appearance
of small bubbles
of gas, which
catch lightthere, and carry small
of
with
them.
This fact has been known
metal
since
particles
are

Bunsen's

time, and

therefore

be reckoned

must

until
electrolysed

with

fused

j the

the

substance

hydrogen
oxygen
It is scarcely
completelyremoved.
for surprise if the mass
is subject to frothing when
matter
a
small
used in conjuncvessels,such as porcelaincrucibles,are
tion
with
rods dipi)ing
and occupying
their carbon
into the mass
must

be

first retained

at

much
8("

have

and

been

space.

long

as

the

fused

contains

mass

water

or

other

oxygen

sulphates,the particlesof metal which


are
prevented from coalescingby a film of oxide which
separate,
forms
their
This is especially
noticeable
surface.
at the
upon
and occurs
if the temperature
even
beginning of the electrolysis,
*
effect
be considerably
raised.
Oettel
has recognisedthe bad
of sulphatesin the electrolytic
of magnesium
from
extraction
fused carnal lite,and
and
has recommended
eflBicacious
a
simple

compounds,

method
matter

taken

such

as

of

removing
here, since more
into account

It
less

or

in the

comparativelyimpure
Many reagents have
*

them.

raw

materials

been

to

sulphate must

preparation

Ziittchrift
ffir Ehktrochemu:,

this V)ook.

is necessary

refer

to

this

nearly always
chloride

of zinc

from

be

the

used.

recommended

at

different times

1895, vol. ii.,p. 394.

See

also

p.

for
17 of

44r"

ZINC.

the

of water

removal

dehydrated

the

oxychloridesfrom

or

zinc

zinc

acid gas in the


of hydrochloric
; for example, the use
of
the
addition
of metallic
the
sta^e
dehydrating process,
the evaporation of the
to the fused chlorides,*and, finally,

zinc

chloride

chlorides
last

air

solution

passing over
commend

not

addition
also

or

in vacuo, or
through it.t

itself to

for other

used

commonly

It has been

very

stated

purposes

(p.393) that

dehydrated

the

Reference

there

therefore

must

is

long since found

proportionof

lead

take

from

iron

lead is absent.

experiments
chlorides

This

containing

observation
above

described

of lead

by

on

shows

zinc

vessel

scale

methods

what

to

said

was

galena.

there

far less

is

in

The

certain

tendency

employed

than

course

of
electrolysis

the

apparatus

of the

any

confirmed

was

of the

manufacturing

that,when

out

present, the
the

available

no

made

be

is
suffices)

end

chloride.

of blendiferous

treatment

galvaniserhas

the

of zinc

of pure zinc on
chloride prepared

J concerning the

up

acid

towards

for the extraction

stated.
above

in the manufacture

dehydration process

from

as

process does
likelyone, and the

Inst-named

The

author

of well-dried

current

hydrochloricacid (the concentrated

of

suitable

the

with

the

to

when
of the

fused

zinc ; and the possibility


of using simple
iron melting pots for the electrolysis
thus indicated.
vessels was
As
alreadyexplained,zinc containinglead is obtained in this
and

containingzinc, and tliis can he purified


methods.
Although, therefore, the advantages
of
and, therefore, small size of
(use
very high current-density,
from fused chlorides
apparatus)of extractingzinc electrolytically
way. as well
by well-known

are

very

the

use

The

works
works

as

lead

great, it appears
of the process
Uses

of

in the form
for

the

Zinc.

be

to give up
necessary
for the direct extraction
of pure zinc.
"

at

The

of cake

or

desilverisation

present

to

zinc is obtained

from

metallurgical

dust ; and these are


used in silver
works
of work-lead, in chemical

hold
reducing agent, in the foundry for the production of houseimplements, architectural ornaments, and alloys,and in
of galvanicbatteries.
It has
electro-technics for the electrodes
in
the
of
iron
extensive
a
use
("galvanised
protection
very
a
as
roofingmaterial,
iron"). The sheet rolled from zinc serves
and
and is used both in the household
well as for
in building,
as
"fec.
printing plates(in photo-zincography),
The
obtained
zinc compounds are
for the most
products
part as byand metallurgical
in the treatment
of zinc-bearing
ores
metal
The
forms
products from the working of other metals.
the startingpointonly in the manufacture
of zinc white.
as

*Lyte, English Patent

11,190, May

t Steinhart, Vogel, and


t Compare pp. 3S9 and

Fry, English Patent


391.

5, 1897.

19,878, Sept. 19, 1897.

446

ELECTRIC

SMELTINO

AND

REFINING.

CADMIUM.

Properties

and

blende

and

of

Occurrence

the

Metal.

Silesian

"

in cadmium

rich
especially

are

mine
cala-

carbonate

and

sulphiderespectively.The last-named
compound (Greenockite)
found
alone.
Cadmium
and
white
is very
is a very
rarely
malleable
metal
of
structure.
lustrous,soft,
crystalline
(regular)
Its specific
gravitylies between 8 6 and 8*7. It fuses at 320* C,
boils at 800"

and

the

In

C.

molten

condition

alloys very readilywith most


alloys,those with bismuth, lead,and
other "fusible
tin (Wood's, Bose's, and
metals") are the best
of their low fusingpoints.
known, mainly on account
for a long
At the normal
remain
temperature, cadmium
may
in dry air; but at higher temperatures it burns
time unaltered
more
even
readilythan zinc, to which metal it is very closely
allied in its chemical
properties.It dissolves with ease in the
and nitric)
more
important inorganic(sulphuric,
hydrochloric,
acids,forming salts,which are derived from the oxide, and are
The
oxide
and hydroxide are
capable
very soluble in water.
in solutions
of dissolving
alkaline
of
hydroxides,forming salts,
derived from the hydroxide,but Laving the cadmium
in the acid
is precipitated
radical.
Cadmium
from its salts by zinc and
by
metals.
more
electro-positive
; and

metals

other

Extraction
tlie sole

obtained

of

it

of its

Cadmium.

Its extraction

"

is nowhere

The
objectof a metallurgical
process.
the
in
extraction
as
a
by-product
of roasted

reduction

zinc

it

ores

occurs

as

metal
of

the

is

zinc.

made

always
In

the

first product of

and is chiefly
found mixed
with varyingproportions
distillation,
of zinc, in the second (oriron)condenser.
This deposit,
which
is
less brown
or
generallycoloured more
by the oxide of cadmium,
reduced
and
the first portions conredistilled,
repeatedly
densed
always containingthe largestproportionof the cadmium.
these have
When
been sufliciently
purifiedfor zinc, they are

is

rods, and

into

cast

f'mployedis
the retorts
is too

to

thus
that

to retain

Electrolytic

into
used

usuallysmaller

are

porous

The

similar

sent

and

the vapour
Production

The

commerce.

in the

of cast

made

of cadmium
and

apparatus

extraction

of zinc, but
iron,since clay

well.
sufliciently

Befining

of

Cadmium

*
have
requirescarcely
any description.As Mylius and Fromm
be
conducted
under
almost
the
out,
pointed
they may
same
conditions as zinc extraction,
but do not requiresuch great care.
It is necessary
here also to maintain
acid reaction and
a
slightly
a

of

brisk motion
a

powdery
the
*

of the solution,in order


or

spongy

statement, made

to

deposit. Mylius
in

the

prevent the formation


and

last edition

Fromm
of this

also

firm
con-

book, that,

Zeitachrift
fur MiorganischeChemie, 1896, vol. xiii.,
p. 157.

447

MERCURY.

under

otherwise

suffices
equal conditions,a lower current-density
than for the formation
of a dense
depositionof cadmium
results with
deposit of zinc. They have obtained satisfactory
for the

current-densities

50 to 100 amperes
[4*6to
per sq. metre
had quoted 60 to 150 amperes
the limits.
as
[5-6to 14*4 per sq. ft.]
per sq. metre
Cadmium
is mainly used for the proof Cadmium.
Uses
duction
of from

sq. ft.l whilst

9*3 per

the author

"

of very

fusible

alloys. The

compounds

of cadmium

are

solution, the

from the metal, either direct or after


part made
haloid salts being used in photography, and the

sulphide as

pigment.

for the

most

CHAPTER

VI.

MERCURY.
and

Properties
of native

of

Oocurrenoe
are

mercury

the

Small

quantities
as
generallyoccurs
subthe
frequentlyas
other
and
quicksilver),

Metal.

"

found, but the metal

sulphide,HgS, in cinnabar,and less


chloride, Hg2Cl2, in calomel (or horn
metal that
is a bluish-white
compounds. Mercury or quicksilver
is fluid at ordinary temperatures, the freezing point beinij
It is specifically
39-4" C, and the boilingpoint 360** C.
heavy
for
solvent
most
gravity 13*5). Mercury acts as a
(specific
metals (gold,
silver,lead,bismuth, tin,zinc,cadmium, alkali- and
known
alkaline-earth
as
are
metals). The alloysof mercury
amalgams.
Pure
is unaffected
by the air at low temperatures,
mercury
the

but

at

300"

about

oxidised

0. it becomes

to

the

red

oxide.

halogensunite with it at ordinary temperatures.


readilyonly in nitric acid and aqua regia
Two
series of compounds are known
acids.
the common
among
the mercurous
(protoxide)compounds, of which the type is
and
mercuric
the
compounds, corresponding to the
Hg20,
in which
the
The
sulphidealso forms thio-salts,
type of HgO.
and

Ozone
The

the

dissolves

metal

"

occurs

mercury

in the acid radical.


of

Extraction

exclusivelyfrom

Meroiiry.
cinnabar.

"

Rich

Mercury
ores

are

is extracted
treated

in

almost

retorts,

by mixing
material
with some
(lime,limestone, iron,"S:c.)
capable of
combined
and
them
to a
absorbingsulphur,
submitting
process
of roastingand
distillation.
The
escaping
mercury
vapours,

poor
them

from

ores

the

chambers.
ores.

The

partlyby

in shaft-

or

often
reverberatory-furnaces,

condensed
in
furnace, are
The
greatest loss occurs
condensed
distillation.

metal

is

systems
in

of

tubes
the

and

working
poorest
purifiedpartly by filtration,

448

SMELlINti

ELECTRIC

It has often

REFINING.

been

for the somewhat

treating

AND

mercurial

methodsproposed to substitute electrolytic


wasteful and uuhealtlty
smelting processes for
The
direct electrolysis
of the ores
ores.

difficulties that are met


with
would, however, present the same
and
in the treatment
of copper, zinc,or lead ores
if
electricity
;
is to

find

applicationin

an

this

it will be by chomical
field,
by electrolytic
separation. At

followed
of the mercury,
few
n^sults
have
however,
present,
solution

cinnabar

that

is

been

readilysoluble

obtained.

It is noteworthy

in solutions

of alkaline

sulphidescontaininghydroxidesof the alkali metals, and that the


be precipitated
quantitatively
by the electrolysis
may
mercury
method
of such a solution.
As yet, the only analytical
in use is
that devised
Vortmann.
In
to
of this
a
use
by
regard
possible
it
scale
be
stated
in the
remarked, as was
may
process on a large
previousedition of this book, that the experience gained in tlie
of antimony are instructive
experimentson the electro-deposition
in
this case.
to all the
as
important points
Engelhardt and
Nettel*
have
made
also
to
experiments in the same
appear
in
obtained
a
189G, they
direction,for,
patent in the United
States
for the leachingof mercury
ores
by alkaline sulphide
the
o
f
solutions, followed
resultingliquid.
by electrolysis
Calcium
hydrosulphidewas found to be a good solvent in place
of sodium
Uses

sulphide.
of

Mercury.

"

In

the

metallic

state

mercury
barometers, and other

is used

scientitic
largelyfor thermometers,
it
is
In
the
"amalgamation processes
apparatus.
extensively
of gold and silver from their ores,
employed for the extraction

very

"

and

it also

amalgams
t
hydrates.

for the intermediate

serves

in

the

formation

of alkali-metal

producing alkaline
used in other
amalgams are largely
chemical
of the
Mercury is also employed in some
processes.
in
so-called
anti-friction alloys." Other
used
amalgams are
the manufacture
of mirrors,and as fillings
for teeth in dental
the
is
metal
the
for
Finallv,
generally
starting-point
surgery.
of nearlyall the mercury
the manufacture
compounds employed
in the chemical
and
industries.
The
the
sulphide(vermilion)
oxide are
mercuric
valuable
chloride
is
a
pigments ;
germicide;
and fulminate
of mercury
plays an important part as a primer
The

electrolytic
processes

for

alkali-metal

'*

in connection

with

explosives.
*

IT.S.A.

t See

Patent

AlhiH-iivt'iJ

568,843.

AlloySj

p. 68.

450

SMELTING

BLECTRIC

BEDUCING

AND

CALCINING

1.

TIN.

CRUDE

A.

REFINING.

AND

FBOCESS.

containingsulphidesand arsenides are always subjected


before they are smelted
roast
to an
oxidisingand volatilising
of iron and copper
If largequantities
of tin.
for the reduction
made
is
the
roast
sulphatising,
oxidising
sulphidesare present,
metals
these
be
removed
that
two
as
80
sulphates
by
may
metal
which
Ores
rich
in
that
in
tungsten, or slags
leaching.
still retain a fair proportionof
has been concentrated and which
roasted
with
soda,
tin, are
whereby sodium tungstate is formed ;
the
then
be extracted
with
and
this compound
water
can
Ores

removed.

is thus

tungsten

of the ore,

llie further treatment


of

simple reduction
in blast

either

with

furnaces

carbon

the necessary
fluxes,
the
latter
reverberatories,
being

in

or

prepared as above, consists

and

with

The
same
procedure is adopted in the
commonly used.
and
of waste
of
tin
treatment
products from
slagscontaining
works, in which case the iron contained in the liquationresidue
acts as a precipitating
reagent for the tin present in
(hard-head)
the slag.
Apart from a few general suggestionsin patent literature,
in electric furnaces, no
including the smelting of tin ores
the
author
is
known
to
publication
concerning experiments on
Danneel
and von
a
practicalscale in this direction.
Kiigelgen
results
in
research
a
have, however, obtained
very satisfactory
the
in
solution
of
this
the
Institute
new
aiming at
problem
of Metallurgy and
to the
Royal
Electro-metallurgyattached
now

Technical

the

at Aachen.

LEACHING

2.

No

School

High

have

results

so-called

wet

AND

been

way,

obtained

either

electricity.*The mineral
and is,moreover,
electricity,
obtained

been

Electro
Besidues
tin from
into

an

from

And

Tin

in the
oxide

Patent

13,641,1896.

German

of

is

Patent

of

conductor

poor
Better

"

electricity.

of

Treatment

73,826; Glaus

ores
by
of
application

the

results have
very insoluble.
of waste
productscontainingtin,

the assistance
Works.

of

treatment

without

or

The

Tin-plate

Scrap

removal
electrolytic

tin-plate
scrap has, during the
important industryin Germany.

"Burghardt,
German

with

-ohemioal

with

stannic

in the treatment

only,however,

FBECIPITATION.

last few

About

years,

35,000

and
of the
grown
of

tons

and
Cf. Vortmann
Spitzer,
Sutton, English Patents 297,
1895,
'"

40,682.
and

"

451

TIN.

cuttingsfrom

tin

worked

plate are

2 to
up annually. About
800 tons of tin are recovered

numbers
2-5 per cent., or in round
from them, the value being about
The
and

"100,000.
experiments for the treatment

proposalsand

of the residues

from

tin works

of the scrap

divisible into two

are

groups

namely, those using acid and those using alkaline electrolytes.


there have
been recommended,
Among the acid electrolytes
*
Gutensohn
has,
sulphuricacid,acid sulphatesand chlorides.
for example, patented the use
of sulphuricacid for the purpose.
The 6rm
" Halske
of Siemens
a
plant to work the
put down
Smith
written
has
and
f
a
descriptionfrom which the
process,
taken
this
the tin-plate
In
case
:
followingis
scrap contained
from
3 to 9 per cent, (averaging5 per cent.) of tin, and
was
the
aid
of
w
ith
solution
of
acid
of
a
or
electrolysed
sulphuric
yieldingferrous sulphateand iron liquorsin addition
sulphates,
tin.
A Siemens
to metallic
C^gdynamo, absorbing 6 H.P., was
used, and afforded a current of 240 amperes at 15 volts. Eight
cells were
employed, made of wood 50 mm.
[2 ins.]thick,lined
and placed
of 3*5 mm.
with india-rubber
to the thickness
[^in.],
internal
from
the
The
at a height of 1 metre
[39*4ins.]
ground.
in length by 700 mm.
in width
dimensions
were
1,500 mm.
by
On
ft.
ins.
in
2
ft.
ft.
3
x
x
mm.
1,000
depth [5
3|
3| ins.].
dissolved
each side of the vats was
placed a tank in which were
the cuttings that had been stripped of tin ; after solution had
concentrated
in pans
taken
placed at a
place the liquid was
the ferrous sulphatewas
in
lower level,and, finally,
crystallised
tanks sunk beneath the ground level.
The scrap was
packed with great care, neither too closelynor
in
too
bars, the
loosely, strong baskets composed of wooden
of the frames
in length by
internal dimensions
being 1,200 mm.
in width and 850 mm.
in depth [4 ft. x 11| ins. x 2 ft.
300 mm.
"

"

8A

the contents

and
ins.],

kilogrms. [130
inserted

in

the

of

mass

the

baskets
tinned
mm.

basket
the

frames, were

time

tin
of

utilised

and

The

were

copper
thick [4 ft.

3 ft.

1^

ins.

006

and
in.],

plate were
packing, and
conductors

as

charging
emptying
effected twice
daily. The cathodes
long by 950 mm.
plates 1,200 mm.

current.

60 to 70

from

weighed

strips of

cuttingsat

the

these, projectingabove
for

of each

lbs.].Small

150

to

of

anode

the

consisted
wide

by

of
1*5

cathodes,

two

placedin each electrolyte


togetherwith one anode basket, were
The
cell.
edges of the cathode plates were
strengthenedby
and
the
of
allowed to
strips square section,
plateswere
copper
of
the
sides
the tanks, placed at the distance
at
rest in grooves
of 100
baskets
to

[4ins.]from

mm.

the cathodes

and

prevent injury to
*

German

fJoum,

the

the
were

anode

frames.

providedwith

rubber

lining of

Both

the anode

india-rubber
the

vat;

Patent 12,883.
8oc. o/Ckem. Ind,, 1886, vol. iv.,p. 312.

and

rollers
both

452

ELECTRIC

anodes

SMBLTINO

could

cathodes

and

electrolyteby

be

of

means

AND

REFINING.

raised from,

into,the

lowered

or

The

travellingcranes.

solution

wtA

up at the beginning of the experiment by mixing 1 volume


of water.
of sulphuricacid (of60^ B.) with 9 volumes

made

With

of 240

current

depositionof about
expected per hour, but, as a
was
obtained, a largeproportion

amperes
4*25 kilogrms.[9*35lbs.]
might be
a

of

matter

fact,only about

of the current
the

half this

being expended
hydrogen. After

depositionof

total

in the

solution
for

use

became
saturated with iron, and
electrolyte
for the recovery
of the ferrous sulphate. The
allowed

not

was

been

used

the

to

sulphuricacid vats,

four

workmen

coupled in
employed ;
turned

it may

not

series

the

0*95

density

up

the

anode

each

metallic

of

tons

tin, which

into tin salts.


repay

is

produced

be

to

of the

current-

eight baths

(on

concerned

the

in

the

from

cumstances,
cir-

published
employed to work
inevitablybe produced in this

many
at

Smith's

author's

that it is

own

to

after conversion
material

would

used, seeing that

it

an

works,
metallurgical
exceedinglycheap rate.

statement

the

or

addition

other

stripthe tin from


quantityof

The

such

the former

sulphuricacid

the market

enormous

sulphate,in

whether

outlayon
a by-product in

it.

these

The

of scrap [perweek],which
is the
of this size,there would
be obtained

the

as

per sq.
for the

method

ferrous
crystallised
be
sold as
might

completelyto
with

current-

volts

would, under

excessive.

of the

must

vats

upon
it is evident from

an

somewhat

of 15

were

lysis,
electro-

evidently

was
electrodes)

use

was

of 6 tons

is thrown

means,

the

that

be

It is doubtful

the

even

But

tin-plate

could

area

slime, which

output
28

of

and 1*9 volts


amperes
cathode
surfaces
that

mention

treatment

maximum
about

and

In

per sq. in.]. The


nearly 1-9 volts per vat,

or

tin

process.
By the

3 tons

pletely
com-

Three

appear
makes
no

account

left unattacked.

handle

[0*0645
amp.

eight vats,

tin

readilyand

2-28 sq. metres


and
the
[24-5sq. ft.],
but little more
therefore
than 100 amperes

was

metre

of the

of 240

only

as

towards

1-2

whole

the

treated

those

current

and

the available anode


2

was

was

gathered

be

high.

very

iron

being

tin

required to

were

was

the

where

residual

scrap per week.


From
this account

density used

then

in this way ; but after the scrap had


transferred
for from five to six hours it was

dissolved,the
or

weeks

to dissolve

anode

as

iron and

of

seven

the

that

if it

iron

by electrolytic

latter metal

would

were

be

experiments pointto the

tended
insolved
disclusion
con-

the whole of the tin from


impossibleto remove
is employed. Hence
for the
any use
than
other
the
manufacture
of
ferrous
waste
product
unprofitable
sulphateis precluded.
Bohne's
Less ferrous sulphate was
Frooess.
produced hy

iron when

an

acid solution

"

453

TIN

this

it

but

process,

The

process

still

was

used

was

for

some

than

more

could

be

in the works

years

disposed of.
of Robertson

of slag
Hamburg, for the treatment
and hard-head
The
well
those
as
alloys).
(iron-tin
slagsused, as
which
are
produced in the smelting,both of purer and of less
valuable
tin ores, are extraordinarily
easilyand quicklyattacked
by hot dilute sulphuricacid,provided they are mixed with it in
is occasionally
stirred.
a
granulatedcondition and the mixture
The
result of this action is a residue of silica,
in part gelatinous
and in part granular(accordingto the nature
of the slagused),
solution
and
acid
a
containing tin and iron. The
sulphuric
residue
usually retains from 0-5 to 0 8 per cent, of tin. The
is first electrolysed
is then
solution
to separate the tin, and
to allow of the ferrous
sulphate crystallising
evaporated down
The
0*5
0*8
out.*
residue
to
containing
per cent, of tin is
returned
Since the hearths of
to the reverberatoryfurnace.
them
with quartz sand,
furnaces
these
are
prepared by stamping
be treated in it if the material
be dried,mixed
any residue can
with
fresh quartz sand
in the proportion of 1 of slag to 3 of
Si

Bense,

sand, and
The
is

Tostedt, near

at

into the furnace.

introduced

then

granulationof the

run

fusion

off the
is

of the

surface

complete, and

be very

slagcan
metal

readilyeffected

in the

is collected

furnace

immediately in

as

if it

soon

as

tank

of

next
to the kettle into which
placed in front of the oven
When
the tin ores
is tapped directlyafterwards.
or
fllagsare smelted in blast furnaces the resultingslag can be
into a vessel full of water.
The
tapped through a slag run
finely-granulated
slag,after passing through a sieve,is placed
water

the

in

tin

wooden

lined

vats

sulphuric acid.
with

The

the

aid

with

lead

to

be

treated

with

hot

dilute

of dissolvingis readily accomplished


process
of a Eorting stirringapparatus.
The

eulphuricacid soon attains a temperature of from 60" to 70* 0.,


which
amply suffices for the attack on the slag. The solution
containing the tin and iron extracted from the slag is diluted
either in the old-fashioned way,
cooled,and filtered,
sufficiently,
"or by passing it through a filter-press
; it is then ready for the
The electrolysis
is
depositionof the tin by the electric current.
with
such
anodes
of tin containingiron,
is produced
effected
as
The
tin
is
in a
in the last slag-smelting
deposited
process.
is
electrical
it
condition
as
or
granular
always
by
spongy
treated
in the smelting of
Tostedt
then
At
methods.
it was
The process is,however, no longer in use.
the ores.
that the decompositionof the tin slag is more
It is claimed
and
economically effected by Dr. Brandenburg and
simply
Wey land's process t in which the crushed material is introduced
into a boilingsolution of bisulphate; the tin silicate is com"

German

t German

Patent
Patent

96,198, March

10, 1897.

123,764,Jan. 22, 1901.

454

SMELTING

ELECTRIC

BEFININO.

AND

becomes
mass
pleteljdecomposed and the whole
gelatinous
the
silicic
The
acid.
of
to
solution
separated
owing
separation
from the silicic acid is then electrolysed.
The
unsatisfactoryresults of experiments aiming at the
removal
of tin with the aid of acid electrolytes
does not appear
well recognised as
the latest
to be sufficiently
yet, for even
fresh proposalsin this direction.
literature on the subjectshows
Thus, in Meyer's process^ the scrap is electrolysedin dilute
while
hydrochloricacid with the aid of a high current-density,
the use
of tin sulphate
Quintaine,tlike Bohne, recommends
solutions as electrolytes.
Works
use
employed in the removal of tin from scrap now
alkaline
before
the
Even
first
only
proposalsin
electrolytes.
this direction found

their

into

way

the
j"atentliterature,

process

chemical
works
formerly
employed at Th. Goldschmidt's
of
in Berlin, now
The
method
Essen-on-the-Kuhr.
at
same
into the more
working has been introduced
recentlyerected
works
of the Electrochemische Fabrik
Kempen, on the Rhine,
was

and
works

of H. W.
both in
treat

now

13,000
|

tons

this

has

in

process

in Holland.

year, and

given

the

Orefeld,and

at

and

Germany

Menniche

tons.

in

der linde

von

an

the

account

last-named

smaller

into other

Goldschmidt's

works

Works, 10,000
experience gained

Kempen
of the

works.

According

accrued

from

number

of works

and

addition

in

have

been

down

for the

put

the

his

in the

addition

removal

of tin,
of

manufacture

produced
bought which contains solder
also
as
lacquer,
lead),
fattyand colouringmatters.
to

much

scrap
scrap is

tin-plate
ware,
(and therefore
in a new
Beatson,||
patent, restricts
metal
hydroxide solutions, such as
"

the

to

of
advantage
chemicals
other than
those formed
to the electrolytes
during
electrolysis.
The
author
[Borchers]has already referred in the earlier
edition of his work
of adding potassium
to the undesirability
the
which
has
of
recommended
been
use
by
cyanide,
repeatedly
He
excellent
has, however, obtained
Beat8on" and others.
results by adding sodium
chloride in experimenting with clean
tin-plate
cuttingson a small scale. These experiments cannot
be regarded as decisive,
conducted
as
they were
nearly twenty
American
he returned
from which
factory,
years ago in a small
in the year 1887
without
the opporhad
to Germany
having
tunity
of making a test on
a
a
large scale. Meanwhile
large

statements,

has

no

now

himself
are

to

also

the

use

of alkali

recommended

by

U.S.A. Patent 660,116.


+ German
Patent 118,258,May 18, 1900.
t Zeitschrift
fiir Mektrochemiet 1902, vol. viii.,pp. 315, 357, and 381.
Weisahtechab/cUlen,
vol. vii.,of
Menniohe, Wiedergevnnnwig dea Zinna von
Ahrens'
Sammlwig chemischtechnutcfier Vortrdge,Stuttgart,1902.
"EngU8h Patent 11,067, Sept. 18, 1885.
ilEnglish Patent 12,200, 1892.

455

TIN.

Price*

Ooleman

and

eolations and,

and

But

Oruickshank.t

alkaline

hydroxide

been used
for many
It is
in
the
German
named
above.
works
years
obvious
that the whole
of the sodium
hydroxide cannot remain
in

the

soda

have

condition

free
of

assistance

naturallytherefore,caustic

dissolve the tin with

it would

oxygen,
and stannates;

moreover,

unavoidable

this

of

atmospheric

the formation
vessels

of stannites

used,

are

which

is

dioxide
will be taken
case,
up,
the
of
free
sodium
greater
hydroxide in the
quantity
the more
solution,
rapidlywill the absorptionof this gas take
and

in

if open
carbon

the

without

during electrolysis.Even
in the presence
especially
electricity,

the

place.
is
of the process, the work
account
According to Menniche's
begun with a solution containingat most 9 per cent. NaHO,
which
corresponds to 7 per cent. Na^O. This quantity (6 to 7
during the whole process, but
per cent.)of soda is maintained
The
the
free
of
in
condition
not,
course,
throughout that time.
soda

the average,

is,on

distributed

NagO, free, as hydroxide.


Na^O, combined with 3 per
per

cent.

Sn)

1*7 to 2*8 per cent. NajO, combined

When
a

largerproportionof

stannic

up

acid

regenerationof
Menniche

the

among

pounds
com-

"

3 to 3 '5 per cent.


1 to 1*5 per cent.

taken

follows

as

:
during electrolysis

formed

becomes

as

cent.

with COj.

carbon

dioxide

becomes

follows

2*34

SnO^ (=

stannate.

than

in the

the above

baths,so

in the
precipitated

the solution

writes

as

necessary.
place above

is

that

quoted

cerning
con-

of removing the tin :


the apparatus and the work
anode ; the cathodes
either
tin plateserves
are
as
"

"

The

the

The

number

walls

of the

of baskets

tank.

used

Iron

iron

best, the
plate or
cheapest,and the most generally suitable electrode material,
is not
although its use
entirelyfree from objections. The
tanks
are
joined up to the negative conductor, whilst the
bars or tubes, which
is
to copper
are
placed
positive connected
the
insulated
edges of the bath.
supports lying along
upon
The baskets
charged with the tin-platescrap are of such size
and weight,and are
with
so
loaded, that they may be handled
ease.

actual

in each

tank

for example, be three.


it may,
indifference;
wide
made
of stout iron-wire
of fairly
gauze

strong angle-iron bands.

These

bands

is the

are

is

The

matter

baskets

of
are

mesh,

bound

with

bent

into

hooks

direct on to the copper


ductors
conby
with the
basket is brought into immediate
contact
positiveleads. A basket of about 3 cb. metres capacityshould
hold about 50 kilogrms.of tin-plate
scrap [or1 lb. per cb. ft.].

above,

so

gripping them

that

the

EnglishPatent 2,119, Jan. 25, 1884.


EnglishPatent 15,402, July 27, 1899.

456

811ELTING

ELECTRIC

It is made

so

auspended
"of the

to

as

REFINING.

AST)

exactlyfib the

capacityof

The

tank.

the

bear a relation of 3 : 5 to the volume


may
sufficient space
being thus left between the

baskets

bath,

"electrodes to

prevent

resistance

the

of

the

formation

short

of

reduced

is thus
electrolyte

The

circuits.
to

minimum.

by side, and if it is desired


iron platemay
be hung between
to increase the cathode
area
an
baskets.
"aoh pairof
In this case, the baskets must be separated
The

"

baskets

little further

the

between

from

at the

service

side

suspended

are

another

one

baths

requiresgreater

electrodes is not

the

platescrap and

the

and
prevent short circuits,

to

altered.

of
impossibility

care

The

; but
nature

charging the

the distance
of the

anode

tin-

baskets

mitted
uniformly on a large scale,although equal quantitiesare submakes
it impossibleto providea constant
to electrolysis,

luiode

area

per

-conditions

bath.

this and

For

other

constantlychanging,and
"conclusions only from
the total work
The
to
pipes carrying the electrolytes
insulated

and

connected

the main

with

the current-

reasons

it is

are

done

possibleto draw
day to day.

from

and

from

the

conductors.

tanks
No

are

special

for the regulationof the flow of the


been laid down
noted
It
that the dischargepipe is probe
electrolyte. may
vided
and
with a screening arrangement
overflow
for the
rules have

of holding back
purpose
tin.
Diaphragms are not
"The

the

suspended particlesof

spongy

used.

required for the complete extraction of the tin


is dependent not
only on the current, but
scrap
the temperature and the strength of the
also very largelyon
well
the nature
of the raw
material
itself.
as
on
as
electrolyte,
time

from

the

The

writer

[Menniche] has

referred

to

the

last named

at

the

normal
conditions
with
beginning of this article. Under
(t.e.,
in
with
uniform
no
irregularitiesworking),
working
temperature
and
composition of bath, and with fairlyhomogeneous scrap,
the time required for strippingthe tin plate,with an average
potentialdifference of 1*5 volts between the terminals of the
hours.
baths, is from five to seven
with
continuous
9,000 tons annually,

In

other

words,

to

treat

running of the works for


of
required consisting
each of about
3 cb. metres
^0 cells,
cb.
[106
capacity,and
ft.]
each taking three baskets with a charge of about
50 kilogrms.
basket.
But
of
cells
the
some
be always
must
[110lbs]per
for cleaning,
out of use
or
rechargingw*ith anode material,or
300

the

working days, a

like,and

"The
iron

be

would

be

well,therefore,to

increase

the number

to 60.

of tanks
of

it would

plant

scrap
forks

is

constantlymoved
during the progress

apparatus

the

electrical

resistance
that the

is afforded

to

tin-platescrap

contact

the
be

and

loosened

of the
is

current.

with

good,

process.
and
no

It

is most

thoroughly loosened,so

the

With

aid
this

permanent

important
that

there

458
in the
it

SMELTING

ELECTRIC

AMD

REFINING.

solution,it

is necessary
to remove
is most
conyenientlyeffected
6* C.
to about

at

This

down

least the bulk of

by coolingthe liquid

The scrap from which the tin has been removed


is lifted out
of the baths in the baskets,drained and washed, after which it
is transferred to the open-hearthsteel works.
The

depositedtin-spongeis,accordingto Menniche, washed,


rapidlydried,and, if pure enough, melted in a bath of
pressed,
Otherwise
fusion in shaft or
tin.
reverberatoryfurnaces is
the
i
f
for
is
connected
with works
preferable,
especially
plant
the treatment

of tin

Menniche's

account

ore.

of the apparatus used

in the

electrolytic
in largeworks is
tin-plate
scrap industrially
the only one
this giv^ the
available,and even
practically
that
he had not
the
practicalelectro-metallurgist impression
described all that he had seen.
With
the excepquitecorrectly
tion
removal

of tin from

of the

anode

arrangements, which, from

obviouslydiffer from

employed, must

scrap
the same

mechancial

found

been

components

for the

could

serve

as

of the apparatus which


electrolytic
separationof

also
is

always

for the
the

case

removal

under

have

these

circumstances

alloy

from

tin

electrolytes
to
actuallypreferable,
The

circuit.

be

may

of tin

alkaline

now,

are
used, it is not only permitted,but it is
in the
connect
up the tanks as cathodes

which

used,

hitherto

arrangements

convenient

plate. When,

of the

the nature

those

made

tanks,

of iron, are

mended
only cathodes used ; but it is always to be recombe hung between
that iron platesshould
the anodes in
order to increase the cathode
surface,the subsidiarycathodeplatesbeing connected up to the tank containingthe solution.
All the suggestions
and processes at present known
provide for
used
either
when
the tin-plate
contained
as anodes,
scrap being
latter
in specialperforatedholders or after compression. The

the

sometimes

does
the

not, however, appear to have


former
The
anode
method.

baskets

of wire

mesh

with

the electrical connections

an

met

so

much

receptaclesare

iron

between

with

framework,

the

sources

anode

favour

now

which

as

usually
complete

of energy and the


alkaline solutions at

Iron is but little attacked


by
scrap.
Baskets made
of cane
the anode.
or
rush, or

other

stances,
organicsubelectrolytes.

obviouslyunsuited for use in alkaline


and Davies**
apparatus has been designed by Matthews
for moving the scrap in and out of the solution by mechanical
There is no doubt that
means
during the progress of the work.
material
facilitates the stripping
the movement
of the anode
of the tin. The
proposed for this purpose by
arrangement
and Davies
Matthews
certainly
city,
givesthe impressionof simpliavailable
for
the
of methods
the number
but
already
are

An

purpose

would

appear

to

be

sufficient

to

make

"English Patent 21,533, Nov. 28, 1900.

the

further

459

TIN.

inventions

the

of

kind

pressing need

any

for

for

would

answer

by

Ooleman

be far too

and

be

which

the

when

even

many
in
purpose
the purpose

similar

should

there

strippingprocess,
anodes are stationary,
of the mechanisms
already employed
and
work
metallurgical
electroplating

hours

occupiesonly a few
it is probable that

If

unnecessary.
hastening the

least

at

well.

as

Cruickshank

An

apparatus proposed
the author

to

appears

to

complicated.

Becker

f recommends

to be
specialform of anode receptacle
tank for use
of
in the treatment
suspended in the electrolytic
kinds.
o
f
all
These
of
consist
metal-scrap
rectangular
receptacles

cages

with

above,

open

of
discharge

the

sides

made

strippedscrap.

above the cages to conduct

removable

Metal

the current

rods

to

facilitate the

laid

are

lengthwise

to the material

which

is

to be

and pointedcross
rods are brought from these
electrolysed,
that
so
they penetrate deep into the charge. The
whole arrangement
is undoubtedly very simple,but the patent
the
contains
in regard to
contradictions
some
specification

downwards

material
to

of which

the

made.

are

cages
which
are
electrolytes

use

The

inventor

proposes

attackingiron for
of zinc from
galvanised
the alkaline hydroxides

capable of

not

the

strippingof tin from tin-plate


scrap,
iron,and for such work generally. But
the principalelectrolytes
available for this purpose
are
;
he employs perforatedwood
the
for
sides
of
his
plates
cages, he

will

strippingthe

introduce

soon

tin from

metal

the

if

process

of

scrap.
B.

The

difficulties into

and

anode-

PURE

obtained, either

TIN.

by

extraction

from

the

or
ore
by
products,always contains
lead.
less iron, copper, antimony, and
In tin works
more
or
these impuritiesare removed
by liquatingthe crude metal, and
then
under
Electro-chemical
it
melting
oxidisingconditions.
of refining
the crude tin have been proposed,but, so far
methods
it is possible
of the practice
to judge from published accounts
as
adopted in tin extraction,they do not appear to have had any
lastingresults.

the

treatment
electrolytic

The

has
[Borchers]

author

of bismuth
extracted
bismuth

of waste

elaborated

lead.
containing

In

ment
process for the treatthis process
the lead is
a

alloy by melting the crude


oxychlorideunder a cover
consistingof
the

from

of NaCl

KOI

mixed

with

good results,it is natural to expect


also be purifiedby melting it with
chloride and
"German
t German

an

alkali-metal

metal
fused

with
ture
mix-

As

this gave
that tin containinglead may

little NaOH.
the

double

haloid,which

Patent

119,986, May

Patent

118,249 ; EnglishPatent

is

salt of stannous
more

stable when

18, 1900.

3,524, Feb. 22, 1900.

460

ELECTRIC

connection

which

with

melts

The

at

Uses
and

first

the

the author's earlier

of

between

temperature

publicationof any
be deferred
course,
metal

Even

REFINING.

in
quantitativeteats, made
in
the
lytic
electroexperiments
of tin-plate
treatment
scrap, proved that the process was
workable.
the author's suggestion,
these experiments have
At
been
continued
the
in
laboratories of
lately
electro-metallurgical
The
the Technical High School
first student who
at Aachen.
in
this
work
has
lefb
the
school
without
was
engaged
reporting
the results of his experiments. Peetz, who
at present has the
in hand, has alreadyobtained
results by
matter
very satisfactory
smelting the tin containinglead with a double salt of stannous
chloride and potassium chloride which
is easilyprepared,and

exposed

to the air.

AND

SMELTING

until the

Tin

are

SOC*

and

400*

The

C.

conditions

of the

account

must,
working
experiments are complete.

very
other

In

numerous.

the

form

of

of pure

metals (tinplate,
tin on iron)
or
coatingon
of
and
for
utensils
household
use.
largely
general
very
It also playsan important part in many
valuable alloys(bronzes,
which
bearing metals,solders,"fec.).The foil,
formerlyconsisted
of sheet tin rolled very thin, is now
usually lead, coated with
tin,obtained by rollingplatesof the two metals together. Most
of the compounds of tin, which
are
chieflyused as pigments
(mosaicgold,tin oxide, "c.)are prepared from the metaL
as

it is used

CHAPTER

VIII.

LEAD*
Properties

and

lead, which

is

Occurrence

of the

found
occasionally

Metal."

in small

Apart from
the
quantities,

native
metal

the

chieflyas
sulphide,PbS, Galena, from which, in the
deposits,
largequantitiesof the carbonate,PbC03,
White Lead Ore or Cerussite are formed
naturally. Among the
less commonly
occurring ores are :" Anglesite,PbSO.; Pyrooccurs

case

of many

morphite, PbOl., 3Pb3(POJo; Crocoisite,PbCrO^; Wulfenitc,


PbMoO^ ; and "Stolzite,
PbWo^. Vanadmite, SPbgVgOgPbCl^
contains
also some
P2O5. Lead is a bluish-greylustrous metal,
of specific
malleable,but of very low
gravity11 4, exceptionally
it
be
the
with
cut
tenacity;
knife,rolled into plate,
easily
may
330"*
It melts at
or
pressed into wire.
0., and boils at a white
.

heat,but

becomes

heat.

When

well.

It

vaporisedto

fused,it is

a good
noble)metals.
At
the ordinary temperature,

is true

that it oxidises

marked

solvent
lead

extent

resists

at

even

for other

red

the
(especially

chemical

either
superficially

action

in air

or

in

461

LBAD.

iwater,bat

the

film of oxide

absent

never

beneath

from

natural

further

it from

or

carbonate

(forcarbonic acid is
air) protects the metal
chloric
Similarlysulphuricand hydrosurface of the metal, by reason

water

attack.

acids act

or

only upon the


formed.
Nitric acid,
of the salts that are
insolubility
is
however, dissolves lead readily,forming the nitrate,which
soluble in water.
acetic
such
as
acid,
Many organicacids,also,
form easilysoluble salts with
lead in the presence
of oxygen
the oxide, PbO, and
the
(air).Lead forms two simple oxides
With
peroxidePbO^. A hydrate of the former is also known.
lead
forms
lead
one
sulphur,
only
important compound,
sulphide,
PbS, which combines readilywith other sulphidesforming lead
mattes.
those which
Among lead salts,
originatefrom the oxide
those (plumbates)in which
contain the metal
in the base, while
of the

"

the

lead

forms

peroxide
Thus

first in the

named

ores

lead

ore

The

of the metal.
a

by

^are

"

maintain

to

radical

plant

above

far the most


others do not

in constant

list

largelyused
occur

material

use,

for

intermediate

the

with

extraction

example, litharge,an

hearth, which

is

mixture
oxide

lead

of

of this metal.

oxide

A.
in the

case

LEAD"

of the

ash

slags,consistingchieflyof

antimoniate

CRUDE

heavy

WORK
metals

as

Among these
the cupellation

of lead ;
clay,lime, and bone

of lead ; mattes
silver,gold,zinc,copper, bismuth, "c.

lead with

well

into consideration

lead

an

tuents,
consti-

vanadinite.

products,as

with

skimmings,

quantity
they are at

valuable

more

saturated

for the extraction

where

be taken

containinglead,must

in connection

As

the

in sufficient

and

appliesspeciallyto

by-productsand

of

number

which

remark

are,

from

namely, galena and

"

present worked, it is for the sake of their

waste

derived

are

PbaPbO^.

The
white

acid

hypotheticalhydrate,plumbic acid, H^PbO^.


be regarded as a lead plumbate having the
may

or

minium

formula

of the

part

its

; and

or

marl,

silicate ;
alloysof

LEAD.

alreadytreated of,there

available
for the extraction
of lead
principalmethods
the
with
materials
other
and
raw
cerussite,
together
galena
These
alternative
above.
mentioned
methods
are
:
Smelting ;
the
former
The
and
and
is,
however,
precipitation.
leaching
in
scale
practice.
only one used on a large
two

are

from

"

1.

OF

SMELTING

THE

LEAD

OBE.

Sulphide ores are in part converted into


This
oxide is
oxide by roasting under
oxidising condition.
then allowed to react with undecomposed sulphideduring the
meltingperiod,so as to produce lead and sulphur dioxide.
Boasting

Process.

"

462

ELECTRIC

Reduction

and

Boasting

AND

SMELTING

REFINING.

Frooess.

In this process,

"

ing
roast-

oxide and silicate,


as
product,containingthe lead, chiefly
and as nearlyas possiblefree from
is
sulphur, obtained during
the first stage. This
product,by the Huntington-Heberlein
obtained
with
is
process,*
greater certaintyif lime is added
before roasting. The
second stage consists in a fusion process
under
conditions.
reducing
Preoipitation ProcesB.
Sulphide ores are so melted with
the addition
either of iron or of easilyreducible compounds of
iron, that the principalreaction consists in an
interchange
between
iron and lead sulphide,
forming lead and iron sulphide.
"

It is unnecessary

to

detail,especiallyas
will
electricity
made

describe

it is not

be involved

the above

in greater
processes
of
that the assistance

probable
improvements

in any

that

be

may

in them.

LEACHING

2.

FBECIPITATION.

AND

of
Although, with the possibleexception of the treatment
lithargecontainingbismuth, there is no questionof the practical
of leaching and
in lead- extraction,
use
precipitation
processes
yet,having regardto the fieictthat it is in this direction that the
introduction

it is desirable to
made
1835

become
feasible,
processes would
which
have been
of proposals
account

of electro-chemical

give some

for the recovery


So long ago as
of lead in the wet
way.
1840 it occurred
to Becquerel to expediteand
or
improve

the treatment

lead ores
of the electric
argentiferous
by means
the
which
he
current.
account
According to
gave at that time
French
to the
to be so
Academy of Science,! the ores were
treated that the resultingcompounds of silver and lead were
soluble

in

of

are

solution
then
*The

has

saturated
chloride
been

of

sulphateof lead.

state

to

where
receptacles,
in

their GermaD

February 28, 1897) that CaO, is formed


and that this compound then assists the

salts; these

common

made, it is allowed

placedin wooden
inventors

solution

of silver and

become
the

pounds
com-

After

clear,and

the
is

decompositionof

(95,601, of
patent specification
at

the

removal

beginningof

the

process,

of the sulphur by giving

The only carrier "3


This view, however, is incorrect.
calcium
be
is
formed
can
a
plumbate, CaPbO, or CagPhO^.
ox^^gen
This
is confirmed
made
by exx"erinients
by L. Huppertz in the author's
these
[Borchers*]lahoratory. From
found, as the
experiments it was
author expected,that the roastingof the bulk of the ore could be carried
out in one
(without preUminary roasting)by blowing air thronsh
operation
the charge in suitable converters.
It was
the
to control
only necessary
after
the
small
reaction,
starting
quantitiesof
by introducing
temperature,
calcium
plumbate. This salt can readilybe made by roasting in a reverlatter is produced
which
heratoryfurnace a mixture of lime and litharge,
intermediate product in every lead work.
an
as
up

half its oxygen.


which

fComptea JRendua, 1854, vol. xxxviii.,p. 109; Dingier'


8 pciytechniKhea
Joum,, 1854, vol. cxxxiii.,
p. 213.

463

LEAD.

the metallic salts is effected with

and

either

couplesof

iron,
lead

used instead

or

and

immersed

masses

of well-burnt

The

the

in

metallic

couplesof

sheet-zinc

carbon ;

elements
electro-negative
of lead
zinc
of
or
plates

bags,filled with

in sail-cloth
and

of

or

copper,
the same

of the above.

the aid

solution

saturated

solution;

the

other

may
are

be
closed
en-

of salt,

plates are

is made

between
liquid,and communication
the two sets of platesby metal bars.
When
zinc platesare employed
electro-chemical
the platesopposing them
receive
an
consistingof all the
depositin the form of very fine particles,
metals that are readilyreduced, such as silver,
copper, and lead ;
leaden
but when
platesare used the deposit consists of silver,
which is more
less
or
pure accordingto the proportionof lead in

placedin

the latter

the solution.
In

placeof

sail-cloth

made

of

been

subjected to

wood,

several

bags

it is

millimetres

the

action

preferableto
in

of steam

thickness
in order

use

either boxes

(which has
to

extract

first
any

matter),or vessels of half-burned


clay,filled as full as
In this
with piecesof amalgamated zinc and mercury.
possible
and
the quantityof zinc
more
regular,
way the action is made
consumed
is in atomic proportionto that of the metal deposited.
By varying the components of the voltaic couple each of the
metals present in the saline solution
be separatedsuccessively.
may
soluble

The

work,

experiments, of
made

with

which

the

results

quantitiesof mineral

are

recorded

in
from

my

100

varying
quantityof silver recovered in
twenty-fourhours ranged from a few decigrammes up to 1 or 2
tages
kgms., so that it has been possibleto estimate both the advanmethod
of
and the disadvantages
of the electro-metallurgical
the
minerals
of silver,
lead,and copper, but particularly
treating
troublesome.
of the former
two, of which the preparationis more
the
in
treatment
was
Usually
completed
twenty-four hours,
but by operatingwith the aid of an independentcouple,of which

grammes

the

were

up

to

temperature

1,000 kgms.

is raised

by

The

means

be effected
of steam, it may
that this
It will be understood

of that time.
three-quarters
is
joined up in voltaic circuit with the other apparatus,
couple
which
is then provided only with sheets of lead,of which
set
one
is made
the electro-positive
and the other the electro-negative
elements
of the pole; and also that the lead acts directly
upon
the silver chloride and decomposes it. The
two
rents
opposing curwhich
result from this action do not appear
to be injurious
there
to the effect of the independent couple. In this manner
is obtained
combination
of
the
direct
a
tation
precipiadvantagesof a
of silver by means
those which
follow
of lead, with
from the electro-chemical
action of the independent couple,that
transforms
each apparatus at the ordinary temperature into a
voltaic couple.
in

464

lead

When

after

solution

various

that

20

tons

of

ore

Mexico, Peru, Chili, Siberia,Freiberg, Markirch,


in France, had been successfully
treated in Paria.
places^

Traiie d'ElectriciU

1855,

in

author

treated

beyond

at

the

et de

contained

called electro-chemical
be

the statement

contains

and

from
The

REFINING.

platesare used there is nothing left in the saline


few operationsexceptingchloride and sulphate
be decomposed with the aid of lime.
may

later account

AND

lead,which

of

SMELTING

ELECTRIC

works,
The

once.

Ifagnetisme,
publishedby
account
a
interesting
very
in which
has

process

about
never

1 ton

of

the

same

of
ore

so-

could

extended, however,

experimentalstage.
In

recent
more
a
process, ])atentedby
Lyte,t the lead is first converted into chloride,and this is
in the molten
then electrolysed
condition; but it is doubtful
the process will ever
be applicableto actual practice.
whether
Crude
lead is fused, and is oxidised
by a blast of air in a
is then stirred with hydrochloric
acid in
converter
; the oxide
vessels until it is completelyconverted
into chloride.
stoneware
At the same
time the chlorides of other metals {e,g,,
of silver)
of lead chloride by the application
extracted from the mass
are
and
acid or of brine.
The washed
of strong hydrochloric
dried
in a vessel,the suitlead chloride is then finally
ability
electrolysed

ProoesB.

Lyte's

"

that
is very doubtful.
It would
almost
seem
of fused lead chloride upon the material of which
the
and
the
the
latter
electrical
of
composed,
properties

of which
the action
vessel
were

was

not

known

to the inventor

patent specifications
with

the

references

this process.
Process.
SaJom's

"

at

drawn

were

The

the

up.

time
The

I appended, may
inventor

of lead

that

his

numerous

above

bined
account, comtherefore suffice for

of this process

for the direct

of
galena gave an account
the
Electro*
American
of
a report
meeting
chemical
Society,at Philadelphia,on the 4th of April,1902 ;"
from
and this account
was
completed by a communication
The
W.
J.
Eichards. II
ores
are
carefullydressed in the wet
fine
then
crushed
and
to
are
a
powder capableof passing
way,
16
20
metre
sieve
of
about
meshes
to
to the linear centithrough a
[40 to 50 meshes to the inch]. This powder is then
[1 in.]in pans made of hard
placed to the depth of 25 mm.
These
lead containing dilute sulphuric acid.
measure
pans
and
610
the
457
about 380 mm.
to
across
mm.
bottom,
[15 ins.]
the edges; they are about 152 mm.
across
[6ins.]
[18to 24 ins.]
extraction
electrolytic
his methods

in

to

from

the

*
Dingier'3 polyteehnischea
Joum,, 1869, vol. cxcii.,p. 471.
Patents 72,804, 74,530, 75,781, 77,907, and 78,896. EngEsh
t German
U.S. A. Patent 510,276.
Patents 7,264, April 8, and 7,594,April 13, 1893.
and Borchers, Jahrhuch
der Elektrochemie for 1894.
t Of* Nemst
Electro-chemiccU Society,1902, vol. i.,.
" Transfictiona of the American

p. 87.
IIMectro-ehemicai

Industry,1902, vol. i.,p.

18.

466

SMELTING

ELECTRIC

REFINING.

AND

dead-roastingthe ore with an


and then leaching,
successively,
addition of zinc and copper sulphides,
with dilute sulphuricacid to dissolve zinc and copper,
with strong caustic soda to extract
lead, and with potassium
cyanide to take out the noble metals.
yet. The

as

consists in

process

The

well-known

fusion

used in lead works.

LEAD.

SOFT

LEAD"

PURE

OF

MANUFACTURE

lead is still exclusively


process of refining
By this process, very impure lead is

subjectedto fusion under oxidisingconditions,mainly to


Then
it is
remove
sulphides,arsenides, and antimonides.
treated by the Pattinson
crystallisation
by the
process, or
the metal
of
Parkes process for desilverising
means
zinc;
by
lead
which
contains
which
either of
yieldstwo products,one a
first

but

littleof the

the

noble

metals

noble

metals, and

the

are

other

The

concentrated.

lead

latter

in which

alloyis finally

treated by the cupellation


process, in which the lead is converted
into lead oxide,and a crude silver is left. The desilverised lead
have
been
forms
the soft lead of commerce,
any zinc that may
of
left after the Parkes process being first removed
by means
8team"
The

considerable quantity of
Reference
bismuth that may
troublesome.
be present is more
in
the
tempts
Atthis
will be made
Bismuth.
to
matter
chapter on
have been made
lytic
for many
years to substitute an electroof
purification

lead

from

any

depositinglead for the various fusion processes


The first experiment on
at present employed.
a
large scale
York
tried by a New
was
operatingwith a process
company,
invented
which
has been given to this
Keith.
The
attention
by
of

process

process
on

necessitates
the

detailed

subjectin the

reference

Keith's

to

tion
communica-

AUnirtgJoum"d,*

Engineeringand

section,
Fig. 226 shows a cross-section,
Fig. 227 a longitudinal
and Fig. 228 a plan of a plant,which
was
arranged on the basis
of 10 tons of lead.
of a turnover
Figs.229 and 230 are side and
of
end views
a
singletank, the letteringindicatingthe same
in
each.
is partly in elevation,
The former
partly in
parts
section.
The

work-lead

is melted

kettles,
a, a, and
cast plates,
5, (,are

the

at

in the

thence

The

400

[1 ft. 6

ins.

4 ft. X

mm

and
I in.],

lowest

flow
x

are

possibletemperature
platemoulds.

direct into

1,200
fastened

mm.

to metal

mm.

thick

bars, c,

suitable

c,

by
clamps,d, d, and with the aid of the rack, ", ", are
enclosed in close fitting
muslin.
bags of coarse
The decomposition
of wood;
vessels are made of boiler-plate
or
1*5
5
about
3
1*5
5
metres
x
x
x
they measure
[10 x
ft],and
are
chargedwith a solution of lead acetate or chloride. The
*

Engineeringand Mining Joum., 1878, vol. xxvi.,p.

26.

467

LEAD.

cathodes

rods, 0, restingon
of

long side

one

plateswhich are supportedby metal


the upper edge
strips,
py placed along
vat.
Along the rim of the other long

metal

thin

are

copper
of each

=Q

Rj^^j^iFirn
Fig. 226.

Fig. 227.

sf

( 22 I

21
17

18

13

10

"

plant Longitudinalsection.
"

1j 25 I

24

Cross- section.

26

[27 [28 "I

[ 32
]
I 20n^^^
n^
I (35 I 36 f
I 16^^
I 12 [137 I 38 I 39 [IT
I 8 [[ I^ [ 43 [
I 47

I 19
I 15
IU
[7

31

30

34

44

41

TTTT

Keith's plant

Keith's

"

23

"

48

46

45

~=

S"B

Fig.228."

Keith's

plant" Plan

Fig. 229."

Keith's

vatlead-refining

Half seetion,half elevation.

side
aa

to

is

well

second

a
as

from

copper
the vat

the work- lead

anodes

Keith's leadCrossrefinine vat


anodes.
showing
section,

Fig. 230."

"

bar, q, which
itself;this
which

TT

are

is insulated
serves

to

0 and
p^
the current

from

convey
in bags as

suspended

above

468

ELECTRIC

described.

The

AND

SMELTING

anodes

REFINING.

transportedfrom

are

racks

the

the

by

travelling
suspendedbetween the cathodes,in
crane. A, and are
with
from the walls of the
contact
a, and insulated from p and
The
baths are arranged in groups
of four,all the vats
vessel.
in each group
and
1, 2, 3,
4, or 5, 6, 7, and 8) being in
(4,g,,
whilst the twelve groups
of four cells each are
parallelcircuits,
coupled in

connections

successive

between

groups

The
Fig. 230.
is deposited
which
in
the
is
cathodes
crystalline form,
upon
that a free space,
so
separates continuallyfrom the plates,

by

made

are

The

series.

lead
and

the

conducting rod, r,

in

shown

as

them
to allow for its accumulation.
y, is left beneath
The method
of cleansingand re-chargingthe vats

is

usually

follows : The crane


brings up the cathodes to the bath, and
meanwhile
the solution is run
out through x to the reservoir, w^
it may
whence
be pumped again to any
required vat. The
from
their
anode-bagssuspended
supporting rods are carried to
tlie reservoir,
and the residual solid matter
the platesis
from
washed and returned to the meltingpot
The slimes suspended
in the wash-water
is drawn
allowed to deposit,the water
are
of^ and the residue is filtered through the filters g, h, i,j^ k, L
as

"

These

slimes

iron,and
As
from

be

may

soon

antimony, arsenic,silver,gold,copper,
treated by any suitable process.

the solution

as

the cathodes

pressed into
into the

more

way.
each

In
31*1

cakes.

into

moulds,

suitable

solution

The

lead which

off,the

run

is then

has

fallen

and

there

pumped

once

empty tank, the cathodes from the next tank are


it,and fresh anodes, enclosed in bags as usual, are

group

the

of

of
kgs. [68^lbs.]

is then

adjoiningvessel

baths
lead

of twelve

[9tonsl

has

is shovelled

hard

suspended in
placed in position
;
same

and

contain

there

should

thus

per
be expected to

groups may
of lead in twenty-fourhours.

be

precipitated

the whole

that

hour, so

treated in the

tion
installa-

yield about

The

12 H. P. for this purpose.


analysisof these numbers
gives the

9,000 kgs.
sume
generator will con-

about
An
For

depositionof 68^ lbs. of

the

lead per
The
necessary.

wiJl be
8,000 amperes
stated,and a determination

pairof

platesunder

therefore

followingresults

hour, a

"

of about

current

E.M.F.

required is not
potentialbetween each

of the fall of

the conditions indicated

in the above

sketch

As
shown
in Fig. 230,
by the author.
wide
and
1*2 metres
0
4
metre
hangs
anode-plates,
bars
in
each bath.
long,on each conductingbar, and 20 of these
The four baths coupled in parallelhave therefore a total anode
was

Keith

surface

made

four

and the
[4,140
sq. ft.]
sq. metres
is thus found
to be 20 amperes
per sq. metre
Under
these
it
conditions
not found
was
sq. ft.].

less than
chloride

of 384

0*4 to 0 5 volt when


was

employed. But,

solution

even

if

current-density

[1*86amps,
possibleto

of lead acetate
one

were

to

or

assume

per
use

of lead

that.

469,

LEAD.

Keith

been able to obtain

had

electrical

an

pressure

possible,for example,
12

out

anodes,
copper
0*25 X 8,000 watts

through the

amperes
to

the

statement,

use

each

to

drive

of baths.

groups

of about Jfi
H.P.
only ; and

of 12

This

H.P*

would

8,000
spond
corre-

Keith, however,
the

on

of

current

this

strength of

of cost, of an
unattainablyfavourable
presented by various technical journalsand

estimate

an

character,has
handbooks.

in order

in

consumption

speaks of

the

twelve

with
current-density
is
such
as
bath,
solutions
of copper
electrolysis
have
been
must
dynamo
giving
volt

the

in

crude

with

desired

the

of 0*25

been

that

They state commonly


twenty-four hours with

refined in
H.P., and from this it is reckoned
to effect the reBning of 1 ton

an

that
of

10 tons

of lead

be

may

expenditure of only
148

lbs. of coal is

12

sary
neces-

the basis of 3*9 lbs.

lead,on

being consumed
per H.P. hour.
From
the figures
given above, it will be clear that it would be
safer to reckon
upon a consumption of three times the quantity
other source),
of fuel (or of power
from some
quoted by Keith
for the refiningof 1 ton of lead.
It is, moreover,
against the
Keith
that
desilverised
the
is
lead
not
pletely
quite as comprocess
as
was
audi further,that the lead
anticipated,
originally
condition.
This is especially
is always obtained in the spongy
when
lead chloride solutions are
the case
used as electrolytes,
if
solutions
the
acetate
cost of the process
are
whilst,
employed,
of acetic acid,
of the gradual oxidation
is increased by reason
and
of
of
the
formation
lead
deposits
by
peroxideat the anodes,
well as by the dischargeof hydrogen ions at the cathode.
as
Tommasi
has been at great pains to neutralise
this difficulty
far as possible,
and considers that he has done so, by restrict*
as
that occurs
the polarisation
with acetate
extent
to
a
ing
large
of
solutions,by a brisk agitation the liquidand by the constant
of coal

removal

of

the

lead

depositsin the spongy


in this direction have
not

seem

which

which,
form.

even

The

undoubtedly

under

these

circumstances,

results of short
been

successful

desirable to use these,as Tommasi


to estimate the cost of working

has

experiments
; but

done,

for

it does
a

basis

largescale. As
frequentlypointed out, electrolytic
processes
with aqueous
solutions can
be carried out with an expenditure
of only a few horse-powerunits,and all the conditions
met
with
be reproduced in a singlecell. It is therefore
can
industrially
ascertain
t
o
possible
by an experiment lastingover a long period,
whether
is practicable
not any given process of the kind
on
or
a
Under
these
it
is
scale.
circumstances
to
not
large
necessary
go
the end of a
more
minutely into Tommasi's proposals. Towards
treatise publishedin Paris'^ in 1898, he states that he possesses
the means
of renderingspongy
lead unoxidisable.
He, however,
on

the

author

wishes
*

to maintain

Proc6d4

on

has

de

secrecy

as

to this

means.

dee
IHwirgeiUation
Electrolytiqne

He
Plombes

describes

the

At'gentifhrts^

470

ELECTRIC

SMELTING

AND

REFINING.

lead prodaced electroljticallj


spongy
other oxides of lead and of
and
litharge

of applying the
poftsibilitj
in

the manufacture

lead, concluding his treatise

white

prospectsfor the

favourable

work

to

was

of

process have

Results

it.

with

prophecy

and

new

to

as

the company

the

which

process
the practicalapplicationof the

of

to the author^s

knowledge.
account
Applioations
physicalproperties
lead is largelyused for casting,for bullets,for safetyfuses in
electrical installations,
and in making pipe joints. By reason
not

yet

come

of Iioad.

of the readiness

with

in the extraction
forms

On

"

which

and

of its

it dissolves

series of useful

alloys.

is used

metals, it
metals, and

other

noble

refiniogof the
Thanks

to the chemical

it also
ties
proper-

metal, lead is largelyemployed for pipes intended


to
water, acid, or gas for the production and
lining
convey
of chemical
and
for
the
manufacture
electrical
of
apparatus,
of the

accumulators.

CHAPTER

IX.

BISMUTH.
Properties
the oxide,

and

Bi^Oj,

bismuthine;
for

of

Ocouirenee
as

bismuth

work.
metallurgical
and
arsenical
sulphide
Bismuth

lead, and silver.


brilliant

and

lustre

specific
gravityis 9*74

is

to 9-8.

brittle that it may


be
so
In spite of its low thermal
of

has

not

1,100* and

metals,
The

copper,
alloysof bismuth
low

cobalt, nickel, copper,


with

Its

ordinary temperature it
down and ])ulverised.
it is a relatively
good

conductance

been

melts

with

at 264"* to

270"* 0. ; its

accurately determined,
In

alkali
the

fused condition

the

addition

nickel,the

cadmium,

sulphide,Bi^S.^,
provide material
found as sulphide in
to

readilybroken

C.
1,600**

in
(chiefly)

;
as

structure.
crystalline

the

At

excellent solvent for many


metals, and
by these and other metals ; among
and

bismuth

Native

brightpinkish-greymetal

Bismuth
electricity.

boiling point
between

of

ores

"

the

It is also

large foliated

is

conductor

and

in sufficient abundance

occur

small

various

Bismuth.

ochre;

but

lies

it is

an

is itself readilydissolved
the
to

and

latter

are

the

noble

these, lead, tin, zinc,


alkaline-earth

first-named

metals

are

metals.

guished
distin-

melting ))ointswhilst those with copper


(bismuth bronzes)are exceedinglyhard.
ing
At the normal
temperature, bismuth is capableof withstandfor a long time
weak
or
influences,
atmospheric
oxygen,
but
at
acids;
higher temperatures it oxidises comparatively
has but
readilyin air,but not quite so easilyas lead. Steam
by

and

nickel

very

471

BISMUTH.

little action

ordinary

on

the

metal

when

even

it is red-hot.

acids, hydrochloric acid attacks

the

Among
only in

hismuth

the

of oxidisingagents, slowly even


in the presence
of air ;
presence
nitric acid acts more
dilute
hot
if
it
be
not
too
centrated
conrapidly
;
sulphuric acid dissolyes bismuth, with evolution of

sulphur dioxide
several

oxidation

The

neutral
or

production of

products;

derived

compounds
soluble

and

salts

almost

but

sulphate.

It

forms

only the oxide, Bi^Og,and the


interest
technically.
any
the
into
difficultly
easily

from

are

the

it possess
converted
very

insoluble

basic salts.

is precipitated
Bismuth
from the solutions of its salts by a
other
of
metals, such as zinc, manganese,
iron,
large number
nickel, cadmium, tin, copper, and lead,as well as by the alkali
and

alkaline-earth

with

the

It is

metals.

refiningof bismuth

that

of note

worthy
lead

can

in connection

separate this metal

from fused oxides and basic salts.


completely even
of
In
the extraction
of bismuth, account
be
must
treating
taken
not
above, but of lithargeand
only of the ores named
silver
that
metal
the lead and
from
refineryslags containing
works.

Preliminary

of the

Treatment

Ores

usual
^Liquation. Formerly it was
native
but
this
bismuth;
"

"

contained
on

of the residue which


smelted separately.
Chemical
Concentration.
In
account

to

and

Waste

Products.

liquatethe
always

contains

much

which

ores

is not

economical

bismuth

and

has

to be

"

bismuth,

the

bismuth

treatingsilver
passes

and

first into

lead

the

ores

taining
con-

lead, and

is

oxidised

during the cupellationprocess so that it is found


the oxidation
litharge. It is true that [speakinggenerally]
that of the bismuth, but there is no
of the lead ]"recedes
line
of
separationenabling only lead oxide to be obtained
sharp
side and
the one
oxide
the other.
Even
on
on
only bismuth
the first the lithargewill contain traces of bismuth
from
oxide,
the end of the cupellation
considerable
and towards
quantities
As
the lithargecontains
from
1 to 2 per
over.
soon
as
pass
it is collected with a view to further
cent, (or more) of bismuth
This
concentration
is efi*ected by repeatedlyreconcentration.
ducing
the galena to the metallic state and re-oxidising
the metal
in bismuth, which
to obtain
then
a lithargepoor
be
as
so
may
i
nto
and
oxides
worked
lead,
finally
containinga larger proup
portion
These
of bismuth.
samples of lithargewhich have been

then

in the

so

enriched

as

together with

to

contain

hearths

at

from

least 20 per cent,


refiningfurnaces

of bismuth

oxide,

slags from the


fine-silver process, are
treated
Rossler
with
hydrochloricacid
If sufficient acid be used, a fairly
after they have been crushed.
chloride
is formed, togetherwith
soluble bismuth
lead chloride,
which
being,comparativelyspeaking insoluble,separates out for
the most
part. On running this solution into water, hydrolysis
or

472

ELECTRIC

takeg

place,and
ozjchlonde and

SMELTING

the

bismuth

AKD

RSnNINO.

chloride

hydrochloricacid

becomes

conyerted

into

On

partiallyneatralising
completely. The
precipitates
lead
of
the
chloride
which
had
portion
passed into solution
remains
The bismuth
dissolved.
oxychloridethus obtained is in
submitted
and
in
to
part
reduction,
part used in the refiningof

the latter with

soda, the

bismuth

the metal.

A.

EXTRACTION

Bedaotion

The

smelted

Frooess.

the hearth

upon

crucibles,in

OF

admixture

of
with

CRUDE
Oxidised

and

products are
reyerberatoryfurnace, or in
soda,limestone,slagsfrom previous
"

BISMUTH.
ores

small

When
salts are
basic bismuth
to be
operations,and carbon.
treated (the oxychloride in particularpresents itself now
and
again)they must not be smelted until theyhave been thoroughly
with
burnt
slaked
mixea
lime.
This
be effected by
or
may
the
of a mill, or by stirring
with
milk
of lime and
means
ore
other
suitable
that the
or
so
by
subsequently drying,
means,
other
that
substance
is capableof forming
chlorine,or any
present
volatile compounds and causing loss of bismuth, may
be
combined
with
lime.
soda
the
in
The use of
charge should not
be too sparing,because it gives to the slag an additional
fluidity
which
is necessary
owing to the comparativereadiness of bismuth
The
to volatilise.
ingredientsof the charge should be so proportioned
that the slag consists of a silicate intermediate
in
The bismuth
a bi- and
a mono-silicate.
so
composition between
obtained
is not
but
contains
some
lead,
nearly always
pure
such
arsenic, and antimony, frequently with other metals
as
in addition.

copper
The

Preoipitation
and

Process.

"

araenical

be

As

the
lead-smelting,

in

treated

fusion

with

phide
suliron.

ores
by
may
slightlybasic slagis used, and scrap iron is added
in kind
to the charge,the fluxes being the same
in the last
as
somewhat
in proportion. The
in the
case, but altered
copper
into
nickel
Cobalt
matte
and
ore
as
are
sulphide.
usually
passes
^compauied by arsenic, and in this case a speise is formed ; but
in spite of this a little arsenic
always flnds its way into the
Lead
and
bismuth.
fore
antimony also enter the latter. It is there-

In

this

case

in this instance
necessary,
metallic product.

B.

the

PREPARATION

OF

as

in

PURE

the

last, to

refine

the

BISMUTH.

smelting process referred to above the lead and bismuth


present pass almost completelyinto the bismuth, together with
a
part of the arsenic and antimony in the ores or other material
used.
Of these impuritieslead, arsenic,and
antimony may be
In

474

ELKGTBIC

8MELTINO

Bolation,there

in aqueottB

is

AND

no

BEFININO.

need

to describe

the

apparatus

further.
The

of

Applications

restricted
practicallj

Bismuth.

the

to

of bismuth
is
fusible
easily
(Wood's,

productionof

Rose's,lapowitz*,
"c.)and
of

The

"

use

and
(bismuth bronze)alloys,

of hard

compounds, such as bismuth subnitrate


used for pharmaceuticaland cosmetic
are

some

which

CHAPTER

ANTIMONY

AND

and

oxychloride,

preparations.

X.

VANAPIUN.

AKTIMONT.

but

rarelyso, iu
native
It occurs
more
abundantly as oxide,
and
and
as
(valentimte
sulphide,Sb^S,,
Sb.03
senarmontite),
The
phide
sulantimonite.
antimony-glance, grey antimony, stibnite,
is also combined
with
other sulphidesin many
sulphoassociated
but
these
with
other
are
salts,
sulphide
usually
and
arsenical
metal-like
of the
ores.
Antimony, the most
metallic
lustre.
Its
is
has
and
non-metals, white,
a good
specific
gravity is 6*7. The fractured surfaces of pure antimony show
a
largely foliated crystallinestructure, whilst on the outer
so-called
surface
of the
antimony regulus,"a star-shaped
and
is
observed.
crystalline
marking
Antimony is very brittle,
440" C,
be easilycrushed
It fuses at about
to powder.
may
and
boils at a temperature between
Antiand
C.
1,400"
1,100''

Properties

of

the

condition.

the

Metal.

Antimony

"

occurs,

'*

is the most

mony

of

element
electro-negative

is therefore

series,and

thermopiles.
Oxygen and water

at the normal

valuable

alike

are

in the thermo-electric

material

almost

temperature. Among

without
the

for the construction


action

on

antimony^

acids,hydrochloricacid

slightsolvent action ; nitric acid oxidises it to the pentoxide; strong sulphuricacid first oxidises the metal, and the
of acid.
resultingoxide then forms a sulphate with the excess
Chlorine
with metallic antimony, and the reaction
reacts directly
of
be utilised in the production of anhydrous chloride
may
chemical
forms
With
pounds
commost
metals, antimony
antimony.
alloys),which exhibit a certain
(speiseand antimony

has

hardness

chemical

to

has
of

and

an

as
brittleness,

influence.

extended

use

protectivemetallic

well

an

films

great power

of resistance

the metal
properties,
addition
to alloyin the preparation
and of metallic pigments.

Thanks

as

as

to

these

475

AKTIMOKY.

forms

Antimony
the
is

of technical

simple oxides

two

trioxide,Sb^O^,and pentoxide,SbgO^,of
acid
chieflybasic,and the latter is more

importance,

which
in

the

former

character;

but

the alkalis and


capable of acting as an acid towards
salts in which
basic
substances.
those
other strongly
Amongst
antimony is the base, almost the only compounds for which
there
is any
practicalapplicationare the haloid salts, SbClg,
double
compounds of these with alkali-metal
SbEj, SbCl^,some
each

is

salts, and

the

in
derived

acid

So

antimonates.

of

compounds

known

the

the

mony
anti-

trioxide,

or

antimonites, whilst those

the

as

contain

pentoxide,or antimonic oxide, are designated


also the correspondingsulphides,Bh^^ and

the

from

salts which

the

radical,the

oxide, are

antimonious

Of

emetic.

tartar

thio-salts,similar
compounds just described,and

SbgSg, form

All

thio-antimonates.

these

in

constitution

known

salts

as

and

thio-antimonites

for the

are

oxide

the

to

most

part produced

only as intermediate
products in the preparation of
of
metallic
antimony compounds or
antimony.
oxide and
the chief
above
The
are
sulphide ores mentioned
used
For the productionof
materials
in antimony extraction.
antimonides
(antimoniallead,or hard lead),however, there are
obtained
the
as
employed large quantitiesof the antimoDiate
first oxidation
product in the refiningand cupellingthe lead
lead aud

from

silver

easilyfusible
be

of

Treatment

Preparatory
so

ores.

that

concentrated

Ores.

Antimony

is

Stibnite

"

part of the antimony present

the

in

liquation. In

ore

this

simple process oi
almost
antimony trisulphide
way
residue
and
much
in
free from
sisting
conlargerquantitya
gangue,
considerable
of the
a
quantity
retaining
gangue
of SbgS^.
amounting, it may be, to 20 per cent.

can

there

by

obtained

are

valuable

"

"

Beduotion
the

OF

EXTRACTION

A.

All the raw


Process.
of oxide
in the form

(forhard lead). Sulphide ores

followingprocess,

otherwise

they

must

or

contain

by

direct

small

shaft

treated

be

can

crucibles,reverberatoryfurnaces,

in

furnaces

which

materials

"

antimony

reduction

ANTIMONY.

CRUDE

be worked
by the
may
be roasted
to oxide and

reduced.
The

Precipitation

based
The

on

richer

8^83,

are

concentrate

is then

Process.

"

This

method

the

following reaction, SbgSg +


sulphide ores, containing 50

smelted
the

melted

direct,the

poorer
cmtimonium

sulphide,as
in crucibles

or

ores

3Fe
to
are

crudum

of reduction

Sbg

is

3FeS.

90

of
per cent,
first liquatedto
; the

reverberatory furnaces

sulphide
along with

basic additions.
For the latter,a mixture
of
scrap iron and
carbon
which
sodium
is
and
sodium
used,
sulphate
yields

476

ELECTBIG

8MELTINO

AND

BEFINING.

oontains
heating. The antimony thus obtained
be
used
to
directly,and is
impurities(iron,"Src)
many
submitted
will
to a repeated refiningoperation,as
therefore
In
be explained in treatingof the purification
of antimony.
this
furnace
either
a
conducting
reverberatory
operation,
may
be used, or plumbago crucibles,of which
number,
up to
any
The
in
chamber.
a
40, are commonly placed together
heating
crucible smelting process is described
tioned
fullyin the under-menjournals.*
Solution
and
Precipitation. Poor sulphideantimony ores
and the residue from the liquation
of richer ores
yieldadditional
solution
after
in
if,
crushing,they
antimony sulphide aqueous

sulphide on
too

"

with

treated

are

metal
form

and

solutions

of

and

alkali-metal

alkaline-earth

they combine to
readilysoluble thio^antimonates, Na^SbS^ or Ca3(SbS^2"
These
solutions
thio4mtimonites, Na^SbSg or Oaj^SbSg),.
sulphides.

Under

these

circumstances

be

evidenced
with the greatest ease, as was
so
electrolysed
1880
the
worked
out
as
Luckow,t
long ago
by
by
processes
Classen,and Ludwig.J
The
author
during the year 1886, made a series
[Borchers],
of careful experiments to determine
the conditions
necessary
for the industrial extraction
of antimony. These
experiments
proved that the antimony was depositedin equal quantity both
may

from
of the

the

thio-antimonate

sulphur

therefore

be

and

thio-antimonite,and

required for the

saved.

If

sodium

thio-antimonate

is necessary to add either sodium


proposed by Classen and Ludwig, or sodium

used, it
to

prevent

the

separationof sulphur at

of this addition

must

be

such

of the

formation

the

that

some

former
solution

may
be

sulphide,as already
hydroxide,in order
The quantity
anode.

that, after

the

removal

of

the

antimony, there is at least one atom of sodium for every atom


the
of sulphur. Under
these conditions
the experiments gave
followingresults with a sodium thio-antimonate solution.
The

relative distribution

experiment is shown

in the

of the elements

followingtable

before

and

after the

"

*Joum.
Soc, Chem.
fur atige*
Ind., 1892 (voL xi.),p. 16. JSeitdchri/t
wandte
Wiist and Borchers, HiUtenxotsen,Leipzig,
Chemie, 1S92, p. 146.
1879 ; [and Enfflish metallurgical
text-books].
\ ZeitHchr^ftfiir
ancUytischeChemie, 1880, vol. xix.,p. 14.
dexUscheti "hemischefi
tBei-ichte der
1885, vol. xviii.,
Oesellsehc^Jft,
Ed.
A.
1104.
durch
Electrolyse,
QtuiiUitative
Classen,
3,
Analyse
p.
Berlin, 1892.

477

ANTIMONY.

cipitation
antimony (3 grms.)is here so small that the preThe
considered
be
as
quantitative.
practically
may
loss of sodium
(72 grms.) and sulphur (100grms.)is explained
by the fact that the solution clingingto the antimony after the
powder had been removed was not added to the rest of the liquidi
in describing
will be explainedhereafter
which
for reasons
The ratio 72 : 100
metal.
the method
of treatingthe deposited
the above
confirm
well
with
to
1,768 : 2,460
agrees sufficiently
obtained
must
The
statement.
actually
quantity of oxygen
and
the
in
than
also have
that
been
same
shown,
larger
portion
proThe

In

loss of

be 300 instead of 288 grms.


; it should,therefore,
which
the next
electrolysed,
experiment a solution was

contained

3*400

kgrms.
SH^O, correspondingto
made

up
in
the electrolyte
was

the

to about

the

Sh^^

of

and

formula

the

same

previous case,

kgrms. of Na^S +
tion
Sb2SQ+ SNagS. The soluspecific
gravity as that of
7-200

and

quantity (2 to 3 per cent.)of common


same
system of recording,the results
shown in the followingtable :

small

"

was

also mixed
salt.

of the

with

Adopting
experiment

the
are

478

SMELTING

ELECTRIC

REFINING.

AND

Here

again the depositionof the antimony was


practically
The
sodium
of
loss
and
of
quantitative.
(59 grms.)
sulphur (82
grms.)is due, as proved by the proportionexistingbetween them,
to the solution
adhering to the pulverulentantimony deposit.
The ratio of 59 : 82 is sufficiently
to that of 1,321 : 1,838
near
and the proportionof oxygen
indicated
for this proportion,
in
the table must
therefore be increased to 311 grms., to correspond
this.

with

These

that, with
experimentsprove the peculiarcircumstance
of
the
of
same
same
expenditure current,
quantity antimony
whether
it exists in the solution in the trivalent or
deposited,
the pentavalentcondition.
The
first practical
lesson to be

the
is
in

learned from

this is that

of sodium

it is unnecessary
thio-antimonate
in the

to

aim

at

the

duction
pro-

leachingof

antimony
produce that compound entails the addition of
sulphur during the leachingprocess, and of sodium
sulphide
The
actual
reactions
which
or
hydroxide during electrolysis.
take placeduring the electrolysis
not completelyexplained
are
the
author's
and
later
researches
in this direction
by
experiments,
by Durkee,* Scheurer-KeRtner,t and Klapproth J have not yet
led to perfectenlightenment. The
only inferences whidi can
drawn
from the electrolytic
at present be
phenomena are as
To

ores.

follows

"

It has been
direction

that

ascertained

hydrogen

cathode,while at the
sulphide,and, under

by
is

all who

have

with
deposited

experimented in this
the antimony at the
productsof sodium

appear oxidation
certain circumstances,

anode

even

free

oxygen,

free

sulphur,and antimony sulphide. Ost and Klapproth have,


observed
that when
the electrolytes
thio-antiare
moreover,
if the solution does not contain much
sodium
monates, especially
t
he
reaches
anode
the
in
a
sulphide, antimony
complex ion; they
be accepted that when
sufficient
believe, however, it must
sodium
sulphide is present,this substance alone is electrolysed.
It appears
from their researches
that the antimony is pentavalent
in these
solutions.
of thioAt
present the electrolysis
solutions

antimonate
industrial
ar^

The
purposes.
in addition

formed,

various

need

electro-chemical

be

not

taken

into

consideration

for

and NagS^Oj
fact,however, that NaHS
that
to NajS^, at the anode, proves

takingplacesimultaneously.
dischargedat the cathode,
and
this would
of sodium
for the formation
account
hydrowhilst the productionof sodium
is readily
sulphide,
thio-sulphate
explained by the dischargeof oxygen or hydroxyl ions,and by
the action of atmosphericoxygen
are
upon the solutions,which
maintained
in brisk
motion.
Alkaline
hydrosulphides and
There

is

no

reactions

doubt that sodium

are

ions

are

Zeitachrijl
fUr Elektrochemie,1896, vol. iii.,
p. 153.
i-IbicL,1897, vol. iv.,p. 215.
t Ibid.,1900, vol. vii.,p. 376.

479

ANTIMONY.

sulphidesin aqueous
thio-sulphates
by means
tank-waste

from

Fraotioal
is
following

solution
of

be

completelyconverted
in the

as
air-blast,

into
of

treatment

alkali manufacture.
of

Working
a

an

can

short

sketch

the
of the

Electrolytic
conditions

Process.

that would

"

The

obtain

in

and working an
installation
of this process
layingdown
the
with
illustrations
vessels
of
on
a
scale,
large
electrolytic
the
The
for
recommended
sulphuricacid, sulphate,
purpose.
and sulphide manufactures
books
better dealt with in the handare
these
than
the
of
manufacture
substances
to
relating
they
could be in the space here available.**^
The leaching of the ore
is effected in the conical iron
a
(Figs.231, 232),the sodium sulphide solution being
and

vessels,
heated,

of steam
introduced
agitated,
by means
the
h
.
solution is boiling,
as
steam-pipe, As soon
the finely-divided
is sprinkledinto it. Any antimony comore
pound
used
in
soluble
be
that
solutions
sodium
is
of
readily
may
sulphide. The presence of sodium
hydrosulphideor of polyis
not
objectionable,
sulphides
providedthat the proportion of
sodium
is kept (by the addition
the
of soda)within
sulphurto
limits alreadyprescribed viz.,
lysed,
that in the solution to be electroofoxidisable
by an
sulphurshall he (iccompanied
every cUom
the use
On this account
atom
of sodium capableof neutrcUisation,
of sodium
sulphidemust not be too sparing. For example, the
is
productionof an aqueous solution of SbgSo+ Na^S + 2NaOH
but
the
unstable
mixture
is
so
even
that^
during
quitepossible,
of antimony compounds
the clearingof the solution,
a separation
may take place.
Antimony glance is best suited for treatment, and even
since antimony
be worked
advantageously,
may
very poor ores
soluble
dilute
is
solutions of
in
extremely
trisulphide readily
at

the

time

same

throughthe

"

sodium sulphide.There should be present in the solution three


of sodium
molecules
sulphide for each molecule of antimony

trisulphide
; and
should
3 per

cent,

not

of

after the extraction


is complete the concentration
exceed 12'' Baum^
(or9* to 10** if hot). About

salt,reckoned

common

on

the whole

quantityof

both to assist
should
serves
electrolyte,
clearingof the solution by the separationof dissolved
sulphide of iron,and to reduce the electrical resistance of the
If the spent electrolyte
be ultimatelyworked
solution.
up into
the
sodium
is
sodium
chloride
out
thiosulphate,
separated
again
during the final evaporation.
the requisitequantity of ore
has been
added
After
to the
the
in
extraction
the
is
stirred
mass
liquid
apparatus,
thoroughly
by a current of injectedsteam for an hour or longer,
according
the ore has been reduced,
to the degree of fineness to which
then

be added.

This

the

Lunge and Hunter, Theoretical and Practical


factureof Sulphuric Acid and Alkali,London.

Treatise

on

the Mami^

VjOOQ
fiy

Digitized

IC

482
From

time

operationof

air

time

to

AMD

SMELTING

ELECTRIC

REFIKING.

with

is admitted

the

the

bj

steam,
the steam-pipe,
6.

injector,
c, on
have been continued
When
sufficiently
stirring
long,the insoluble portionof the charge is allowed to deposit,
and the clear solution is afterwards (aftertwo to three hours)
off through the pipe. Since, however, the height of the
drawn
depositin the vessel varies in diffe^nt charges^the bell-shaped
that only the clear
siphon arrangement, d, is used to ensure
This
of
is
drawn
consists
ofL
tube, open
a wide
liquor
siphon
below
and closed above, suspended by a chain or wire,e, in such
steam

the heatingand

that it may

way

down
the vertical
over
up and
The
the leachingvesseL
within

moved

be

up-turned end of the pipe,/^


height of this tube and of the bell is governed by
the vessel.
With
the deposit stands
which
within
similar

character

the variations

raisingor lowering the bell


liquid off from just above

in level

it is
the

the level at
of

ores

greats

By

possiblealways to draw
level of the
deposit in

the

not

are

very

the

apparatus.
solution is at

of the

receiver,^, through
reservoir,Ar,from which it
flows
of electrolyte
tanks, I;
through the correspondingrow
when
exhausted
after
it
is
of
or
thence,
passing through them,
antimony, it escapes through the channel, m, or the floor of the
to the tank, n, placedat a lower
room
level,from which it may
be raised for further
be pumped to another
or
circulation,
may
of sulphur.
or
part of the works for the recovery of thio-sulphate
The

the

the

pipe,A, and

After
tank
The

once

out

channel, t, to the

this solution

has been

again boiled

are

pumped

resultingsolution

off,the slimes in the leaching

run

fresh sodium
sulphide liquor.
up with
is drawn
off exactlyas before,but instead

into the receiver,^, it is conducted


to another
being run
is
where
of
fresh
sodium
it
used
in
leachingvat,a,
place
sulphide
residue
The
in the first vessel
to treat
new
a
charge of ore.

of

is then
into

boiled

one

little water, which


receivers,g, and is used again in

up

of the

twice

with

is

off

run

leaching a

subsequent charge.
exhausted

The

the bottom

at

last

with

then

drawn

off

leachingtank into
and
liquidare separated,

little hot water.

The

through

filter,
p,

which

on

wash-waters

the

on

the
from

of 1

[6

as

200, would

to 8

cwts.]of

in

Figs.231

suffice for the extraction


in twelve

and

of 300

hours

from

232

they
on

to 400

is

filters

the

are

scale

kgrms.

antimony
poor ores
10 per cent, of the metal.
By increasingthe
the outturn
might easilybe doubled.

only
working

that indicated

the

residue

in the reservoir, q, from which


in the leachingtanks.
extracting-water

again used as
A plant such

valve, a,

which

accumulated
finally

are

of

are

of the

portionsof

rinsed

slimes

taining
con-

rate

Single depositingtanks, with their more


important attach*
shown
are
In the
and 234.
on
a largerscale in Figs.233

ments,

483

ANTIMONY.

iron

tanks, B, hang

the

The

latter

of

replaceableanodes, A, and cathodes, K.


are
clamped to the
plates,which
the
and
rim
of the vessel.
rest immediatelj on
rail,T,
square
The
In order
tank
to
itself,therefore,is used as a cathode.
consist

Fig. 233."

iron

tank"
Antimony electrolytic

Fig. 234." Antimony


the anodes

insulate

H,
iron

the
so

bars,J, are

long side of the upper


positiveleads,P, which
placed that the iron bars

the

on

carry

wooden

tank"
electrolytic

rest
plate's

upon

them.

Section.

Plan.

rested upon

rim

of the

consist
which

the brackets,
these

vessel,and

stripsof copper or
carry the lead anodeof

484

ELECTRIC

The

of

manner

SMELTING

REFININO.

AND

the solution is so clearlyindicated


circulating
little
explanation need be given. The
very
into a
above
the vessel beneath, and overflows

that

in the

drawing
enters
electrolyte
channel, G, by which it passes to the next tank.
be capableof actingas a conductor
not
must
connected

are

This

ment
arrangeif the vessels

up in electrical series,and it consists,therefore,


caoutchouc
of
tube, S. In order that the column

mainly of a
liquid connecting successive vats may not itself interfere wifch
the electrical circuit,the length,and therefore
the resistance, of
be
the column
is made
sufficiently
great. The solution must
because
becomes
it
introduced from
below,
lighter
specifically
of electrolysis.
A
during the progress
three-way cock, D, is
the bottom
be
of the vessel so
that it may
placed beneath
possibleto draw off the liquid through it, and through the
it
with
it. By this arrangement
escape pipe,X, in connection
that no vessel can
is ensured
be emptied until the connection
the one
with
has
closed.
To
been
preceding
provide for the
better distribution
of the solution
through the tank, a bent
the
of
the
is
bottom
vessel on the side of the
plate,Y,
placed at
admission
pipe,and a second bent plate,XT, is so attached to the
wall
that there is only a small space between
the two
side
plates
the
whole
of
side
of
electrodes.
the
The
is
one
along
electrolyte
introduced
This plate,Y, is riveted to the
through this space.
to
bottom, and although it is not quite water-tight,it serves
of the
prevent the deposited antimony lying upon the bottom
tank from being swept out with the liquidduring the emptying
of the tank.
In order to show
this arrangement, a portion of
The
the electrodes to the rightin Fig. 234 has been cut away.
electrical connections
from
the figures. The
are
clearlyseen
decrease
with
the
must
current-density
percentage of antimony
in the solution.
may

Although, with

be commenced

with

concentrated
current

[0*064to O'l amp.


per sq. metre
it to about 40
reduce
graduallyto
more

of the series in

the end
under

metal

accordingto
the

150

to

amperes
economical
i
t
is
per sq. in.],
to 45 amperes
[0*026 to 0*03

parallel.The

necessary

by introducing
of the tanks at
E.M.F. averages

2 volts per bath.

The

separates in pulverulentform
the

bottom,

density of

whilst

that

current

which

used.

readilydetached
by steel wire brushes.
antimony together will be described
Conditions
"

cases

necessary

Suitable

to

It has

been

be too

costly.

to

reaction,and

in lustrous

or

adheres

the

all

lysis
solutions,electro100

be effected either
per sq. in.]. This may
baths into the circuit,
or
by coupling some

amp.

to

of

part always

to

The

the

iron

method

scales
settles

plates is
of melting

later.

Electrolytic

Befining

of

mony.
Anti-

affirmed

purchase

in
that this method
must
by some
Undoubtedly, it would be so if it were

the

if the solution

sodium
were

run

sulphide required for the


had been
to waste
afteiii^it

485

ANTIMONY.

the
electrolysed.But there are circumstances under which
method
of these
might be utilised with advantage,and some
be
here
examined
into
:
shortly
may
would
1. The simplestcase
be that in which
a cheap source
of sodium
sulphatewas available. In countries,or in industrial
main
as
a
centres, in which hydrochloricacid is manufactured
in
the
Leblanc
soda process),
as
product (and not incidentally
sodium
sulphate would be a by-product. The process would
then consist of the following
stages :
Reduction
of
the
(a)
sulphateto sodium sulphideby heating
"

"

with

carbon.

ing,
(6)Leaching of the product; in which case the cost of clearand
the
of
sodium
crystallising,
packing,
freight
evaporating,
sulphidewould not be included,because the liquorswould be
utilised in the next stage.
(c) Solution of the antimony

ore

in

the

sodium

sulphide

solution.

(d) Electrolysisof
antimony.

the

clear

solution,and

of the antimony.
of the electrolyte
by

(e)

Fusion

(/)

Oxidation

depositionof

air,and

of

means

centration
con-

of the

resulting
thio-sulphate.
raw
materials,sodium
sulphate,carbon, and
would
there
be
produced antimony and sodium
antimony ore,
thio-sulphate.
Thus,

from

2. It

is, therefore, evident

the

that

acid
hydrochloric

facturers
manu-

might adopt this process, in order to find a profitable


unsaleable sodium
for the comparatively
use
sulphate. In this
the raw
materials
would
be sulphuricacid, or the
instance
sulphidesnecessary

for its

salt,coal,and

manufacture, common

be

antimony ore, while the marketable products would


acid,antimony, and sodium thio-sulphate.
3. In districts in which

there

demand

chloric
hydro-

hydrochloric
thus :
might be altered but slightly,
of sulphuricacid from a part of the sulphur
recovered at the end of the operation.
{b) Sodium
sulphate and hydrochloricacid prepared from
acid
and
salt.
common
sulphuric
Sodium
(c)
sulphidepreparedfrom sulphateand coal.
(d) Leaching of the antimony ore.
of the antimonite
lye.
(e) Electrolysis
of
Fusion
the
{/)
antimony.
with
(g) Recovery of sulphur from the spent electrolyte
than half of the sulphur
the aid of the hydrochloric
acid,more
the residue
into sulphuric acid, and
being thus reconverted
being sent into the market as such, or in the form of sulphuric
is

no

for

acid,the

process
Manufacture
(a)

"

acid.
In

this

case

the

raw

materials

would

be

:"

njtrat^
So^ljjft^i"
-So^^lijft^injtratek^

(D^itizsdb^Goe

^"

486

BLICTRIC

SMELTING

REFINING.

AND

salt
sulphuric acid plant, common
of the working loss, the greater part of that
(to the amount
Whilst
the
used being reoovered),coal, and antimony ore.
be antimony and sulphur or sulphuric
finished products would
air

and

for

steam

the

acid.
B.
Sanderson's

ANTIMONY.

PURE

Prooess.

None

"

of the

above-mentioned

cesses
pro-

lytic
electroor
producingantimony, whether metallurgical
saleable.
It is
that is directly
in character,givesa metal
either too impure, or it is obtained in a loose and pulverulent
form.
A
wai*, according to
process proposed by Sanderson*
in 1889.
A
with
Vogelytexperimented
by an Englishcompany
solution
solution of butter of antimony in a very concentrated
acidified
with
of sodium, potassium, or ammonium
chloride,
said to resist even
hydrochloricacid,was
great dilution with
for

it

water;

should, therefore,

electrolyte.In

this

be

very

suitable

for

use

as

an

anode-

solution

are
suspended antimony
is passed they are
the current
platescontaininggold. When
and deposited
dissolved
the
graduallyattacked,
antimony being
the
while
sink
electrolytically
gold particles
upon the cathodes,
of the vat, whence
to the bottom
they are removed and fused
have
accumulated.
sufficient
togetheras soon as
The process, however, according to YogeFs account, proved

much
a

too

costly.But apart

chloride solution

can

this,it

from

afford

never

been

has

good

shown

that

deposit,for which

alone

reason

the process would


stand condemned.
phide
ProcesB.
Koppt proposes to treat antimony sulwith
solutions
of ferric salt,in order to obtain

Kopp*8

"

ores

antimonious

chloride,accordingto
6FeCl, + SbgS,

"

the

followingreaction

GFeCl,-h 2SbCl,+

"

Sa

The

reaction takes placerapidlyand completely if free hydrochloric


such
sodium
acid or (better)
a
as
chloride,
halogen salt,
be added.
The antimony solution is then to be passedinto the
cathode compartments of an electrolyte
tank, which is divided
ferrous
into
chloride solution
the
w
hilst
cells,
up by diaphragms
is conducted
mony
through the anode compartments after the antihas been deposited
from it. Thus whilst the antimony is
at the negative electrode,the ferrous chloride is
precipitated
and
peroxidised,
The

electrode.

ferric chloride
latter

solution

is

regeneratedat

is then

used

the

once

positive
more

to

antimony compounds. Both anodes (!)and cathodes


of lead.
The electrolyte
is heated to about 50" C,
in
motion.
In
order
obtain
of a
to
a dense, instead
kept

dissolve
may

be made

and

is

*
German
Patent 54,219, Feb. 26, 1890.
i Zeitscht^Jt
fiirangewandte Chemie, 1891, p. 327.
t German
Patent 66,("47.

487

ANTIMONY.

of
depositof antimony, a current-density

spongy,

[0*026amp.

per sq. metre


Siemens

-HalBke

"

patented a process,'*
by
arsenic,is dissolved
cathode

cells of

40 amperes
is
used.
per sq. in.]
Siemens
k Halske
have
Process.
which
the sulphideof antimony, or of

in alkaline

sulphydrateand

added

to

the

whilst at the anodes


electrolysis-apparatus,
chloride is employed for the sake of
But this method
of electrolysing
thio-salts
obtainingchlorine.
is by no means
happilychosen ; the recovery of chlorine at the
suitable here ; it demands
the use
of a more
anode is scarcely
the
introduction
of diaphragms (for
complicatedapparatus, and
which
suitable material
has yet been found) without
no
offering
any noteworthy advantages. The reactions quoted in the patent
do not take placeso readilyas would be understood
specification
from the equation.
[Thisfirm has introduced into the market electro-deposited
antimony, presumably made by the above process, in the form
of grey plates,
about -^^in. thick,with a rough surface,covered
a

solution

with

of

an

wart-like

other

an

alkaline

excrescences

it had

on

one

side, but
with

the

smooth

on

the

cathode

plate).
and the metal is said to contain ^9*7
crystalline,
to 99-9 per cent, of antimony. Translator.]
The
of antimony has scarcelypassed
extraction
electrolytic
be assumed
out of the experimentalstage ; but it may
that, if
be solved by the electrolysis
of sulphides,
the problem cannot
it can
solution will be
scarcelybe hoped that a satisfactory
The

(where

fracture

been

in

contact

is

"

found

for it.

Treatment
"

^A process

togetheris
consist

of

order, as

of the Crude
or
Electro-deposited
Antimony.
of fusion either for refining
or for running tliemetal
unavoidable

in

The
impuritiesmay
and
other metals.
In
sulphur,arsenic,iron, copper,
far as possible,
of the metal
to prevent the contact
every

case.

with

iron,the impure antimony is melted in crucibles or reverberatory furnaces, in the first place with antimony sulphide
that has been liquatedfrom antimony glance),
by which
(SbjSg,
and
and
afterwards
iron
means
removed,
principally
copper are
with
basic substances,such as potash or soda, togetherwith a
small proportionof oxide or sulphideof antimony. In this way
the metal
with the formation
becomes
of a slag
desulphurised,
containing thio-salts of antimony. The antimony obtained
and
be washed
brushed ofi* the cathodes must
electrolytically
and dried,and is then fused togetherunder a slag of antimony
with basic additions,such aa
oxysulphideor of thio-antimonites,
soda or potash.
have alreadybeen described
The
Applications of Antimony
in referringto its properties,
include
alloying,
they
deposition^
pigments,thermo-electric couples,antimony chloride.
.

"

German

Patent

67,973.

488

REFINING.

AND

8MELTING

ELECTRIC

VANADIUM.
and
in nature, but

Ocourrenoe
It

for the most


in the

less often

occurs

Properties.
form

buted
widely distrismall quantities.

Yanadiam

"

is

part in very
of free oxide

in that

than

of

Among the latter,the lead compound is the most


has not yet been
of vanadium
melting-poitit
determined, but since it appears to approximate closelyto its
in the
it is very difficult to obtain the pure metal
boiling-point,
The
solid
after
fusion.
form
of large
purest specimen
pieces
vanadates.

abundant.

The

yet obtained

of the metal
lustrous
which
into

of

has

gravity 5*5.
specific

powder,
this powder ignitesis
flame

it burns

The

grey
at

temperature

high, and

sprinkled
only with
acid or in dilute sulphuric
hydrochloric
readilyin strong sulphuric acid, in
if

not
very
brilliant sparks. It is

with

soluble in
great difficulty
acid, but dissolves more
acid, or in
hydrofluoric

condition of

in the

been

With

nitric acid.

fused

elevated

At
hydroxides it forms vanadates.
readilywith the halogens,or
with nitrogen.

combines

with

alkali-metal
it

temperatures

sulphur,or

even

Ores containingfree
of the Ore.
Treatment
vanadates
of refractory
oxides, are roasted with soda

Preliminary

oxides,or

"

In this
comparativelylow temperature (400^C. suffices).
small
mixed
with
are
a
produced
only
proportion
way
of silicates if the temperature has not risen too high during
The
with
the roastingprocess.
is leached
mass
water, and a
little silica which
thus passes into solution is readily
precipitated^
in closed vessels.
The
of
of carbon dioxide
excess
by means
carbonate
is then decomposed by adding hydrochloric
sodium
down
is then thrown
vanadate
as
acid,and the vanadium
by
at

vanadates

of soluble

means

vandates

salts of

barium, lead,iron,and
be

obtained

the

like.

The

for the direct

employed
production
may
alloys. Other ores which contain the metal in the
vanadates
of readilyreducible metals, are fused with the
of soda or
lime and iron oxides under reducing conditions,
so

of vanadium
of

form

addition

of

in order to separate the combined


The
slagcontainingvanadates.

metal

slagcan

with
then

Levera
has
Working by this method
of
vanadium
almost
an
yield
quantitative
obtaining
Institute of the Aachen
the ore in the Metallurgical
above.

Vanadium
Beduotion
Process.
which
found
reduced
be
to
most
was

oxide

"

author's
resistance

experiments during
furnace,which

difficultiesencountered
*

See p. 103 above

and

has

the
been

by

Moissan

pp.

62, 63

1887

to

be treated
succeeded

as

in

oxide from
School.
one

was

readilyin the

years

the formation

of

course

those
of the

1890, using

repeatedlydescribed.*

his

The

t in his experiment in fusing


of the

book, published in 1891.


fComptes Rtiidxu^1896, vol. cxzii.,p. 1297.

first German

edition

of this

490

ELECTRIC

83IELTINO

AND

REFINING.

the

The other haloid salts also (the relatively


alkali metals.
stable flaorides not excepted)can only with difficulty
be obtained
in a form suitable for electrolysis.
has
Uses
of Vanadium.
Up to the present time vanadium
"

only

been

certain

experimentally.As

varieties

presence
no

used

Swedish

of

of vanadium

iron

in the

doubt,soon
industry.

be made

have

been

ascribed

to

the

experimentswill,
in the
alloysapplicable

metal, exhaustive

the vanadium

on

specialpropertiesof

the

iron

CHAPTER

CHROMIUM,

XI.

MOLYBDENUM,

URANIUM,

TUNGSTEN,

MANGANESE.
CHBOMIUM.
chromium
is mainly found
in Nature.
In nature
if ever,
in
oxide
chrome iron ore, FeO
as
CrgO,,which rarely,
correspondsaccuratelyto this formula, the FeO being in part
Ooourrence

"

replacedby MgO,
Grocoiaite is

the
practically

FropertieB
and
lustrous,

and

the

chromate

of

only

one

CroO" in part by Al^Oj

lead,PbCiO^.

used

Chrome

for the extraction

Chromium
is a
of Chromium.
with
hard
metal,
ciystalline
very
"

or

Fefiy

iron

ore

is

of chromium.

brightgrey, very
a specific
gravity

with
fusingpoint has not yet been determined
but it is a little higher than that of platinum, or
accuracy,
approximately2,000* C. Chromium
containingcarbon melts at
The
between
0.
and
a temperature
1,600'
alloyingpro1,800**
perties
those of
of chromium
have not been so fullyexamined
as
other metals on
of the metal ; and
of the infusibility
account
the
and chrome
steel) are
only
alloyswith iron (ferro-chrome
of any practical
importance. Since a metal containingcarbon
is yielded by most
of the processes
employed in extracting
ascribed in the books to pure
chromium, many of the properties
chromium
in reality
carbon
carbide alloy. Pure
its
to
or
belong
the
chromium
cold
air
oxidises very slowlyin
; but, on heating,
surface becomes
readilycovered with a thin film of oxide,which
it
Even
in oxygen
may
possess any colour from yellow to blue.
does not burn
with
combines
as
readilyas iron. Chromium
sulphur and with the halogens,evolving a very considerable
of heat.
with carbon
amount
It is especially
to combine
prone
and
silicon,and it has already been stated that it is almost
impossibleto obtain by simple reduction processes a metal that
of 6 to 7.

Its

491

CHROMIUM.

is free from
such

but

carbon.

Carbides

metal

have

rich

very

in

isolated

yet been

not

Carburised
chromium
is much
harder, and
than does the pure metal.
influences far more

The

and

chief

the

so-called

chromic

resists

the

acid, CrOs, are

as

easily obtained.

is

carbon

chemical

oxide"

CrgOu,

comfiounds

with

that are of technical importance; the first-named


oxygen
forms a series of (chromic)salts with acids,the latter a series of
chromates or chromic acid salts with bases.
The
Beduction
for the manufacture
the chrome
iron

being an

Prooess.
of iron
iron

This is effected almost


to

be

obtained

with

chromium

fused

reduced

iron
known

in
exclusively

in the

be

alloys,
may

and

which

Chromium,

in admixture

ore

alloy of

"

ore,
as

crucibles.

the

from

product

ferrixhrome.
If the alloyis

it will be

condition,

used

is to be
direct

to

necessary

employ regenerative
gas-firing.

Fig.235.
The

metal

pure
method

of

tedious.

divided

only

can

oxide,but

even

be

then

obtainingthe
A

Borchers' electric furnace.

"

chromate

unalloyed by treatingthe

obtained
it will not

oxide

from

be free from

chrome

is first obtained

iron

ore

carbon.

The

is somewhat

by calciningthe finely-

potashor soda in the presence of air,and from


this the oxide is produced by roastingwith sulphur. The oxide
formed in this way
the alkaline sulphates
is washed
free from
the
with
treatment
produced during
sulphur, and it is then
reduced
by heating it with carbon in plumbago crucibles. In
this manner
metallic powder is obtained,which shows no
a grey
has been emwhen
even
ployed.
signof fritting
regenerativegas-firing
The metal can
fused
with
aid
the
be
of
electricity,
only
for which

ore

with

an
purpose
electrical resistance or

apparatus

heated

either

by

means

of

an

the aid
by the arc may be used. With
of the former apparatus (which has alreadybeen described)
the
fused
chromium.
This
first successful in obtaining
author was
in
convenience
this
for
be
at
figured
apparatus may again
place
used
Within
in
the
illustrating principle
heating (Fig.235).

492

ELECTRIC

left between

the space
chromium
which

SMELTING

oxide

forms

and

the

B C D F S, a mixture
of
around
the carbon rod, k^

A
firebricks,

is

carbon

packed

bridge between

REFINING.

AND

the

thick

lies in the midst of the mixture.


of 8 to 10 amperes
per sq. mm.

thus

The

passage of a powerful
of cross-sectional area
of

current

the

rod

small

raise the
oxide
The
it

[5,000to 6,500 amps,


of the

temperature

is

and

reduced,

the

of this furnace

use

was

Furnace.
of the

use

sufficient
that

extent

an

upon it here.
described
the

chromium,*
shown

apparatus

of this miniature

has

who

obtainingnon-carburised

the
hearth

further

to dwell

Moissan,

"

in.]is

to

the

fuses together.
resultingchromium
earlier
chapter,and
explained in an

is,therefore,unnecessary

Moissan's
method
of

per sq.
to such

mass

rods, K, and

carbon

in

consisted of

furnace

at

firet

best

mended
recom-

Fig. 236. t The


limestone
block

{pierrede Courson),in which a rectangularcavity had been


lined with
prepared. The walls of the cavity were
magnesia
[0*4in.]thick,and then again with carbon plat^
plates10 mm.
of the

thickness.

same

through

one

course,

cut

and

make

so

Two

stout

oppositeside

each

that

so

away

it

or

were

introduced,

wall,the carbon

it did

with

contact

carbon rods
not

start

liningbeing,of
touch the rod at any point
electric arc
At right
an

lower level,
but at a somewhat
a carbon
anglesto the electrodes,
The tube may be set level,
tube is passedthrough a third wall.
at any angle of less than 30* with the horizon,and
to
or
serves
the substance

contain
massed

f0-4

through it.
the

in.]below

chamber,

like the

plate,then

of

to

The

be
end

heated,which
of the tube

electric

be
of

some

in
10

or

is

mm.

the

melting
furnace,consists,first of a carbon
of a limestone
magnesia,and, finally,
arc.

cover

of the

body
slab

The

either rests

should

of

block.

Fig.236."

Moi8san*8

electric furnace.

Furnabe.

Fig.237." Chaplet'selectric fumaca

ChapletJ seeks to distribute the heat


by submitting the tube containing
The
the charge to the influence of a largernumber
of arcs.
furnace
main
consists of two
portions,an under part, a, and
Chaplet'8

more

evenly in the

"

furnace

Comples BenduSf 1894, vol. cxix., p. 185.


iComptes Rtndus^ 1893, vol. cxvii.,p. 679.
t (German

Patent

77,896.

49a

CHROMIUM.

are
portion,b, which
The
lower
(Fig.237).
part,a, is

upper

an

of the

out

hearth.

whole

hearth

The
that

transferred

from

o,

It

be

part

of

the

electrodes,
c, in

of

opening

of

V,

the
of

the
The

sufficient

number,

the

whole

be
tube, d, may
Additional
electrodes,

in

the

heated.
c

an

escape

disposed that

mass

of the
between

them

prevent

may

modified
Chaplet*8

Fig. 238."

electric furnace.

the mouth
arranged near
tube
containingthe charge, so

are

tubes

muffle

and

charge (Fig.238).

so

the

may

doubled,
with

narrow

allow

are

consist

material

V-form

molten

made

collectingwell.

also

may

to

replacedeasily. The
movable, so that it might be

having an opening,
point,through

the

into

possess
the
at

may

molten

the

flow

wheels

lowest

its

which

on

run

and

moved

electrodes. The

and

simple tube
at

to

or

lowed
holthe

extending over

to slide

use

well,e,

inclined
sufficiently

is

downwards,
a

furnace,or

is made
be

of

form

one

upper
the movable

muffle

in the

well to another.
collecting
portion of the furnace contains

The
and

hearth
it may
also be

rollers,so
part could
upper

or

of the

in

together when

luted

that

the

the solidification of the

playing

arcs

at this

mass

point.
of Crude
Chromium.
made
be
it
of
a mixture
(whether

BeflLning

other
tend

refractorymaterial)and
to

the

prevent

oxide

and

the

of

of the

charge

pure

mixture

itself

free from

chromium

of chromic

description. The
has ingentherefore
Moissan
must
iously
solved this problem by adapting to it the principles
of the
steel
lime
with
chromic
open-hearth
By heating
process.
carbon

in

an

apparatus

well

the

as

electric furnace
carbon

of

this

be refined.

oxide he obtains
as

clay and

smelting of

resultingmetal
basic

containingtube
graphiteor of any

the

Both
carbon

the

formation

carbon, silicon,"c., by

"

of

basic substance

fluxingof the
be lined with

which

for the oxidation

serves

impurities. If the
this calcium

chromite

and

silicon present in the metal


that
will be oxidised and removed
by the chroniic

eliminated
that they are
from
way
iron in the open-hearthprocess.
As

far

as

made
appears
carbon

to

may
in
be

by adding

iron

by

hearth

of

mixture

an

the

is heated

upon it
oxide, in the same
means

of oxide

of

predictedfrom some
preliminaryexperiments
electro-metallurgical
laboratory, there
of obtaining a metal
free from
possibility

be

the

aluminium

oxide

to

the

mixture

of chromia

494

ELECTBIC

oxide
As

carbon

and

shown

was

This

oxides

is obtained

are

expenditure of
of calcium

with

can

by

energy,

In

of

method

an

of this
in the

ease

oxide, but when


metal
contained
in

the first case

aluminium

second,an alloyof chromium


after
only be decarburised

means

chromite, the

edition

the greatest

of the

none

carbon.

in the

carbide,which

chromium

in the electric furnace.

also of chromium

alone,

free from

formed, and,

is

is true

reduced

these
them

REFINING.

in the first German

oxide is reduced

electric furnace.

carbide

the author

by

AMD

for the reduction

used

aluminium

work,

SMELTING

with

great

of chromium

excess

oxide

indicated

by Moissan.
A
oxide, equivalent to the alumina
quantity of chromium
be
of
used, may, however,
placed on the top of a mixture
with
alumina
the proportion of carbon
its
tion.
reducto
necessary
On electrically
heating this lower layer to the temperature
alumina
is reduced,metallic aluminium is formed,
at which
carbide.
The
together with a small quantity of aluminium
the
aluminium
and
and
as
layer,
vaporises
penetrates
upper
the latter has attained
a
soon
as
high temperature
sufficiently
condensed
(not readilymeasurable),it reacts with the aluminium
and with
the aluminium
carbide lying beneath
in its midst
it,
and becomes
of heat, and so yields
reduced with great evolution
The dynamos (thelargestwas
fused chromium.
only 12 H.P.),
or

the experiments
in the temporary laboratories in which
the process cyclically
not sufficient to carry on
were
tried,were
carbon
reduce
alumina
the
re-formed
to
namely, by adding

available

"

the

during

that

reduction

of

would

have

institute

at

attached

to

were

between

reaction

oxide, 80

made.

the
more

chromium,

been

continued

Aachen,

and

that

The

Heroult

the

process,

These

on.

so

the

in

the

same

the

for the

experiments

laboratories

new

which

the chromium

be available

may

opened in 1902, if
they had when

them

and

tbe aluminium

resultingaluminium

of

interest

preliminary

will be described

the
had
tests
more

provides for the

Iron,
chapter
preparation,
minutely
which
have
a
entirely free from carbon, of all the metals
end
and
attains
this
and
form
to
so
carbides,
simply
tendency
such
with
to
simple plant, that it seemed
quite unnecessary
direction
The
the experiments in the
continue
suggested.
affected by considerais not
tions
principleof the Heroult
process
in

as

on

to whether

alumina

or

any

other

metallic

oxide

is best

preventionof carburisation in
or
alloys.
smelting
Heibling* has proposed so to smelt,
Heibling's Prooess.
which
tend
and
to
with
lime
carbon, those oxides
produce
the minimum
of
be produced with
carbides,that a metal may
the
for
with
most
slags composed
carbon, together
part of
carbide.
This process
is worthy of careful attention,
calcium
the
furnace
for
its applicationdoes not show
although
proposed
adapted

to the

decarburisation

of chromium

tbe

or

of its

"

"

German

Patent

86,593, and

Marx,

Lu

Proc4cUs

Heibiing,Paris, 1897.

495

CHROMIUM.

stmction

and

Process.
with

chromium

oxide

author

the

scale,but

has

shown

does not

appear
the
in view

used, having
chromium.

pose
proposal*to decomis
sulphides quite feasible,
by experiments on quite a small
to have much
now
prospect of being
present positionof the metallurgy of
first patent he referred

Aschermann's

In

Precipitation
fused

its

Process.

salts

chloride

chromium

con-

metallic

sulphide of antimony, and in


of other sulphidesalso.
the use
The

to

Aschermann's

"

of

from

regard

ase.

Aschermann's

as

in

reqairements soaght

of the

complete grasp

by

the

^The

"

he

separationof

use

protected
chromium

zinc, and especiallyfrom


chloride of chromium, and
au
of

means

the double

or

later patent

to the

The
by Wohler.t
yield is very
The
is of great purity.
alkali metals have
small,but
also been used for the decompositionof chloride of chromium.}
An
Gtoldschmidt's
Process.
especiallyremarkable
process
has been
discovered
by Gold8chmidt" for the separation of
alkali metal

first e"fected

was

the

metal

"

chromium

from

readilybe

conducted

with

chromium

oxide

aluminium

its oxides

molten

the

in
the

condition.

It

can

of the

aid

simplest apparatus,
of heat energy
and owing to the largeexcess
developedby the
reaction,it does not require the use of external heating,or of
electricity.A thoroughly dehydrated oxide of chromium, preferably
heated
with
shortly before use, is mixed
powdered
and
aluminium
Here
it is ignited with
placed in a crucible.
the aid of a priming charge of barium
with
peroxide mixed
The process completes itself with a brisk evolution
aluminium.
of heat, and while it is taking place,a further quantity of the
and

until,at last,the
by little,
On
cooling,a well
charge.
found

the

at

bottom

equally well fused

with

be

to

Bunsen
merits

fused

of the

OF
of

is

CHROMIUM

added,
of the

little

melted

chromium

with

is

slag

of

in the

Fused

or

Anodes.
field of

COMPOUNDS.

"

Chromium

If any

one

work

pounds
Comdeserves

it is
electro-metidlurgy,

the

production of chromium
especialrecognitionnot only on
on

be

nearly full
regulus of pure

crucible,covered

Dissolved

Insoluble

foremost

crucible

may

alumina.

EIiECTBOIiYSIS

Electrolysis

mixture

that

by electrolysis.
||
account

of the

of
It

tion
observa-

and
itself,

but
*

because
German

of the arrangements
devised
for the experiment,
at the time at which
it was
accomplished,electrical

Patents

93,744 and 94,405,of 1896.

dtr Ckemie und Pharmacie, voL cxi.,


Amutlen
Liebig's
p. 290.
der Ckemie uiid Pharmacie, vol. Hi.,p.
t Peligotin the Annalen

Patent 96,317, March


578,868 and German
fur Mektrochemie; 1898, vol. iv.,p. 494.
Zeitsckrijt
WPagg. Ann,, 1854, vol. xci.,p. 619.

SU.S.A.

Patent

244.

13,

1895.

496

ELECTRIC

SMELTING

AND

REFINING.

measuring instruments, and other requirements were


It should
be
nearlyso readilyavailable as they are now.
whom
time or opporpointed out to modern
experimenters,to
tunity
has failed for the study of the classics of electro-chemistry,
than forty years ago, Bunsen
showed
the result "^
that, more
instances on the densityof the
to he dependentin many
electrolysis
energy,
not

His

current.

Bun8en*8

of his observations

account

Experiments.

"
"

The

ran

follows

as

densityof

"

the current

(that

is to say, the relation of the strength of the current


to the
of the electrode at which
is taking place) exerts
electrolysis
influence

the

on
important
for example, if a current
through a solution of chloride

most

Thus,

surface

the

upon

of

area

of

resultingchemical

the

reactions.

unvarying strengthbe passed


in water, it depends

of chromium

the electrode
chromic

effected,whether

hydrogen,

metallic

shall be obtained.

chromium

area

at

which

reduction

chromous

or

is

oxide,

or

of the constituents
important is the relative mass
which
the
is passed. Thus,
current
through
electrolyte
if with a constant
the proportionof chloride of
current-density
in the solution be gradually increased, a point will
chromium
be reached
which
oxide
at
the separationof chromous
soon
will be accompanied,and this will presentlybe succeeded
by a
**

Not

less

of the

reduction of the metal.


of
I adopt that of a current
current-density,
1
the
surface
of
is
1
on
intensity
sq. mm.
I,
density,D, will then depend upon the absolute intensity,
the area, O, of the polarsurface measured
in sq. mm.,
thus
unit

''As
which
The
and

(1)D

the

of

absolute

with

I is found
=-pr ;

the aid of the tangent

galvanometer

RT
from

formula

(2) I

galvanometer ring in
galvanometer needle

tan

-"

mm.,

is

p, in which

f is the

is the radius

angle through

deflected,and

is the

of the

which

horizontal

the
ponent
com-

of the earth's

magnetism (Gauss'measurement). In this


T
a
formula, requires specialadjustment according to time and
by the
place. This is most simply and accuratelydetermined
calculation
the known
of water, basing the
electrolysis
upon
the
If
of
water.
electro-chemical equivalent
quantity of water
decomposed by the current, I, in t seconds be termed A, and
electro-chemical
the known
equivalent,or the weight of water
(inGauss' measure),be called
decomposedby an unit of current
a,

then

according to Faraday'slaw (3) I


this with

equation (2),it will

be

seen

^'^
T=
atB, tan

^*

""

that

Now, by

bining
com-

498
the

REFINING.

AND

SMELTING

ELECTRIC

the cathode.
npon
The
8 to 10 volts.

this

is about

case

likelyto be

applied on

requiredin

E.M.F.

The

state
crystalline

process is,therefore,not
But
scale.
apart from the

technical

decomposition,other objections
necessary
the
in
found
the
are
to
rapidheating of the solution and
process
of acid vapour.
the evolution
of largequantities
high

for the

KM.F.

The
Placet-Bonnet
and
Placet
Bonnet*
of
to
[Borchers]
It was

stated

which

were

FrooeBS.
s

process

does

not

practicability

the

Although

"

to the

appear

author

be very promising,it is necessary to refer to it,as


in several journalsthat certain blocks of chromium

shown

in the

Exhibition

American

with

made

were

its aid.
the electrolyte
According to one of the patent specifications,
of
100
mixture
a
preparedby warming
parts by weight of
with
100
of
and
chrome
10 to 15 potassium bisulalum,
water,
to the strength,
as
phate. The electric current
(details
pressure,
and densityof which
not given)at once
are
depositschromium
The
the cathode.
originalstrength of the solution is
upon
either of chrome
alum alone, or of
maintained
the
addition
by
alum
and alkaline bisulphate. An
of chrome
a strong solution
overflow
tank serves
tube attached to the electrolysis
to keep
If
the level of the solution at a constant
chrome
alum
height.
is

alone

be

added

of the

water

bath, a time will


solution,togetherwith the
to

it,will have

in

now
electrolyte

the

passed away
consists

through

of salts which

arrive

are

all the
dissolved

pipe. The
either by
liquefied

overflow

the
can

which

at

salts that
be

longer necessary, and the mass


of salt is consequently heated
to its fusingpoint. Potassium
chlorate and boric acid,benzoic acid, or
analogous salt are
water

by

or

heat.

Water

is

no

"

**

to

now

be added

to the fluid

mass

there
bisulphate,

for

potassium
sulphate or the bisulphateof

at intervals.

may
soda

be used

as

As
a

substitute

flux either

the

ammonia, the phosphate,


borate,chlorate,silicate,
chloride,fluoride,
"c.,of the alkalis or
alkaline earths,or mixtures
of these salts ; and in lieu of chrome
alum

or

other

be employed.
salt may
easilyfusible chromium
for the fusion of
a
very high temperature is necessary
electric current
is ''ordinarily"
used
for the
chromium, an
The
electrodes
of carbon
purpose.
may be compressed mixtures
oxide or salts,with reducing and
and chromium
fluxingagents,
or
they may be composed of metals such as copper, aluminium,
alumina
zinc,nickel,silver,
"c.,or of oxides of these metals (e.g,,
In
the
latter
chromium
obtained.
case
are
electrodes).
alloysThe inventor
also that neutral or reducing gases, or
recommends
metallic powders (suchas zinc or aluminium) be blown
through
criticism of the
hollow electrodes
during electrolysis.
Any
any

Since

above
*

is

obviouslysuperfluous.

German

19,344, 1890

Patent
;

66,099, Dec. 5, 1890. English Patento 6,751, 1893;


22,854, 22,855,and 22,856, 1891.
U.S. A Patent 526,114.

499

CHROMIUM.

Holler

and

Street's

patents of Moller
Company, which

Process.

Street

and

and

The

"

descriptionof the
Electro-Metallurgical
both inventors, gives

of the

probably co-operatedwith
lytic
a striking
insightinto the difficulties which attend the electrochromium
of
from
when
solutions
it is
separation
aqueous
attempted as a regularindustrial operation. These specifications
the advantage that they are at least based on experiments
have
actuallytried. In one example quoted,the composition of the
was
1,500 parts by weight of each of the following
electrolytes
substances
:
Water, chrome
soda-alum, and sodium
sulphate.
acidulated
The water
with 5 per cent, of sulphuricacid of
was
The solution
66" B^.
in the anode
cell consisted only of water
acidulated
with
acid
The
above.
cathode was
as
a
sulphuric
brass plate,which
bent
into tube form.
The
or
was
copper
of lead.
An
anodes were
apparatus prepared in this way should,
at a temperature of TO""C, have given about 0*2 gramme
[3*1grns.]
if
of chromium
of
40
a
current-density
per ampere-hour,
amps, per
"

[3*7amps,
sq. metre
A certain more
or

be maintained
at the cathode.
per sq. ft.]
less considerable
quantity of the substances

present in the cathode

but gradually,
constantly,
passes over
This
compartment.
quantitydepends upon the
the
of
cells.
the
anode
and cathode
nature
diaphragm separating
For example, 0-562 kilogrm.[1-2lbs.]of CrOg and 0-963 kilogrm.
added
in this way
to the anode
[2-1lbs.]of NagSO^ became
cell after the lapseof twenty-fourhours in an experiment during
which
23-5 kilogrms. [51-7lbs.]
of chromium
were
separated.
of
Sulphuric acid, in quantity corresponding to the amount
chromium
also
the
of
at
course
bottom,
separated,was
produced
As an example of the quantity of the
in a diluted condition.
sulphuricacid set free,the inventor states that in a factoryof
would
which
the outturn
of chromium
be 1 ton
in twenty-four
hours, there should be produced 3 tons of HgSO^ as a by-product,
diluted
with
considerable
a
Actually,
proportion of water.
contains at most
10 per
since the process yieldsa solution which
be
of
there
would
about
30
of solution,
tons
cent,
sulphuricacid,
into

the anode

and

it would

solution

therefore

of water.

already
chromic,

contains
been

sulphur

salt

of

shown,

the

solution

anode

dioxide

in

sulphate.
bichromate

"

sulphuric,acid

as

sodium

of

English

as

followingsystem

chromic
mixture

evaporate

in

owing

into

it.

This

order

to

re-convert

It is then
is added

the

solution
the

concentrated
in sufficient

Patent

18,743, Sept. 1, 1898

working.

to

diffusion

is treated
acid

chromic

German

with
into

produce a

H2SO4,
Patents

of

SO""B^., and

quantity to
and

has

As

cell contains

the

to about

equivalentquantitiesof CrOg

105,847, 1898.

27 tons

some

presents itself in the fact that the


well as sulphuricacid.
The
inventors

the

sulphate

chromium

to

necessary

devised

well

as

be

here
difficulty

therefore

have

cell

without

104,793 and

500

ELECTRIC

SMELTING

AKD

REFINING.

be produced. This
sulphate that would
in
leaden vessel
into
stream
a
a
finally
gentle
of melted
which contains a slightexcess
sulphur at a temperature
of 130* C.
chromic
the sulphur and
The
acid oxidises
chromium
forms
sulphate. The solution having been diluted
and the excess
of sulphur filtered off,it is ready for use
again as
the
in
chamber.
The
cathode
leads
cathode
reaction
electrolyte
in the cathode
cell becoming constantlypoorer
to the solution
while
in chromic
the
sulphate,
sulphate
proportion of sodium
remains
If the separated chromium
is
practicallyconstant.
the
sodium
of
addition
of
the
replacedby
sulphate,
separation
the ever-increasing
sary.
quantityof sodium sulphate becomes necesThis is effected by cooling and crystallising
the solutions
tank.
outside the electrolytic
In this way the inventors
have finallyarrived at the following
Tnsatment
solution containing chromic
of the anode
process :
acid with SO^ as above ; and saturation
with Or2(OH)g. The
be
chromium
obtained
hydroxide can
by reducing chromates
phides.
with
alkali-metal (or, better, with
alkaline-earth metal) sulBaS
is especiallysuitable, because, in addition
to
Cr2(0H)gfit yieldsHaS04, ^l^i"^b can be again reduced to BaS
af^r leachingout the chromium
hydroxidewith sulphuricacid.
The
little else than
contain
an
lengthy patent specifications
of the observations
the
in
made
inventors
account
coarse
by
of experiments made
with the object of separatingchromium
from sulphatesolutions.
electrolytically
The second
inventor * relates to a process
patent by the same
of
for the regulationof the conditions
for the precipitation
and
In
of
o
f
chromium.
course
metals,
especially
experiments
of chromium
in the recovery
from sulphate solutions,Bunsen*s
confirmed
observations are
namely, that the character of the
Thus, for example,
depositvaries with the current-densityused.
the
and
the
of oxide
current
same
same
bath, a precipitate
using
the sodium

regard to

is

solution

run

"

"

obtained

was

with
which
18

bar

with

15

mm.

in

mm.

increased

in

in diameter

continue

well, and

obtained

at

all.

bar
[cathode]

diameter

with
These

mm.

in

diameter,

good deposit was

thickness
received

with

efficient

results.

deposit,which, however,

bar

numbers

20

mm.
are

thick

whilst

obtained
A

bar

did

not

deposit was
only quoted by way of
composition of the bath
no

example; they vary greatly with the


and the proportionof free acid present.
With
a
given bath, and with a current which gives a good
to tind a diameter
deposit on a bar 15 mm.
thick, it is possible
of bar (test-bar)
when
in
which,
parallelwith the first
placed
bar in the same
solution, receives a depositof chromium, but a
deposit that
present

fails to increase

in the

bath, no

chromium

"German

If too much
acid be
The
is depositedon the rod.

in thickness.

Patent

104,793, 1898.

501

CHROMIUM.

proportion of acid
pointis reached, at
The
be

so

such
bar
it

chosen
limits
be

may
on

with

of the

one
a

gradually reduced until the desired


slightdepositagain makes its appearance.
diameter
of the test-bar and the current-density
may
that the proportionof acid can
be varied between
is an average
that the yield of metal
The
testone.
made
this result automatically
to show
by hanging
is next

which

of

arms

which

contact

acid increases.

other

closes the circuit of

The

the normal

given current, and under

simpledeposit,not

the

becomes

bath

weight of
the

the bar

acidified in order
automatic

an

Faroe's
with

even

was

increases,and
electric

the

the

Glaser's

from

solutions

arranged

that

with

the

excess

of
*

of

case

sq. metre

the

bath
In

be

must

this fashion

is effected.
electrolysis
has

obtained

very

pure

potassium-chromium chloride,

grammes
of potassium chloride.

Experiments."

depositthickens,the
weight is used to close

the

current-densities.

litre,266*5
per

the diminution

bell to silence.

of the process
Feree
Experiments.

grammes
180 amperes

to avoid

In this

belL

to reduce

low
relatively

per
233

nearly neutral

control

metal

soon

action

"

silver-white

as

of the apparatus, only


increasingin thickness,is thrown down. If

more

of the

circuit

provided

bell

"

to stop the ringingof the bell. In order


of the acid present, the test-bar is so

is

arm

electric

an

deposit that is to say, if the proportionof


bath is then only neutralised justsufficiently

the bar has lost its

as

The

balance.

of

The

tained
conelectrolyte

chromium
The

chloride,and

used
current-density
per sq. ft.].

[14*4amps,
G. Glaserf has studied

exhaustively

current-density,
temperature,
the electrolyticdeposition of chromium.
electrolyteson
Chromium
solutions
chloride
containing 100 grammes
the followingresults:
chromium
per litre gave

the

influence

of

and

concentration

of

of

"

Bulletin Soc. Chim,, 1901, Series 3, vol. xxv., p. 617.


Bericht aii die detUsche
elektrodiemische
ZetUchrift/iir
EleklrocJiemie,
1901, vol. vii.,p. 656.
t Neumann's

Oesellschaftin

502

SMELTING

ELECTRIC

Under
form

AND

REFINING.

these conditions the chromium


separatesout in a coherent
below 50* C, but as a black powder above that temperature.

Alterations

followingtable

as

shown

in the

has

patented

"

Process.

Krupp's

affect the results

in concentration

The

"

firm of Friedrich

Krupp

free from
carbon,
process* for the depositionof chromium
ferro-chrome
in
contains
anode
(which
using ordinary
carbon)as
of fused alkali-metal chromium
chloride.
an
electrolyte
consisting
well
for
The
does
jiot
promise
practicaluse,
process, however,
it requiresthe employment of earthenware
as
diaphragms which,
a

is well

as

The
is almost

known,

Uses
the

not

are

Chromium.

of

only

in fused

durable

very
"

^The

salts.
chrome

production of

of metallic
application

steel

chromium.

MOLYBDENUM.
and

the
the
Metal.
Among
compounds chieflyfound in nature, the sulphide,MoSg (Molybdenite),
and the molybdate of lead, FbMoO^ (Wolfenite),
alone
used for the productionof molybdenum and its compounds.
are
Occurrence

Molybdenum
metal, which
in the

is

Properties

"

white, extremely lustrous, and

it has
fused

of

hitherto

been

condition.

hard
very
exceedinglydifficult to obtain

Its

specific
gravity is 9*01. Its
melting pointapparentlyapproximates to that of chromium, and
should therefore lie between
liSOO*"and 2,000''C. The alloys

pure

molybdenum

of

in
solubility
In

the

have

other

not

the

air it begins
exception of nitric

molybdic acid,

yet

been

studied, but

in

respect of

metals

acids

it appears
chromium.
to resemble
to oxidise at high temperatures.
acid

which

converts

scarcely affect
*

German

Patent

it into

molybdenum.

81,225.

With

oxide
Of

or

the

503

MOLTBDEKUM.

numerous

molybdic acid,
produced; it is
thio- salts

is the
acid

trioxide,M0O3,

important

most

in character.

alkaline

with

characteristic

the

compounds

oxygen

The

sulphides.

and

the

the

so-called

easily
sulphidesreadilyform

All

the

most

oxides

possess

colours.

Produotion

of

Molybdenum.

The

"

method

of

producing

from
molybdenum depends upon
molybdenite or from oxides produced from minerals containing
the metal;
limation.
by roasting,leaching,and precipitationor subwhether

either

In

sulphide by

the

case

it is to

furnace

electric

dissociating
process,

be

and

obtained

is

for

for the

used,

oxide

the

by

reduction.
Production

trom.

molybdenite
heated

dissociates

into

electric

furnace

in the

experiments, which
oxidisingeffect of
product contained
considered

crude

so

with

in

being

by

carbon

that

shown

the

that

sulphur
of air.

when

In

his

crucible,the
carbon, the

carbon

much

of

use

scarcelybe

it could

The

theoretically
only 5 '88 per cent, of carbon, whilst the
fused
from
molybdenum obtained
denite
molybby Guichard
found
iron
consist
91*8
of
to
was
Mo,
containing
per
Fe,

the

"

the

exclusion

checked

2-1 ; and C, 6*64.


In
of Oxide.
Beduction

cent.

has
and

molybdenum

conducted

were

air

Guichard^

"

metal, but should rather be regarded as


carbide, MogC, actually produced by Moissan

as

carbide.
contains

Sulphides.

author

has
[Borchers]

shown

earlier
that

edition

both

the

of this
and

oxide

work
the

comparatively volatile trioxide,M0O3, *^" readilyreduced by


heated
His
of electrically
carbon.
means
experiments on the
conducted
reduction
of the trioxide were
during the years 1888
furnace
described
to 1890, using the resistance
on
pp. 103 and
In these experiments the product always contained
491 above.
carbide than metal.
less
more
or
carbon,and therefore held more
of
Moissan
f who, at a later date, accomplished the reduction
obtained
with
fusion
carbon
in
the oxide
furnace,
an
arc
a
by
metallic
looking material containingfrom 9*8 to 9*9 per cent,
He
took the precaution to use
then
of
of carbon.
mixture
a
molybdenum oxide with a quantity of carbon insufficient to
then so heated
in his
reduce
mixture
it completely. The
was
that
whole
the
electric furnace
of the charge contained
in the
crucible

carbon

quite
charge was
not

fuse.

contained
It
*

is

not

up

to

fused,and

Under

formed

the reduced

and

was

these

metal,
99*98

the

between
which

per

scarcelynecessary

that

conditions

was

cent,
to

carbon
almost

the
a

p. 1320.

metal

did

layer of unreduced

walls

of the

free from

crucible

carbon

and

of

molybdenum.
point out that

Comptes BenduBy 1896, vol. oxxii., p. 1270.


R"ndus, 1893, vol. cxvi., p. 1225,

f Comptes

reduced

and

alloysmay
1895, vol.

be

cxx."

504

ELECTRIC

produced
and

direct

other

TJBes

REFINING.

AND

by reducing

of

mixtures

metallic

of

Molybdenum.
the metal

molybdenum,

molybdenum oxides
of alloysof this
Sargent.''^

A
oxides.
large number
examined
obtained and
by

been

have

nature

SMELTINQ

these, however,

Owing

"

has found

is its

of

sources

applications.Among
production of molybdenum

the

in

use

the restricted

to

but few

steel.

TUKOSTEN.
and

Ooourrenoe

of

PropertieB

the

the
Among
tungstic ochre,

Metal.

"

naturallyoccurringcompounds of tungsten are


and
The
latter
wolflpwn,FeWO^.
WOj; scheelite,OaWO^;
mineral
frequentlyaccompanies tinstone, a fact that was men"
tioned in the chapteron Tin,
Tungsten forms a grey crystalline
powder, or after fusion, an almost white, very lustrous and hard
metal, having a specific
gravityof 19. Its fusing point cannot
be quite as
high as those of molybdenum and chromium,
although it is commonly reported to be so, for the author has
succeeded
the powdered metal
in fritting
togetherin a regenerative
at
to
cause
a
furnace,
high
sufficiently
temperature
gas
the softeningand collapseof the best Hessian
while
crucibles,
introduced
and molybdenum
at the same
powdered chromium
time
and
chief
The
remained
unfused.
quite dry
alloys of
"

that

tungsten
have

found

studied

those

are

in the steel
specialapplications

only beginsto
the air.

been

have

Of

oxidise

the

(the trioxide

at elevated

iron;

these

industry. Tungsten

temperatures when

simpleroxides, WOg

two

with

and

heated

WO3,

the

in

latter

tungsticacid) is most easilyformed ; it is acid


in character.
The trisulphide,
WS^, also functions as an acid,
thio-salts
with
other
readilyforming
sulphides,those of the
alkaline sulphidesbeing soluble in water.
or

Treatment

Preliminary
duots.
be

the

Slags containing tungsten

"

considered

tungsten, in
The
above.
If the

of

ores

among
addition

the
to

raw

the

and
Waste
Ores
from
the tin works

materials
natural

for the

Fromust

extraction

of

tungstates enumerated

tungsten is also present in these slagsas tungstate.


are
not required for the direct smelting of tungsten

alloys,they, like

the

slags,must

be

treated

so

as

to

obtain

tungsten from them in the form of the trioxide,WO3, or


This is eiSected by roastingthem
so-called tungsticacid.
with
The
thus
is
soda under
conditions.
verted
conoxidising
tungsten
the

into
the
acid

is

solution

which
tuiigstate,

sodium

metals, such

as

iron, form

precipitatedby
of the sodium

means

is soluble

insoluble
of

oxides.

in water, while
The
tungstic

hydrochloricacid

from

the

salt.

*Joum,
of Anier. Chem. Soc,, 1900, vol. xxii.,pp. 784
schri/t/tir
L'Uktrochemie,1900, voL vii.,p. 433.

to

792.

ZeU-

506

ELECTRIC

SHKLTIKG

AND

REFINING.

UBANIITH.
of

Properties
Pitchblende

Metal.

the

The

"

which
(Uraninite)

is

only noteworthy
urano-nranic

is

ore

oxide, U3O.

hard
is a white, lustrous, very
2U0-). Uranium
metal
01
high uisingpoint (not yet accuratelydetermined). It
is specifically
heavy, its specific
gravitybeing 18*6. It oxidises
in the air only at relatively
high temperatures.
when
heated
It ignitesin pure
Of the
to 170" C.
oxygen
at
even
finely-divideduranium
halogens, fiuorine attacks
chlorine
b
romine
attacks
it
at
at
ISO'',
ordinarytemperatures ;

UOj

210*, and

at 260"

iodine

and

in each

C,

with

case

with

It combines

of heat

evolution

about

500^

G. to form

sulphur
light.
1,000" G. to
sulphide,and with nitrogen at about
divided
the
nitride.
When
metal
finely
produce a yellow
activity
radiothe
normal
The
at
decomposes water
temperature.
at

black

of melted

is remarkable.

uranium

the
precipitationprocess was
in
Peligot,* 1842,
it from the fused chloride by
obtained the metal by precipitating
used
sodium
in place of
adding potassium. Zimmermannf
chloride
posed
is, however, readily decompotassium. The uranium
and
action
of
of
the
the
the
in
moisture
air,
by
oxygen
Process.

Precipitation

first used

and

for the

these

preparationof uranium.

methods, therefore,as

generallyyielda
double

brisklywith

of

uranium

sodium,

and

sodium,

with

evolution

'4 per cent, of uranium.


There
still
Process.
are
"

in which

by

(German
result

shown,

UCL

ties
quantistable

2NaCl,

of neat, and

which
gave

containing99

Reduction
oxide

since

has

impure by considerable
Moissan, therefore,prepared the more

reacted
metal

Moissan

rendered

metal

oxides.
chloride

of

"

means

it is said

to

be

The

of carbon.

some

impossibleto
author

chemical
reduce

books
text-

uranium

in the
[Borchers],

edition of this work,


of his

all oxides

were

published in 1891, stated,as


during the years 1887 to 1890,
heated
by carbon if electrically

observations
reducible

He

had

also at that time

first
the
that
to

effected

sulHciently
high temperature.
the reduction
of both naturallyand artificially-produced
oxide of
both
carbon
ui*anium, although the resultingmetal contained
This
and
and
was
nitrogen (carbides
nitrides).
owing to the
of carbon
fact that he employed an excess
in the charge,and the
then available was
resistance
furnace
not adapted to protecting
the metal
from the nitrogen of the air.
Moissan, in 1896, also
tried similar experiments with the same
result,the carbide or
metal
produced containing from 2 to 13*5 per cent, of carbon,
"
Annalea
CJiemie und

Pharmacie, 1842, vol. v., p. 5.


1842, vol. xcvii.,p. 256.
d. ccxi., p. 290.
t Liebig'sAnnalen
der Chemiet 1886, vol.
X CompUs Bendtis,1896, voL cxxii.,p. 1088.
~

de

Chimie

et de

Pharmaeie,

"

'

"

Annalen

der

507

MANGANESE.

the

accordingto
of

of carbon

excess

and

carbon

reduction

Using an insufficiency
ceeded
sucheating period Moissan
nearly free from carbon, but still

obtaining a metal
containinga little oxygen.
in

Methods.

Eleotrolytio

from
electrolytically
sodium

which

from

states, in the

"

the
he

paper

same

had

above

used.

short

Moissan

also

double

chloride

obtained

precipitatedit
refeiTed

with

to, that

uranium
and

of uranium

He

sodium.

the

current

was

from

8 to 10 volts and 50 amperes,


at
kept during electrolysis
of the apparatus and
without, however, statingthe dimensions
and
the
free
of
from
electrodes,
hydrogen,
nitrogen,should be
directed upon the fused mass
duringelectrolysis.The uranium
the
cathode
by this process in the form of small
separatedat
When
which
sometimes
attained
a
crystals,
length of 1 mm.
the
cooled
free
from
washed
metal
was
was
electrolysis
complete
alcohol.
and then with
slag,first with water, as cool as possible,
metal

The

so

obtained

contained

from

99 -27 to 9 9 '48 per cent.

of uranium.
Uses
uranium

of

has

the
not

Metal.

Apart

"

yet found

any

from

experimental purposes,
applications.

permanent

MANGANESE.
Ooourrence
occurs

and

chieflyin the

Properties
form

is the

pyrolusite,
MnOg,

of

of

the

Metal.

oxides,of which

"

the

Manganese
binoxide

or

important, the oxide, Mn^Pg, is


found in braunite,the mangano-manganic oxide, MugO^, in nausin manganite ; a sulphide
mannite, the hydroxide,Mn20o(0H^,
in Hauerite, MnS^; salts in dialogite(rhodochrosite),
MnCOg,
rhodonite
in psilomelane,
which
and
is a
(manganese silicate),
oxide, baryta, and
complex manganite containing manganese
potash with manganic binoxide.
Manganese is a white, lustrous
with
metal
reddish
It is of medium
tint.
a
slightly
weight
(specific
gravity 7 to 8), very hard and brittle,and melts
between
1,200"and 1,500" C, but its exact fusingpoint has not
those
Of its alloysthe best known
are
yet been determined.
and spiegeleiaen
with
and with copper
ivon^-ferro-Trutngaiiese
It
bronze.
is capableof alloyingalso with chromium,
manganese
most

"

"

silver, and

aluminium, tin, mercury,

the

active

other

noble
Pure

metals.

a
ganese
manChemically, manganese
very
oxidises slowly in the air at ordinarytemperatures, but
small
It
a
rapidly if it contain even
proportionof carbide.
readilycombines with the halogens,as with sulphur,phosphorus,
and boron.
It dissolves readilyin all inorganic,
carbon, silicon,
and in many
organic,acids,usuallywith evolution of hydrogen,
and
the formation
with
of manganous
salts.
Alkaline
always
when
hydroxides,especially
oxidisingagents are present,dissolve
forming manganites,manganates,and permanganates.
manganese,

is

element.

508

ELECTRIC

AND

8MBLTINO

REFINING.

oxide, MnO;
compounds the manganous
Among the oxygen
and
oxide,
oxide,
mangano-manganic
Mn304,
manganic
Mn^O, ;
baaic in character, yieldingmanganous
are
or
manganic salts,in
which

MnO^,

The
is present in the form of base.
manganese
the so-called manganic acid,Mn03 (not known

and
state),

combined

the

acid,Mnj07, function as
series of salts,many
a

known
heptoxide,
acids.
They unite
of which

are

also

binoxide,
in the

bases

with

un-

permanganic

as

form

to

of considerable

value

the arts.
forms
The binoxide
acid gives manganates

in

GaMnOj),
manganites {e.g,,
(e.^.,
E^MnO^), and the heptoxide
for
The
choice of an
ore
yieldspermanganates (6.^.,
KMnO.).
intended
to prosmeltingpurposes depends upon whether it is
duce
metallic manganese
the
or
a
Usually
alloy.
manganese
because
is not produced sufficiently
alloyis required,
manganese
in the arts to warrant
cheaply,and has not sufficient applications
For the
the erection of a plant specially
for its manufacture.
and
ferromanganese,manganiferous
preparationof spiegeleisen
iron

and mixtures

ores

Beduotion

of

of iron and

Manganese.
reduction.

effected

ganic
man-

manganese
The extraction

"

be

may

ores

used.
is

of manganese

For

spiegeleuen
e^ud/erro^ianganew
ganese
(spathicores after calcination)or manreducible
with
oxide
mixed
iron
easily
ores, are
ores,
smelted
with
fluxes in blast furnaces (almost exthe necessary
clusively
in crucibles,the fluxes being so proportioned
so now), or
that a manganiferous basic slag which
must, at the highest,be
shall be produced. When
contains
the metal
a mono-silicate
from 5 to 20 per cent, of manganese
it is termed a spiegeleisen
;
solelyby
manganiferous iron

ores

"

"

with
the

which
manganese,
range
up
may
of
blast
the
product
furnace,it is known

to

more

These

in
alloys,

contain
The

addition

as

varying percentages

to

85

cent,

per

in

ferro-manganese.
of silicon,
always

from

4 to 7 5 per cent, of carbon.


extraction of metal free from carbon

(and,therefore,from

of
even
by the reduction
yet been effected,
the pure oxide in the electric furnace, no matter
how accurately
the quantity of carbon
have
added for reducing purposes
may
measured.
been
The
of
metal
reduced
the
at
an
beginning

carbide)has

never

electric furnace

in the

probablycontains

of this
in the

compound, since the


metal
electrically-smelted

above

mentioned

Precipitation
obtained
sodium

carbide
Process.

contains
"

was

Manganese

manganese
a

produced

considerable

tion
propor-

percentage found

the
4 per cent, and
carbon.
of
6*77 per cent,

about

only

Brunner^

carbide.

carbon

lowest

of the

the remainder

exi"erimentrapidlywithdraws carbon from


with
it to form
charge, and combines
carbide,MugC, decomposes water ; and the

considered

that

he

fluoride

by fusing manganese
pure
manganese
in a Hessian
crucible. He
must, however, have

more

manganese
*

silicide than

metal, for,Wohler

Pogg, Annaien, 1857, vol. ci.,p.

264.

had
with

duced
proafter-

509

MANGANESE.

that

showed

wards

the

contained

product

6*4 per

to

up

cent,

of silicon.
oxide
process* for reducing manganese
hj
So
heat
metal.
much
is
a
means
yields purer
generated in the reaction that there is no necessityto heat the
It is only necessary
external
the
from
to kindle
sources.
mass
of an
mixture
by means
ignitingor priming charge having a
of
in order to effect the fusion,
combustion,
higher temperature
of
but also of the alumina
the precipitated
not only
manganese,
slagresultingfrom the operation.

Goldschmidt's

of aluminium

ELECTROLYSIS.
or
Electrolysis of Dissolved
Anodes.
with
Insoluble
Compounds

The

opinion that, given a high

and

metals, as

account

other

well

aqueous
confirm
what

in that

was

exceedinglydifficult to
adhering to it that

so

the

for

short

unattacked.

time

on

f in 1 854,^

separated from

be

The

author

chapter,but

free the

solution

Chapter

of Bunsen

could

chloride.

the

written

Manganese

the

current-density,
manganese-

chromium,

as

of

solution

the
is

was

Fused
In

"

given of the work

Chromium
and of his

an

of

is able
add

must

from

deposited metal
be

can

manganese
The
process,

to

that

it

the

kept only

therefore,is

not

applicable.
technically
order

In

obtain

to

in

proceed exactly as
point of the metal
and

method

In

nium.l

this

of fusion

permit of the applicationboth


under
apparatus already described
mixture

case

by

conducted

be

fluorides
be

and

of this
Alumi-

other

maintained

volatile
non-

in

density,and

of
to

high
The
electrolysis.

in

the

current

exactly as

of

oxide, would

manganese

time, be submitted

same

case

would

of the

salts,with
state

be possibleto
it would
manganese
of aluminium,
for the melting

pure
the

of

reduction

would, at the
operation would
aluminium, only

that a steady
higher temperature; and it is conceivable
maintained
in this
be
of
fused
might
production
manganese
In any case, aluminium-manganese alloysmight readily
way.
at

be

the

serve

same

Soluble
salts of
with

the pure

as

purposes
Fused
of

Electrolysis
Anodes.

"

would, under

these

produced,and

so

In

are
manganese
of manganese

anodes

Manganese

proposed by Yoltmer" haloid


process
be electrolysed
in the fused state
oxide

and

carbon, unless

oxide direct to
the manganese
and
of oxides
carbon
electrolysis.Anodes
of the
"

failure

was

their

proposed by
explained at length under
use

Cf. Chromium, p. 495.


t Cf. pp. 127-129, 145-161.

with

Compounds

to

to add

successful since

circumstances,

some

metal.

was

the

it

were

fusion

have
Deville

never

; the
Aluminium.

ferred
pre-

during
been
cause

The

t Pogg. Annaien, 1854, vol. xci., p. 619.


Patent 74,959.
" German

510

ELECTRIC

AND

SMELTING

REFINING.

that the
conducted,accordingto the specification,
powder, which is then to
separates as a crystalline
manganese
and
the
still clinging
be pressed
washed
to separate
electrolyte
this
of the manganese,
But
to it.
owing to the ozidisability
rise
if
it
last operation would
to
even
great difficulties,
give
could be accomplished
satisfactorily.
Friedr.
ferroThe
of
Krupp, of Essen, by which
process

operationis

so

used

be

manganese

is to

manganese

salts,has

anode

the

as

already been

in

bath

described

fused

of

the

in

chapter

Chromium.

on

book, to reduce

of this

that

to

[BorchersHproposal,made

author's

The
edition

in

employed

productionof manganese,
oxide
of manganese
electrolysis
reduction

fused

process
is similar

dissolved

fluor

and

but

electrolytic
means;

beyond

this

the

fluor spar with


oxides
by carbon.

oxide

obtains

apparatus
the

in

of manganese

spar,

that

to

he combines

in which
dsc.],

'by introducingmanganese

effects this

similar

extractingaluminium,
English patent* [foran

for the

electro- thermic

previous

in Simon's

found

afterwards

by

manganese

the

in

in

bath

from

manganese
he adds
to

He

of electrically
it

the

by

bath

the carbon
for its
oxide with
of manganese
necessary
The
inventor
reduction.
the
to reduce
in this way
proposes
the
electric
he
of
since
that
cost
furnace,
anticipates
prime
mixture

thus
furnace
be considerablyincreased.
may
alone would, he
of
production
by electrolysis
manganese
considerable
scale, require a
considers, if attempted on any
furnace of colossal size. Simon
states that by working in this
the

output

per

The

almost
all the silicon
way
be volatilised in the form
would

be

free

manganese'
carbon

being formed

source

the

in
the

for

the

of water

obtained

is
in

is

the

would

ore

scarcelyto

from

scarcelyconceivable
the

fused

be

this furnace

condition

that
with

contemplated in the Simon


carbide
proportionof manganese

manner

considerable

time.

same

t has developed Simon's

project
of

at

It

obtained

in

It

of fluorides.

carbon.

be

cathodes

furnace, without
Gin

from

would

phosphorus

the metal

that

however,
anticipated,

and

idea in connection

Orlu

at

power

with

larger
ferro-manganese,utilisinga
Thermos
in the South
(Aix-lesa

of

manufacture

France).
Heroult's

by
use

Frocess.

H^roult, and
in connection

"

very
with it,are

have any
of metals, which
and of the alloysof such
"

process proposed in the same


year
simple form of apparatus designed for
A

far better suited

very

to the

production
carbides,

great tendency to form

metals, if

it is wished

to obtain

them

EnglishPatent 17,190,Sept.27, 1900.

t La
Proc^4

JabricationEUctrique du Ferro- Manganese


Simon, Paris, 1901.

en

France, Gustav

Gin,

511

IRON.

of
account
an
repetition,
Iron.
on
chapter
given
of
Applications
Manganese.
Manganese is principally
used
of spiegeleisenand
in the iron industry in the form
for
the
desulphurisationof pig iron, and for
ferro-manganese
carbon.

free from

In

order

proposalswill be

these

avoid

to

in the

"

of steel.

the recarburisation

CHAPTER

XII.

IRON.
Occurrence

of

constituent

of the

(up

to

25

Native
Nature.
earth,is but rarelyfound

Iron

sources

foand

in

the

"

weight) of

in

tons

in

are

following ores

FpgOj ; magnetite

magnetic

met

iron

principalis

Oxides

glance and

an

from

terrestrial
extra-

of iron

are

red

haematite,
limonite,brown

FcoO^ ;
Of sulphides,
FeO(OH)4.
Yefi^iOU)^
iron pyrites,FeSg, which
is employed for the
or

haematite,mmette,
the

with.

Iron

"

original
largemasses

; but

iron derived

meteoric

sometimes

as
ir(yii,

ore,

to

of

sulphuric acid ; after roasting,the calcined


but very rarely,
smelted in
product (purpleore) is occasionally,
The
chief salts employed in the iron industry
blast furnaces.
are
spathic iron ore, FeCOj, and vivianite,Fe3(P04)2. The

manufacture

above

contain
silica and
silicates,calcium carbonate,
may
oxide
and
carbonate, oxide of chromium, alumina,

ores

manganese

ko,, which

be

must

taken

into

in the

account

smelting of

the

metal.
The metal known
in day
The
Properties of the Metal.
everybut
of an
life as iron is never
consists
iron,
always
pure
in
which
the
this
metal
is
but
which
principalconstituent,
alloy
"

also contains

Carbon

and

the

followingsubstances

carbides

of

in

varying proportions:
"

iron,silicon and

silicides of

phosphide,and sulphideof iron,manganese,


nickel,copper,

""c.

Chemically pure
specificgravity of
and shows
a
high
temperatures
1,600"C, and

iron,oxide,
chromium, tungsten,

it is
it is

iron
7*86 j
lustre

has

an

atomic

it possesses

weight of 56 and a
greyish-whitecolour,

At
polished surfaces.
ordinary
magnetisable. Its melting point is about
capable of alloyingwith most metals, even
on

in some
limited.
be somewhat
It remains
cases
solubility
unaltered
latter is
time
in
when
the
long
dry air,but,
oxidises
in the cold. At high temperamoist, it
rapidly even
"tures it is oxidised
even
by dry air,as well as by oxygen, and
if its

for

512

ELECTRIC

the

SMRLTI90

AND

REFINING.

of
Most
being decomposed by the metal.
less
with
some
iron,
more
or
readily
the halogens at ordinary temperatures. It is easilysoluble in
dilute mineral
in strong acids,
most
acids,and with difficulty
but remains
almost
insoluble
(passiye)in strong nitric acid,in
of
the
formation
of a superficial
coating of oxide.
consequence
The
the
of
derived
iron are
from
more
important compounds
FeO, and the peroxide (ferric
protoxide (ferrous
oxide),
oxide),
considerable
third
in
of
itself
is
oxide, Fefi^,
ance,
importFe^Os ^
treated with acid it yieldsonly ferrous and ferric
but when
oxide, FeOg,is not met with in the free
compounds. Another
ferric acid, and
as
acid, it is known
state, but) acting as an

by steam,
the

latter

metalloids

combine

"

"

"

combines

with

bases

ferrates,which, however,

form

to

are

readilydecomposed.
The
melting point,hardness, structure, and other physical
propertiesare mainly afiected (but the chemical propertiesonly
named
in a small degree)by the presence
of the constituents
above as being present in commercial
samples of iron. This is
the influence
of each foreign element
not the placeto describe
but
the
the
short
of the commetal ;
account
mercial
following
upon
that carbon
varieties of iron will suffice to show
playsa
this
the
of
metal
in
most
:
important part
metallurgy
least 2*3 per cent,
1. Pig Iron and
Cast Iron. With
at
of carbon; melting point between
IjOTd"*and 1,275" C. ; non"

"

malleable.
Iron,

(a) White
of carbon

very
; silver- white, lustrous, brittle,

material

raw

solidified without

Oast iron

"

which

from

malleable

any

separation

hard, forming

the

iron may
be made.
which
of the
some

dissolved
(6) (7reyIron^ or cast iron,from
of graphite on solidification ;
has separated in the form
black
it has a crystalline
a
fracture,
structure, and
grey or
the
the colour being due to the graphiteplateslyingbetween
is
material
of
the
and
raw
foundry,
crystals
; it is the principal
carbon

also

2. Malleable
carbon

; the

and

Iron

Steel.

^With

"

fusingpoint lies

between

1*6 percent. of
1,400" and 1,700" 0.; the
at

most

is malleable.

metal

(a) Steel.
"

hardened
then

iron.

of malleable

source

malleable

almost

suddenly coolingit.

(6)Malleable
being

Iron.

hardened

material

brittleness

to

"

by

It melts

which

is

by quenching,and

red

metal

of

being

heat

and

1,600"C.

and
1,400**

between

malleable

capable

heatingit to

scarcelycapable of

melting between

1,600" and

1,700" 0.
As

methods

will be
of

seen

in the

manufacture

short

sketch

the

malleable

given below,
iron

never

in

some

becomes

out of the impure (but easily


perfectlyfluid ; but it crystallises
fused)melted cast iron, so that for the formation of a solid mass
the pure
iron crystalsthat have separatedmnst
he welded together

514

BLKCTBIC

productof
manganese,

the

sulphide,and
copper
The
not

chromium

use

of the

though

even

which

will

made

iron with

iron
silicides,

phide,
phos-

metals, such

other

with

with

so

howeyer,

of this branch

as

that it is

of

metallurgy,
proposals
given
furnace
objectof replacingthe blastof the

shortly be
the

methods.

It

be

may

membered,
re-

that, of all the

the outset

at

metallurgical
of treating
thoroughlyworked

its process

industry,with

industries,the blast-furnace

well understood

electro-chemical

by

process

is

in detail

account

an

alloy of

an

The

in addition.

treat

been

have

often

blast furnace

to

necessary

oxide,

introduced.

so

carbides,silicon and

and

and

be

is therefore

blast furnace

carbon

RBFININO.

AND

they should

that

desii*able

purposes

SMELTING

produced,has been the most


furnace which
has yet attained
out.
no
metallurgical
laid upon this,
Stress
be
must
to so high an
energy efficiency.
the
that the difficulties may
be appreciatedwhich
in order
the waste

gases
There
is

electric furnace

must

in order

encounter

to

the

compete with

circumstances
clearlyexplain
existing blast furnace. These
methods
when
electric
the
in course
time
at
were
why,
heating
of development,the first experiments aiming at the application
extended
of electricity
in the metallurgy of iron were
to the
with
inventions
made
and
of
The
iron.
the
finishing
refining
view of simplifying
or
hasteningpig-ironprocesses by the application
of
and
of electricity
newer
arose
therefore,
origin,
are,
from

the need

to

power

which

has

development
The

become

iron before the


statements

Process.

dynamo

which

return, the

have

invented,or

was

the

appeared in

the

during

is not

which

dressingof
been

have

been
iron
the

of

number

dailypress

of

erroneous

with

His

reference
be

first to

endeavour

methods

by

first electric furnace

in serious

processes

working
a

process
resembled

earnest, and

of
a

existing
smelting by electricity.
blast furnace
in design,

in consequence,
designatedan electrical blast
iu the accounts
given in the technical press.f This

is actually
built and
power

in the

in

Camonica

use

in connection

Valley in

with

scale,to replacethe

was,

even

traced

applied to the electro-magnetic


successfully
ores.
Apart from these, Stassano appears to

practical
experimentson
blast-furnace

later

proposed to
smeltingof

of iron

have

water

the electric

treatment
electrolytic
ores, which
may
confusion
with, and misunderstanding of,various

and

It

"

publicationsrelatingto

to the

to

moderate

so

Fig-iron

Stassano

largelyavailable
industry.

of the

of certain

treat

with

even
utilise,

with

the Brescian

source

furnace,
furnace
of water-

Alps (Northern

edition to a publication
is made
in the German
by
Verein Deutscher
entitled OemeifrfdsdicheDargt^Eisenhuttenleute
DuBseldorf.
lung des Oesamtnten EiaenhiiUemcesens,
Tbanslator.]
der Elektrochemie,
+ English Patent
See also Jahrbuch
11,604, 1898.
*

reference
[Special

the

"

1899, vol. vi.,p. 320.

515

ibon;

Italy),although
furnace
Better

work

who

those

would

have

have

had

experience

predicted the

in

failure of the

electric
process.

obtained

hy Stassano, may be ascribed to


his having departed from the original
In
design of his furnace.
he
also
has, however,
doing 80
given up the production of pig
and
iron by electrical means,
has undertaken
the smelting of
purer

results,since

"

malleable
so

process,

"

direct

iron

modified,will

chapter referringto the


H^roiilt's

century,

be

from

dealt

the pure Italian ores.


The
with
in the portion of this

productionof wrought
Towards

Prooess.
H^roult, whose
"

the

end

of

iron.
the

is identified with

name

nineteenth
the

modern

extraction,took o\it in the various civilised


process of aluminium
countries a number
of patents for the productionof iron and other
The most
allied metals.
important of these patents, it is true,
of pig iron into a purer form of metal ;
related to the conversion

proposalfor the extraction of crude metal, as it appears


deserves
in other patent specifications,
consideration on account
the reduction
of its simplicity. In this process
is effected in a
simple form of electric furnace,which will be described hereafter,
the ore
is pre-heated by the combustion
while
of the gases
produced during the reaction in the electric furnace in a shaft
side of the furnace.
is provided at one
which
The
carbon
to the
reduction is not usuallycharged with the ore,
necessary
but is introduced
of a specialchargingdevice direct
by means
the
electric
furnace.
It
into
can, however, be pre-heatedto the
which
the
takes
reaction
at
temperature
place by passing a
of
air
current
through it,and, therefore,at the expense of
gentle
small
H^roult's intention was, therefore,
a
portion of the carbon.
of the energy
of the carbon
to utilise the whole
by giving
but

the

electrical assistance
it

was

sought
that

to

had

to the process

prevent

the

of reduction

escape

from

; and

the

in this way
of any

furnace

been

completely burnt to carbon dioxide.


This suggestionis undoubtedly based on a good foundation, but
how
far it can
be realised in practiceis a questionto which
no
the
short
be
time
to
answer
can
satisfactory
given owing
yet
that has elapsed since the first preliminaryexperiments were
carbon

not

tried.
Harmet'8

Prooess.

H6roult's

"

Those

who

had

knowledge of
any
have
read with
some

experiments and patents will


surprise
publicationswhich have been made
by Harmet
The
first of these, a pamphlet
during the last two years.
in
Paris
the
on
published
production of iron and steel by
electrical methods, was
nothing but a descriptive
practically
illustrated
of Heroult's
account
suggestions,described above.
The
of
electi-ical
iron
an
drawings
smeltingworks given in the
pamphlet might indeed be taken as an illustration for Heroult's
so
closelydid it express in the form of
patent specification,
of giving effect to his proposals. This
drawings the manner
the

M6

SMELTING

ELECTRIC

drawing
electric

reproduced in Fig. 239. The


smelting furnace, S, into which

side and

is

coke

from

reactions in the

electric furnace

exactlyas explained in
however, seeks

Harmet,

electrical
in

The

the other.

shaft, E, togetherwith

of the

REFINING.

AND

heating,and

furnace, E, the

gases

plant consists
ore

is fed
into

for their

the

air necessary

the

descriptionof the

an
one

the

produced during

introduced

are

of

from
the

ore-

combustion^

H6roult

process.

pre-heatingof the ore by


has, therefore, arranged in various parts
electrodes shown
by thick black lines
to

assist the

Fig. 239.

Fig. 239.
The

"

Drawing

of

an

electrical iron smelting plant,after Harmet.

coke-chargingof shaft K
metal
tapholesof the

is

slag and

from

the furnace

with

arranged

at

the

side of the

electric furnace, so that


first
the slagwithout

no

ore

passing
filtering
layer of coke and so becoming reduced.
The
crude
iron produced in the smelting hearth, on
being
flows
into a refinery,
which
is also electrical,and
in
tapped,
which
form
of construction
used
H^roult*
is
a
at
once
by
recognisable.
has not carried out H^roult's ideas in their
Although Harmet
may

escape

through

Compare

pp.

521-623.

517

IRON.

entirety,the
writers

some

well

cannot

to have

Saint- Etienne
for

on

credited

be

to

Harmet,

as

believed.*

appear
in a communication

Harmet,
Mineral

invention

electric

the

to

the

5th

of

SocUte

V Industrie

de

April, 1902, described

s;neltingworks, in which, by
and
of various
means
complicationsin working, he
apparatus
renders
if not unworkable
in practice,
a
very difficult,
process
worked
out
was
which, as
thoroughly practicable.
by H^roult,
Assuming the country to be hilly,he arranges shaft furnaces,
design

new

above

one

another

temperature by
The

an

material

iron

heats the

and
terrace-wise,
of carbonic

means

pre-heated is

oxide

to its reaction-

ore

in the

highestof

delivered,in

the

these.

first

place,
to
shafts,from which it is transferred
collecting
the actual
blast furnace
These
shafts
two
as
are
required.
arranged on the platform of the blast furnace side by side. A
is provided for the coke at the throat of the
pre-heatingchamber
blast furnace by a prolongationof the shaft of the latter.
This
dioxide
coke serves
of the gases produced
to reduce the carbon
during the reduction, and a certain necessary
quantity of the
into two

so

now

small

intends
the reduction
to the hearth.
Harmet
gases is returned
of the carbon dioxide of the furnace gases to monoxide
to take
in
place initially

cinder-notch,while
Keller's

hearth.

the

the metal
A

The
flows

further

slag escapes
over

into

by

Heroult

illustration

Liirmann
furnace.

of

a
complete
iron-smeltingwork has been given by Keller of Paris,
whose
and
contained
account, with descriptions
drawings, were
in a communication
t by Bertolus to the Congress der Weissen
Xohle,
The
Keller
plant consists of a shaft furnace in which
the electrodes
indicated in Fig. 240.
are
arranged in the manner

Frooess.

"

electrical

two

electrodes consist of two groups connected


parallelelectrodes. They are introduced

the

roof

The

level

into

than,

the

made
hearth

fore-hearth
furnace
somewhat

placed

in

front

in

series,each

of

vertically
through

of, and

shaft ; and
the fore-hearth
wider
the furnace
than

at

lower

is in

quence
conse-

itself.

The

of the

is prepared like that of an open*


furnace,which
in
all
the taphole,
directions towards
furnace, slopes
opposite to which, but at a higher level, is the slaghole.

hearth

Beneath

taphole for the metal, and at one side of the blast


consists of a hearth with
furnace, is the reGning furnace, which
electrodes suspended from above and coming in contact
with the
top of the slag. At a lower level,a pit is provided in front of
the
taphole of this furnace, to take casting ladle or ingot
The smelting of the ore and the reduction
moulds.
of the metal
the
hearth
of
the
shaft
time
After
the
furnace.
on
a
begin
the

*Cf. The Mectro-ehemist


and
1902, vol. ii.,p. 18; and
Metallurgist^
^eitschnftfur Elektrochemie^1902, vol. viii.,
861.
p.
H*Bertolus, Notice
la Fabrication
dea Aciers au
eur
Four
Electriqtief
Paris, 1902.

518
carbon

monoxide

hot

react

to

The

furnace

to

When

sufficient

tapped

into

with
In

"

REFINING.

the

shaft

From

this

crucible,but

become

sufficiently
the

tion
redac-

placealso

in the

moment

takes

completely taken off and


generate heat for drying the
are

has

accumulated

it is

which

on

must,

Keller's arrangement of iron

contain

furnace, the

other

and

the

refiningfurnace

must

latter

is, among

to

metal

the

Fig.240.

the

in

ore

another.

one

gases

manner

he.ited,and

the

AND

of the furnace.

higher zones
suitable

and

with
confined

is not

In

SMELTING

ELECTRIC

quantity
crude

here, according to

in

material.

hearth, it is

of course,

be

pre-

-smeltingplant.

of material

metal

things,decarbonised

the

burned
raw

from
while

Bertolus'

the
in

already fused*
shaft
the

furnace

fused

dition,
con-

proposal,treated

lime.
the

furnace
refiningfurnace we recognise the Heroult
this is the only part of the whole
which
in
plant
electrical
has
of
probably
a prospect
heating
being appliedin the
of
iron.
A
furnace
metallurgy
patented by Keller and tha

again ;

and

519

IRON.

* has
at first sighta resemblance
to
Compagnie Electro-thermiqiie
the Hiroult furnace
in the arrangement
of the electrodes,
and
coald doubtless
be used with advantage in the manufacture
of
in connection
carbides,but it obviouslyneed not be considered
with the refiningof iron.

PRODUCTION

B. THE
In

order

necessary
with the

the

to convert
to

OF

from

remove

MALLEABLE

crude

iron

it those

IRON.

into malleable

constituents

iron,it

which

is

interfere

valuable

plished
propertiesof the pure roetil. This is accomin most
cases
by reducing the proportionof every foreign
almost to zero, and then, if necessary, restoringto the
substance
metal in suitable quantitythose elements
which
may be required
The
to give to it the specialqualities
sought.
separationof the
impuritiesis always effected by oxidation,either with or without
The oxidisingagent is sometimes
fusion.
atmospheric oxygen,
oxide
of iron
the magnetic oxide
sometimes
either
especially
added
from
the
of
iron
oxidation
directlyas such, or resulting
by
"

"

the air.
There
various

is

need

no

here

processes which

have

been

detailed

used

account

different

at

of the

times, and

ment
refiningand treatof iron by oxidation,reaction,adding silicon,
recarburising,
all
well
the
known
while
to
are
or
alloying. They
metallurgist,
the non-technical reader will find them
books
fullydescribed in textand conciselyin the Journal
Inst.
the
Iron
and
Steel
of
For
The
Siemens
Furnace.
reasons
already given, the
to
use
have, for the most
proposals
electrical-heating
processes
this
with
branch
of the metallurgy of
part, been in connection

under

the

into

to enter

varying

most

conditions,for the

"

iron.

Sir William

electric furnaces
of iron.
on

These

Siemen8,t

adapted
furnaces

in

have

pp. 121 to 123 of this book.


Pnrnaoe.
A
De Laval
The

De

means

Laval

without

an

in

for the

1893

the

first to

describe

of considerable

quantities
alreadybeen figuredand described

"

no

1878, was

to the fusion

interest

process and
of their own,

conversion

of

plant,which

pig

was

iron

by
proposed by
into wrought
are

iron.
The

to the
smelting furnace of De Laval is not ill-adapted
recommends
of
metals
The
that
in
inventor
smelting
general.
{
the iron ore
with the usual reducing agent should
be so heated
that the reduced
fused.
The
metal
is not
actually
melting of
metal
renders
further
the
by electrical means
refining
any
and
shaft
is
effected
in
low
a
furnace^
process
unnecessary,
*Jakrbueh
der Elektrochemie,1900, vol. vii.,p. 523; Joum.
qf the Iron
and Steel Inst.,1903, p. 187.
t Eoglish Patent 4,208, 1878 ; and 2,210, 1879.
t Engineering and Mining Journal (New York), 1894, vol. Ivii.,
pw 509.

520

ELECTRIC

ghown

in

Fig.

secion.
a

241

in

vertical

section, and

horizontal

hearth

The

bridge,C,

compartments

in

243

into

in

Fig. 242 in
longitudinal
by
compartments

vertical

small

two

C^

cooling arrangement,

laid tlie electrodes,D

E.

and

In

these

In

startingthe
I,
operation,the fused electrolyte,
is poured through the opening,B,

Fig. 241.
Vertical

REFINING.

cross-section,in

Fig.

is divided

fitted with
are

AND

SMELTING

cross-section.

in

the

cover

of the

at

the

same

time

and

E,

powerful

shaft. A, and
electrodes,

the

connected

are

electric circuit.

of the

in a
up
The
sistance
re-

must
electrolyte

be

great that the bath is maintained


at the melting temperature by the
direct conversion
of electricity
into
so

heat.

is
alternatingcurrent
used in order that the electrolyte
not
(e.g.,magnetic iron ore) may
be decomposed. The
metal
to be
used
is introduced
through B,
the
and, fallinginto
bath, becomes
melted

Fig. 242."

Horizontal

section.
De

electrode

chambers,

An

and

collects

Fig. 243. "Vertical

in

the

two

eectioii.
longitudinal

Laval^B electrio furnace.

where

it accumulates

until

it has

attained

it to flow away
through F or G.
depth to cause
is
of the
constant
by means
electrolyte kept
consists
of a hollow
The
opening, H.
cooling arrangement
flat inverted
metal
with
the
openings, C* and C,
trough, C,
the
which
introduced
through
removed.
or
coolingliquidis
a

sufficient

The

level

of the

522

ELECTRIC

brought

the

electrical

but
circuit,

of

slag,or

metal

to

be

smelted

at

the

same

the metal

between

In this way,

this way

In

and

onlj indirectlyinto the


he introduced
a layerof
heating resistance between

as

the metal.

REFINING.

time

to act
electrolyte,

an

the electrodes and


contact

AND

SMELTING

all direct

he avoided

inevitable

the

electrodes.

carbon

only in this way, is it' possibleto refine iron to


that it contains each
requisite
degree of purity,and to ensure
constituent
in exactlythe required
proportion.
and

the

grammatic
shows the arrangement of the electrodes in a diain section, whilst Fig. 245
sketch of the furnace
from
taken
the furnace
in
a
a
view,
photograph,showing
gives
actual operation. A bath of melted metal having been prepared

Fig. 244

either

in

the

vessel,the
with

electric

itself

furnace

is treated

material

in

or

suitable

other

some

in
electrically

receptaclelined

non-conducting refractorymaterial free from carbon.


with
it is covered
a
layer of slag or of other
substance
which
only acts as a conductor at high temperatures.
The electrodes are immersed
in this slag to such a slightdepth,
a

this vessel

In

and
from
the

is forced to flow
distance apart, that the current
electrode through the slag immediately beneath
it to

at such
one

metal

and

below,

other

the

to

electrode.

This

proportionof the resistance


resistances

of the
the

fluid metal.
should be formed

the

It is neither

they are

immersed.

distance

between

the electrodes

throughout

process, be
the slag which

Only in this way


indicated above.
It is
act

smelted

metal

reagents introduced
be

to

the

can

and

slag

desirable.

on

The

author

followingparticularsof
tool steel smelted

to

say
above

the

the

into

or

thank

the

composition of

quoted

it

can

by

to

P.

the
such

add

Heroult

various

to

way

of

means

object
as

are

for the

samples

of

0*016 to 0*022 per cent.


0-011
"
"
0-020 " 0-023
"
0-092 " 0*138
"
0*840 " 1-080
"

....

be

only

path

0*006

....

percentage of carbon
; that

the

the

"

Carbon,
The

be

Silicon

Manganese,

Dr.

to

should

electrodes.

is

manner

has

the

take

to

that

or

that

should,
spaces
better conductor

metal, whether

constituents

in this furnace

Sulphur,
Phosphorus,

bath

these

arcs

material

essential

made

be

touches

necessary that

therefore a
lies between
the two

current

undesirable

eliminate

electrode

metal

in

sum

electrodes

the

hotter, and

in

to

the

the

the melted

and

is,however,

perhaps hardly necessary


the

on

It

the

than

that neither

layers of

the

and

injuriousnor

in which

so

bath

the electrodes

between

regulated that

metal

be taken

must

the electrodes and

between

between

respectively.Care

through the same


layer of slag
is arranged by regulating the

thence

was

kept

designedlyraised
below

this level

to

the

is shown

figures
by the

525

IRON.

followingcomposition of mild steel : S, 0-008 per cent. ; P,


The pig iron used
0-003; Si, 0007 ; Mn, 0000; and C, 0-008.
for this charge contained:
S, 0*05 per cent; P, 0-129; Mn^
"

"

and

0-89;

0-31.

C,

H^roult

The

also

can

process
scale ; and

small

sufficient for the purpose

carried

be

of 50

current

out

demonstrations

of small

on

tively
compara-

H.P.

electrical

proved

in the Aachea

MetallurgicalCollege.
With

furnace,

has succeeded

Heroult
H.P.

H.P.

300

in

of this

success

the electrodes

the

furnace

be attributed
to the fact
process must
of
the
with
metal
to be
out
contact
kept

new

are

adopted is hardly
to be employed ;

one

has

conceivable,so
since

but

in which

the

of electrodes

use

the

Kjellin* method

the

metal

itself

favoured
The

furnace

sides and
is

consists

and

forms
same

bobbin

The

current

and

the
of

The

has

been

discovered,

superfluous namely,
heating current within
"

inventor

of this process

followingparticulars
:
circular trough, with

covered

In the centre

top.

brickwork
of the circle

enclosed
in a bobbin
plates,
the furnace
above
projects
a
rectanglewhich occupies;in relation to
positionas one link in a chain does to
is connected
to the polesof an alternating-

generator.

of the alternatingcurrent
through the
passage
and induces an alternatingcurrent
excites the iron core
The

metal

in the annular

contained

of coils in the

inverselywith
this way

In

strengthof

use

may

of increased

current

electrodes

wasteful
The
the

consumed

obtained

in
on

produce
strength,and
and largecopper
and

experimenting was
the

technical

economic

is

current

The

generator of high-tension

the
that

steel

too

low-tension

without

the

use

of

Gysinge, Sweden, by

at

ready

for

short, the
was

problem was
question,for

English Patent 18,921,of

furnace

conductors.

erected

was

18.

the

of
in

March

Although
remained

made

be

February, 1900,

of

strength of

in the

is situated

the current.

to

first steel furnace

end

the bath

bobbin

the generator, multipliedby the


bobbin.
The
tension, of course, varies

the

alternatingcurrent

the

core,

number

Since

batb.

the
singleplane around
that
to
produced in
equivalent
in

has

"

of thin, soft-iron
The core
copper wire.

furnace, the

another.

generating the

with

core

square
of insulated

chamber,

is rendered

by induction.

bottom,

the

of

the author

charged,partlyor

were

than
the
simpler method
current
as
a
dynamo
long
that time a noteworthy method

smelted.

metal,

lbs. of steel per electrical


It is evidant that this figurewould

twenty-fourhours.
if
be considerablyexceeded
with
molten
wholly,
pig.
The

cold

startingwith

producing 44

in

that

and

1900 ; U.S.A.

trial.
first

of excellent
thus
the

78

Patent

The

castingbeing
quality.

solved, there
Kw.

time

dynamo

still
fur-

682,038,Sept.3, 190K

524

ELECTRIC

nished
furnace

SUELTINQ

AND

REFINING.

onlj 573 lbs. of cast steel in twenty-fourhoars, and the


capacitywas only 176 lbs. It,therefore,became neces-

Fig. 246.

Fig. 247.
sary
was
once

to

construct

ready for work


proved itself a

new

in

furnace

with

November

decided

advance

largeriron

of the

same

inasmuch

This

cores.

year,
the
as

and

at

output

526

BLBCTRIC

8MBLTING

AND

Fig. 248.

RRFINIHG4

527

IRON.

Repeated

trial

smeltings in
yieldsup to 41

furnace
(electrical)

225-H.P.

twenty-fourhours; and
with the new
300 H.P, furnace Kjellinhopes to produce 44 lbs.
of steel per electrical H.P, in twenty-fourhours.
Mention
again be made of the Stassano process, which,
may
in view of the fact that it produces malleable iron direct from
the ore, without
passing through the intermediate
stage of pig,
has
be regarded as an electrical smeltingprocess.
Stassano
may
and
his
of
shaft
abandoned
now
employs
furnace,
originaltype
electrical reverberatoryfurnaces,or smelting hearths,in which
maintained
the charge of
electric arcs
above
more
one
or
are
One of his existingtypes of furnace
in Figs.
metal.
is shown
furnished

have

248

and

tons

249.*

According to the reports of H.


Patent
by the German
made

with

of the

per

the

Stassano

new

method

furnace

is

Goldschmidt,
Office
in
all

who

witness

to

was

the

missioned
com-

trials

value
1902, the practical
under
the
least
at
doubt,

placedbeyond
where
the plant
prevailingin the locality
tions,
situated (Darfo,to the north of Lago d'Iseo). These condiwas
found
elsewhere.
For instance, the
however, are rarely
for interest and
cost of current, with a liberal allowance
ciation
depreH.P.
of plant,worked
out
at only 32s. per
per annum.
used
is of excellent
Moreover, the Italian ore
quality. The
used
in the experimental plant at Darfo
specular iron ore
new

conditions

contained
FcjOg,
MnO,

of labour

"

93*02

percent.

0-619

"

P,
The

added

SiOj,

S,

had

reducingcharcoal

the

cent,

per

0 058

"

90*42 per cent.


3*88

.......

5*70

used

the limestone

CaO,

3790

"

Moisture,
and

followingcomposition:

Carbon,
Ash,

0-056 per cent.

51*21

MgO,

311

SiOj,

0*90

as

flux contained

percent.

,,
"

:"

F^O:}

0-50 per cent.

"

43*43

"

also given, but for what


pitch was
purpose
is not stated ; probably to prevent the separationof the charge,
of the charge having been
is made
since no mention
briquetted,
This pitch
in which
operationpitchwould be used as a bind.
had the followingcomposition:
An

addition

of

"

Fixed

carbon,

Hydrocarbons,
Ash,

*Lncchini, La

Chimica

59*20 per cent.


40*50
,,
0*27
"

InduUricUef 1902, vol. iv.,pp. 114, 131, and 145.

528

ELECTRIC

The

made

charge was

of

up

"

Iron ore,

As
raw

125

Fitch

120

160

might have been anticipatedfrom


iron was
of a
material,the resulting
contained

In the trials witnessed


lbs. of iron
volts

and

was

Per cent.

P,.
'

H.

by

S,

0*005 toO-029

,,0108

0*05

0109

"

Goldschmidt
hours
in two
furnished

charge of about

with

and

amperes,

0-05

Mn,

smelted

1,000

compositionof the
degree
satisfactory

09-60 to 9970
0-04 "
017
0-048
0-02 "

the
very

"

Per ceut.

155

,,

,,

Fe,
C,.
Si,

80

by weight.

1 ,000 parts

Lime,
Coal,

purity. It

of

REFINING.

AND

SMELTING

current

67*8

of

lbs. of mild

equivalentto an output of 7^ lbs. of iron per


electrical H.P. per twenty-fourhours.
Stassano
givesthe followingestimate of the cost of production
and to turn
in a plant designed for 5 tons
out 30 tons of mild
steel in twenty-fourhours :

steel.

This

is

"

Uk.

32 cwts.
Cost of

of

(1,000 kilos.),

crushing,
charcoal

of wood

Powdering

at

.1-00

Mixing,
electrode material,26} lbs. at 0*30,

of furnace,

Wages,

600
3 00

Electrical power,
General expenses,

4,000 H. P. -hours, at 0*0057 lire,

Total,
Less

900

cb.

Actual

gas,

at

18*00

of iron,

cost per ton

Or

that

only conclusions
experiments that have

been

steel in electrical furnaces


Stassano

favourable
particularly
and
purity and
power,
of Heroult

94*00

approximately"3

The

the

22*80
3*00
112-00

(31,785 cb. ft.)combustible

m.

2oentesimi

3 60
12*00

Supplies,

processes

13*30

6*75

Consumption of

Whereas

11 '25

0'50

.,

lbs. of pitch at 70 lire per 1,000 kilos.,

Upkeep

24O0
4*80

per 1,000 kilos.,


45 lire per 1,000 kilos.,

at 5 lire

of limestone

4 cwts.
5 cwts.
420

at 15 lire per ton

ore

are

be

can

made
:

"

ISs.

from

drawn
on

the

the

largescale
production of mild

"

process
conditions

depends
with

cheapness of
and
Kjellin seem

for its

success

on

regard to cheapness of
the
to

raw

be

materials, the
more

generally

Elektrotechni8che Anzeiger,1902, voL xix.,p. 3181 ; Z./. Eiddrochemie,


Coal Trades Bevieio,
; Iron and
January 15, 1904.

1903, vol. ix., p. 128

METALLIC

COMPOUNDS

CARBIDES

529

SIL1CIDBS.

AND

is not
applicablefor existingblastrfurnace plant. Their success
the
from
coke
water
waste
on
dependent
cheap
power,
gases
and
blast
furnaces forming a useful and abundant
ovens
source
of cheap current.
and
H6roult
Stassano
have arrived at nearly the same
result
of
each
and
of
mentally
fundameans
other,
quite independently
by
different apparatus and methods.
Thus, startingwith
cold scrap iron or pig,they obtained the followingresults :
"

H^roult

(La Praz), 44 lbs. of mild steel \ per


do.
Kjellin (Gysinge),39| Ibe.
j
This
the

undoubtedly

startingwith

when

even

could

output

charge is alreadyin

introduodd

the

into

cold
a

increased

furnace,it

largerplant,
Seeing,however, that
condition

is evident

longer stand

of

in

semi-molten

or

twenty-four

per

hours.

material.

molten

electric

be

1 elect. H.P.

that

when

the

in the

cost

of the

can
no
heating by electricity
way
production of steel by this means, and that the iron industry is
of the advantages of
in a position to make
increasing use
electric heating.
offers most
The
H^roult
advantages, and presents
process
greater securityof working, conjoinedwith higher output.

CHAPTER

XIII.

COMPOUNDS.

METALLIC
CARBIDES
It

has

been

shown

oxides

metallic

SIIiICIDES.

AND

the reduction

that,in

and

oxide

with

ores

smelting of

carbon

is experienced in
furnace, greater difficulty
and
other
metals than the carbides,silicides,
of metals

and

produced

from

interest
mentioned

however,

to

metalloids.
such

In

materials

it
metallurgists,
in

work

restrict

silicides.
The
carbides

on

himself

have

been

far

so

is desirable
the

numerous

the

electric

obtaining the

that

and

are

should

this carbide.

of
be

they
-metallurgy. The author will,
more
important carbides and

longer period than is


recognitionof their technical
the carbide industrydate back
called into existence
by the

known

for

generallysupposed, though the


and
value
the development of
barely ten years, having been
carbide.
calcium
Willson
and
on
publicationsof BuUier
therefore
of the compounds in questionwill
account
commence
with

free

simplecompounds
compounds can be

in the electric furnace

electro
to

as

these

in

Our

530

KLBCTRIC

8HELTIKO

ARD

BBFIMIKO.

CABBIDES.

Strontitim, and

Caloinmi
There
that
will

are

so

of
description

potassium disengaged
with

alkali

an

malodorous

water; but whether


or

alkaline

of them

one

left in the

preparation

combustible

gas when
a carbide

the residue

that
a

treated

ntilisatiou of

too.

found

1836, Davy*

and

the recovery

for the others

serve

In

of

Carbide.

in the preparation
points of resemblance
many
carbides
of
three
alkaline-earth
the
metals
propertiesof the

and

of

Barium

earth

contained

the residue

be stated.

cannot

It is

beyond doubt that Wohler,t in 1862, prepared calcium


carbide
by direct synthesis,and recognisedthe product as a
compound with the formula OaO^. The method adopted was to
in a closed
heat an
alloy of zinc and calcium with carbon
the
and
worker
same
vessel;
prepared acetylene from the
carbide.
resulting
The
present author conducted a long series of experiments
the
of metals by electrolysis,
in 1884-89,and, as is
on
recovery
that
shown
all the
by his reports in 1891,j:demonstrated
be
metallic
oxides
could
irreducible
as
previously regarded
heated carbon.
reduced
by electrically
The
object of these researches was the discoveryof a simple
method
Since the reduction
of preparingmetals.
residues from
and

lime
the

other

author

recognisethe
in the

since it

earths

contained

them

upon
value of the

detract

however,
carbide

alkaline

looked

from

his

as

reduction
claim

electric furnace

product

pointingout
desire

to

great the

this

diminish

excess

the
of

fame

of lime

to

does

produced

not,
calcium

of those

who

of calcium

formation

lime

circumstance,the author
the

he failed

any other experimenters,


that lime cannot
be reduced

easilydemonstrated
heated carbon without
by electrically

carbide, however

have

to

substances,

That

before

be

can

metallic

no

valueless.

over

has not

carbon.

In

the

slightest
subsequentlyrecognised

value of calcium carbide.


practical
and
Moissan, in
publicationsof Maquenne, Travers
1892-3,while describingexperiments in which calcium carbide
both recovered
and recognisedas such, do not indicate any
was
method
of preparingcarbide suitable for technical use.
practical
to
a
According
publicationby Maquenne, " in 1892, that
the

The

worker

heated

of 26*5

of barium
carbonate,
grammes
105 grms. of magnesium powder, and 4 grms. of wood
charcoal,
in a closed iron flask,placedin a Perrot furnace, and obtained
an

mixture

amorphous pulverulentproduct containingbarium


*
Ann. d, CJiemie and Pharmade, 1836, vol. xidii.,
p.
irihid.,1862, vol. oxxiv., p. 220.
t Borohers' Mtktro-tMtaUvrgit, let Ed., 1891.
" Campies Bendus, 1892, vol. oxiv.,p. 361 ; vol. cxv.,

carbide.

144.

p. 558.

METALLIC

One

COMPOUNDS

of this

gramme

when

treated with

CARBIDBS

product

AND

furnished

531

8ILICIDK8.

52-54

of

c.c.

acetylene

water.

Even

40 per
contained
though this product theoretically
over
cent, of impurities(magnesia),
Maquenne's reports show that
the theoretical yieldof barium
carbide was
not attained.
The
high price of the reducingagent employed, the physical
character
of the product, and
the
small
quantity of active
carbide
sufficient
to
present, were
preclude any practical
of the method.
application
Travers, in 1893,* prepared an
impure calcium carbide by
heatingcalcium chloride with sodium and carbon in closed iron
fasks.
The product could only be a mixture
of calcium carbide
and sodium
about
33 per cent,
chloride,
containingtheoretically
of the carbide;but actually
only 16 per cent, of calcium carbide
detected

was

by Travers.
electric furnace,in
a new
describing

In
the

French

Academy
on
followingstatement
of the electric
"When

the

forming the
the

At

arc

This

of

he

error,

had

though
the
not

is formed

furnace

are

thereby discovered

of alkaline

earths

in

easilycollected."
carbide is not liquidat
demonstrated

had

carbide

electric

manufacturing the carbide.


clearer expositionof the

carbides, is

chief

and

when

passed
an

working

follows
''

is not

as

"

the

calcium

glowing

over

method

economical

in the

conditions

alkaline-earth

carbonates

and
specification)

Bullier's

given
patent
further publication
by Moissan " in 1894.
This
descriptionand the wording of the
The
indefinite for the validityof a patent
as

water.

oxide

calcium

is

since calcium

conversion

reduces

heat, and

Moissan

^that calcium

"

from

vapours

red

liquidat

an

Even

impossible

[andflows]like

melts

carbon

lime

the

even

metal

is
be

must

carbon,

of the furnace

3,000" C,

very
escapes in largequantities. It readily
the carbon of the electrodes,
and forms a calcium

the

with

heat.

the

the influence

of lime under

reaches

temperature

carbide,which
red

the behaviour

to

made

"

temperature,

rapidly,and

his communication

1892, Moissanf

in

material

same

combines

of Science

claims
claim

too

were

was

worded

"

method

alkaline-earth

preparationof carbon compounds of the


metals, consistingin heatinga mixture of oxides,
for the

carbonates,"c.,of

the alkaline-earth

metals

with

carbon

electric furnace.''

According to this,the reaction,


CaO
*

into
in

30

CaCj

CO,

Proceedingsof the Chemical Society^ 1893, vol. cxviii.,


p. 16.
t CompttB Bendua, 1892, voL czv., pp. 1031-1033.
Patent 77,168,Feb. 20, 1894.
t German
" Comptea Bendue, 1894, vol. cxviii.,
p. 501.

in

an

532

BL"CTBIC

8M"LTINO

REFIVIKQ.

AKD

in
mvention, a claim precladed evea
pablicationscited above, since these made known

clftimed

was

as

1891

an

by the
of reducing all
possibility

metallic

oxides

carbon, whilst the fact that calcium


at a high temperature to form calcium

the

heated
electrically

by

will combine

with

carbon

been

known

had

carbide

since 1862.

ever

had
The inventor
to suffer grievouslyfor the lack of skill
the German
evinced in the draftingof his patent specification,
in 1899.
Nevertheless, the credit of
patent beins annulled

having founded
to Moissan

far
most

and

Bullier.

America

as

his

the carbide
is

industryin Europe
Willson

can

in 1894
he
patent specification
suitable working conditions,or

commercial

make

though

concerned, even

the

had

of

time

produce

to

so

filing

discovered

not

bow

claim

same

the

at

be denied

cannot

the
usable

article.

determining the questionof prioritybetween the Willson


and
Bullier processes, the chief point in disputewas
the admissibility
of a statement
in the American
No.
specification, 492,377,
"For instance, I have already
effect:
to the following
employed
and
reduce
lime
it (the process
to
produce calcium
claimed)
carbide.'* This remark
occurs
rightat the end of a specification
the
conditions
for
producing an indefinite fusion
describing
conditions
the
but
for producing the
product,
by no means
commercial
calcium carbide,
as
product which has been known
In

"

and

sold

since the year 1895.


carefullydetailingthe difficulties and

in
electrical
the

such

as

After

the

of molten

use

baths

tered
encoun-

oxides

for

the

Willson

separationof

and
specification

defects

of metallic

metals,
repeatedlystates in
claims
that, according to his invention,

be removed
by the addition of sufficient finelypounds
powdered carbon to prevent the smelting of the metallic comto be reduced.
evils

these

can

of carbon
excess
any
of
required for the formation

Now,

the
the

the progress of
consumption of heat, lowers

lime,hinders

hinders
product,and, finally,
itself.

The

entire

when
satisfactorily
nature

The

of the

loss of lime

substance

before

and

therefore

time

process
the addition

the

ready

fusion

the

amount

of the

manufacture

of carbon

is

as

carbide

goes
small

most

on
as

the

close to the
latter is reached.

facilitated the
such

retarded,the greater is the


vaporisingtemperature of this
melting point that loss occurs

of the lime

the
evaporation,

indeed,proceed to
used, the whole of
been

the

being so

even

above

will allow.

case

by

and

carbide, retards the fusion of


the chemical
reaction,increases
the output of carbide in the

of carbide

the fusion

more

over

an

the lime

for the formation

is

Willson

retarded

evaporationof the

extent

that, when

will have

the

may,
sufficient carbon is

vaporisedbefore
place.

of carbide to take

fusion

lime,which

there

has

534

BMILTINO

BLBCTBIO

AHD

BBFIMIKG.

impartialjudge the qaestionof prioritywhich


in Uie Tarioiis

contested

has been

It is

actions.

so

hotlj

that
beyond
of producingcalcium
carbide
the possibility
by fusingcalcium
and carbon in the electric furnace was
established by Wofaler's
of a chemical
discovery of the formation
compound, OaC,, in
of the reducibility
of
1862, and, by the author's demonstration
all oxides,in 1891.
It is now
evident
had
it
not
that,
equally
for the

and

Willson,

continued

of Moissan

labours

been

the

on

for

patent

other, this

struggle is

the

Bullier,on

one

hand,

knowledge might possiblyhave

to slumber

long time

electro-chemists,and.

of

and

doubt

that

in the heads

these

three

and

workers,

writings
now

the

have
been
the
to
generally admitted
industry. The author feels it incumbent
his opinionon this point,because
him
to clearlyexpress
upon
his report againstthe validity
Patent
No. 77,168
of the German
the
side
dictated
ventor
one
was
as
regarded by
by enmity to the into him), whilst the
(at that time personallyunknown
his
other side looked
attitude
with
regard to the reasons
upon
given by the (German patent authorities for annullingthe patent
volte /ace" His
as
a
position has, however, been consistent
his
conviction
invalid,
being that the patent was
throughout,
but not for the reasons
allegedby the patent authorities,
which,
in his opinion,did not in all pointsgo to the root of the matter.

whole

view

in

Hence,
feels

are

over,

of the carbide

founders

compelled

his

of
to

give

attitude

Bullier's claims, he

towards

public expressionto his

opinionon

the

matter.

of the requisiteconditions for the management


Some
of a
carbide furnace and the productionof a marketable
article have

alreadybeen
which

dealt with

in the

and

conditions

of the

course

requirements

have

foregoingremarks,
been considerably

of late,owing to the great advances


in furnace
struction
consimplified
and the weeding out of many
self-styled
improvements.
It is,therefore,advisable
to proceed with a brief recapitulation
of these points,in order to confine further historical data to the
smallest possible
limits.

RAW
Caloium

introduced
from

Oxide.

in the

This

"

into the furnace

limestone

though not

MATERIALS.

in

the most

the

essential
in the

usual

form

manner

economical, ensures

ingredient is generally
of burnt lime, prepared
in kilns.

This

method,

the

greatest regularity
of the resulting
duct.
pro-

working and in the character


It is also possibleto employ native
limestone
in the
than
electric furnace, but this is a more
method
expensive
burning in the kiln. On the other hand, the carbide process
both

furnishes
of carbon
large volumes
monoxide, the heat
bustion of which
be
utilised in lime
profitably
gas might

of

com-

burning.

METALLIC

compounds:

this basis it is

On

oabbides

possibleto

akd

conceive

53d

silicidbs.

analogousto

process

that

for the electrical smelting of iron


proposed by H^roult
but
practical
(seep. 515);
experiencealone could show whether
the total result would
be sufficient to outweigh the appreciable
defects arisingfrom the interdependency
of such a combined
process.
The use

of slaked

lime

was
proposedin the earlydays of the
industry,at a time when great attention was paid to
obtainingthe raw materials in as fine a state of division and as
intimatelymixed as possible.Under such conditions the conversion
of the charge into briquettes
be
advisable,an
might
could
be
that
the
aid
of quicklimeas
performed by
operation
the need for using calcium
a bind, without
chloride,"c.,for this
At present,however, it is usual to employ coarse
lime,
purpose.

carbide

in order

to facilitate the
inconveniences
the
prevent

In

selectingthe
should

alumina

rejected. Despite
quantitiesof clay are

furnishes

and, by
silica
the

be

can

the

carbide

carbide

addition

converted

calcium

limestones

gases, and to
separationof the

the

for carbide

limestone

be

moderate
silicates,
The

liberated

arisingfrom

the mixture.

ingredientsof
limestone

of the

escape

that

of

making, phosphatic
warnings against

the

less to be dreaded.
will disengage hydrocarbons;

ferruginoussubstances, the

silicideswhich

into
formed

the

at

will

separate from

time.

same

Sulphatic

also be excluded.

must

for
^The carbon
Carbon.
necessary
in
carbide
is
the
form
employed
forming

reducing the lime and


of coke, wood, charcoal,
Tar, pitch,asphaltum, and resins
for briquetting
the charge,but are

"

and
have
now

non-bituminous

been

proposed as
rarelyused.

The

materials

rangingfrom
mills

are

are

|^ f
to

binds

used

now

inch in

exclusivelyused
grindingthe

runners

THE

coal.

in

materials

too

Bullier recommended

(fragments

state

coarse

the Moissan

and

roller

and

edge

fine.

FUSING

FURNACE"

ELECTRIC

diameter); stone-breakers
for crushing,ball mills

furnace

THE
for

CHARGE.

smeltingcarbide,

for the work.


unsuited
As a
apparatus is peculiarly
furnace
used a Heroult
of fact,Bullier
at the Paris
matter
also employed by Willson
at
Exhibition,and this furnace was
This was
the earlier type of Heroult
the outset.
furnace,such
of
aluminium
in
the
is
used
as
production
1.6., a low shaft,
but

this

"

At the outset this


of an
consisting
liningserves as an electrode,a function subsequentlydischarged
whilst the other electrode
a simple block
by the carbide itself,
is lowered
through the top of the
or compound plateof carbon
of these early H6roult
One
furnace.
furnaces,with taphole.
iron box

lined with

carbon.

"

"

536

ELECTRIC

SMELTING

AND

charging hole

REFINING.

in the cover, and gas trap, was


work
electric furnace maintained
in continuous
of the

shaft furnace.
metallurgical

The

actuallythe
after the

construction

first

manner

and method

of

working were
simple,and the simplestis usually the best.
the
the furnace
to
According
adjustment of the electrodes,
with resistance or arc heating.
could be worked

Fig.250.

conjointinfluence of the high reduction temperature of


in the reaction,
of heat consumed
large amount
the high melting point of the carbide, and
the good heat
conducting propertiesof this substance at high temperatures,
The

the lime, the

METALLIC

contributes
On

in

of

allowed

was

the

of

one

collect and

to

much

suitable

in the
solidify
be

the

to

apart,differed
carbide

furnace

removed

until the

end

solid form

in the

work, provided the furnace was


other system, the working

In

construction.

industry,two

of the molten

amount

it could

hindrance

of the

considerations

certain

operation,when

without

other

working, which,

carbide.

molten

of the

earlydays

537

8ILICIDBS.

AND

solidification
in the

even

arose,

CARBIDES

ready

far that in the

so

of

the

to

this there

methods

COMPOUNDS

the

principleof the metallurgicalshaft furnace is adopted, the


charge being introduced
periodicallyor continuously,and the
drawn
off
from
time
to time, in order
to secure
tinuity
conproduct
of working.
For
Block
Smelting, the former of the two methods, the
introduced
:
followingfurnaces were
A furnace with portableand tippinghearth
was
employed by
The
the Willson
Aluminium
was
hearth, which
Company.
box
mounted
consisted
of
bottom
with
on
a
a
a
truck,
lining
"

wheeled

of

carbon, and was


electrode,in the

protect the

to

of

form

latter

being such

fuse.

When

the

work

that

molten

shaft
with

of

from

suspended
in

outset

order

proportion to
the

furnace

the

walls

to make

sides
of

the

could

keep

shaft

In

hinged

block

type also,in
of carbide

is drawn
a

afterwards

of the block

undecoraposed.
short

time

When

up
to

stituted
iron, con-

of

carbon

lowered

furnace, and

of
it

at

the

raised in

carbide,until

order

pure,
that the portionof

wide, so

in

block

of

plate of the

bottom

embedded
was

operation,but
this

down.

modifications,consisted

other

block

the

electrode

leaving the

cooled

upward growth
full.

remain

carbide,the

after

the

the

not

had

of carbon

top of the

start

charge did

the

various

The

the

dimensions

the

block

block

the
to

was

and

adjustably

top of the crucible,


hearth to be emptied and

fittings.The

electrode.

one

second

The

was

crucible,the

portionof

reached

enable

furnace,in

iron

shaft, composed

this

core

re-chargedafter the carbide


Another

cell.

carbon,

of the

sides

stopped,to

was

firebrick

of

block

iron

of the
the

bricked

the top of the cell,and charging apertures were


Part
the
of
the smelting crucible.
charge

suspended from
provided above
served

into

to

preserve

was

necessary
charge round the

this furnace

is full

it will go, and


as
it
is
withdrawn
cool,
by

as

far

the furnace
is made
as
opening the bottom
plate. As soon
of
it
be
at
once.
ready
re-charged
Equally,of
course,
can,
the new
charge is introduced from above.
course,
A
the
same
on
simple furnace
principleis that of
very
Clarke.*
The
lower
of carbon, is let into an
a block
electrode,
the shaft is built up to the desired
iron base plate,on which
of dry stonework.
height during the work in several courses
The

upper

electrode is

suspendedcarbon

"U.S.A.

Patent

562,89a

block.

538

ELECTRIC

Meohanism

heating

for

of the

Kiliani, and

8MELTIKO

moving

contents

has

REFINING.

AND

the upper electrode,to secure


uniform
of the crucible, was
recommended
by

likewise

formed

the

subject of

various

new

patents.
A

large number
for the

of movable
of

purpose

immediately solidified

hearths

duced,
introalso been
and
finished
the

have

quickly removing

carbide

from

the

of fusion.

zone

Some

Fig. 251.
of

these

vertical

are

in

the

form

of

rotary crucibles

or
axis,*belt conveyors,!vertical,}

mounted

horizontal

on

"

revolv-

"
Heath, U.S.A. Patent 586,686.
Patent
t Roberts, German
100,476 ; English Patent
17,609 of 1897 ;
U.S.A. Patent 588,012. Maxim, EngUsh Patent 4,075 (1898).
Patent 98,974. Bradly,
t Horry, English Patent 22,521 of 1897 ; German

German

Patent

98,708.

" Nikolai, Jahrbuch


and

Kandler,

German

der

E/ektrochemie,1898, vol.

Patent

103,058.

v., p. 323;

Wehner

compounds:

METALLIC

AND

CARBIDES

539

8IL1CIDES.

after
ing wheels,and risingand fallingplates,

the fashion

of

lift.*
Fomaoes.

Tap
Co.'s

"

In

contrast

to

Willson

the

Aluminium

Compagnie Electro- Metaldes


Gin
et
Leleux,t although working with a
procMds
lurgique
portablehearth, was
arranged for tapping the molten carbide.
hearth
The
was
portable
provided in order to facilitate the
cleaningup from time to time.
necessary
furnace,

that

of

the

former

Fig.252.
The

furnace

electric
formed
the

on

the other
into

the

by
one

the

by

as

far

as

by resistance,the
possibleavoided.

charge. The

hand

by

carbon

crucible.

importance
*

is heated

being

arc

to the

electrodes

the bottom

blocks
The
method

of the

or

of

working

The

contacts

of

above

of the
and

two

the

resistance

and

on

lowered

contacts

the economic

is

formed

are

portablecrucible,and

suspended from

arrangement

formation

is of

results.

Patent 94,641.
Memmo, EnglishPatent 14,022 of 1897. Patin,German
t Borehers, JMe Elektrochemit
auf der Pariser Weltaiisstellung,
1900,
Halle a. S., 1901, pp. 81-83.

540
The

BLBCTRIC

8HBLTIMO

bottom

is lined

crucible

lower

in

one,

direct

AND

BEFINIHO.

with

layers of carboa, the

two

with

contact

the

iron

bottom, being

of

ductor,
superior conductivityand supporting the less efficient conthe upper carbon plate. The objectof this arrangement

is to

the melt

warm

of the crucible

in the bottom

by

the electric

heat

generated in the upper carbon plate,and so prevent it


cooling and solidifying.The upper electrode is composed of
four bars of superiorconductivity
enclosed
in a mass
of carbon
of inferior conductivity. By this arrangement, numerous
vantages
adare

secured.

It is easier

conductivitythan

thoroughlygood
the thin rods,being embedded

in

unavoidable

protectedfrom

to

thin rods

manufacture

thick, massive
mass

of

blocks,whilst

of inferior

material,

by superheating and
combustion.
and
this
is
Moreover,
speciallyimportant^ the
short fragments of electrode
remaining in the holders after a
short time, can
be utilised to the full by breaking them
down,
the foor
mixing them with a bind, and using this to cement
good rods. The bundle of rods prepared in this way must, of
be converted
into a solid mass
by firingin a muffla
course,
The
furnace is charged from the top, the melt tapped,and the
drawn
off through channels
in the rear
wall,so that
gases are
the workmen
are
protectedfrom any injury or inconvenience
tions
from
carbon
and dust.
monoxide
However, incrustaarising
are

of solidified carbide
this
to

naturallyhinders

be

easilyremoved,

alreadymentioned,

and

lifted,
whereupon the

waste

collect in the crucible after

enable

the

work.

the

crucible is mounted

in

blocks

To

addition

the

time, and

this incrustation
on

truck,

as

be

casing
upper
of crust can
be taken out without
of the furnace
do not often need
can

The
other parts
ditiicalty.
the
is abraded
electrode,which
by the
repair,except
upper
descending charge, and acted on chemically by the carbon
dioxide
in the ascending hot gases;
the bottom
even
lining
only needs renewal about once a year.
and
chemical
In order to preclude the injuriousmechanical
the charge,prevent the scaffolding
action of the hot gases on
of the
descending charge, and obviate other inconveniences.
Rathenau*
electrode
encloses the upper
in a charging hopper
that the
of carbon
which
in such a manner
is mounted
plates,

productsof

gaseous
its outer

walls

and

the reaction
the

are

inside walls

compelledto pass between


With
the
of die furnace.

the electrodes inside the gas


same
object,other inventors mount
trap,tor make use of hollow electrodes through which the charge
is introduced or the gases are drawn
off.|
Price " has designeda furnace intended to prevent the aocumu*
German
t Siemens
T Siemens

S6,226 and 99,232.


Halske, English Patent 17,491, of 1897.
" Halske, German
Patents 97,406 and 106,049; Eldridge,
ft CUrke, U.S.A.
Patent 1]9,4"7.
Patent 683,618; Brand, German

Wright
"U.S.A.

Patents
",

Patent

672,312.

METALLIC

COMPOUNDS

solidified

lation

of

With

this

electrodes but
the

in

forms,

the

over

one

the

it

it and
being situated between
raised
which
is
a
electrode)
of electrodes

system

maintained

at such

is

matter

of the

length
through

breast

the

the

the

the

the

that

over

heating
All

hearth.

the

charging hopper,

electrode,however,
furnace, the taphole

the
furnace

little at
that

furnaces.

final

this

tap temperature

height

of

tap

of electrodes

intervals

The

541

8ILICIDE8.

crucibles of

such

full

furnace.

were,

AND

number

introduced

are

Bathenau

as

in

object
arranges
sloping hearth, at

is extended

as

CARBIDES

he

long,narrow,
zone

carbide

bottom

(thecounter
With

point.
of the

the accumulation

melt

this
can

be

of solidified

precluded.

Another

furnace, by Keller*

new

(Compagnie Electro-Ther-

" Co.),is designed for


mique, Keller, Leleux
accumulation
the
preventing

the

same

purpose

of

solidified

of

in

masses

naces,
fur-

tap

also to enable currents


to be employed.
amperage

and
of

high

Keller, however,
electrodes,or, for
either

only two
naces,
large fur-

uses

very
of electrodes.

two

rows

case

all the electrodes

into the crucible

down

The

covered

with

the

latter

both

rope

or

is

tive
conduc-

In

electrodes

be

furnace

layer of

starting
lowered

are

carbon

the
layer,
constitutes a heating resistance
so

between
this

as

the

carbon.

lump
work,
to

of

bottom

hang
can

and

regulated,as required,by
chain hoists (Fig.253).

In

them,

layer

has

that

and

as

become

soon

hot

Fig. 254.

enough, the charge is introduced.


layer should
be sufiicient to prevent the whole
of the current
passingthrough
the melt collects on
As
the carbon
it at the outset.
layer,the
diminishes
resistance
in proportion,
and a graduallyincreasing

It is

important

that

of current

amount

uniform

the

resistance

traverses

tension

and

must

be

the

of the

furnace.

carbon

In

order

to

tain
main-

strength of current, the positionof


changed in proportion as the melt
collects in the apparatus.
be seen
in Fig. 254, the
As
can
be raised and
electrode
lowered
one
can
only,while the other
be
moved
can
laterallyas well, so that finallyit occupies a
the
over
taphole,as shown in the figure.
position
this
melt and supplementary
By
arrangement of the electrodes,
that the strength of current
be
resistance,it is evident
can
the

electrodes

"Nemst

and

Borchers, Jdhrb,

der

Elekirochemie,1900, vol. vii.,p. 523.

543

SMBLTINO

BLBCTBIO

reduced

to

whilst

minimam,

maintained

in the

AKD

REFINING.

at the

the melt

time

same

of

requisitestate

be

can

the

fluidity
t^hole,
by the productionof an arc at this pointywhere the resistance
layer(melt and carbon bottom) attains its greatest thickness and
the resistance heatingis consequentlylowest.
used tor experimental purposes
A similar furnace was
by the
The
hearth
author
in 1898.*
and
was
narrow
sloping,and
need
in case
of
electrode as contact
for a
as
an
designed to serve
conductive
diBtributed
charge. On this hearth the charge was
to be thinnest
at the tapholeend
in such a manner
as
occupied
On includingthe charge
by the electrode for producingthe arc.
of a specialcarbon contact^
in the circuit,through the medium
the bottom
carbon layer on
or
plate,it becomes
progressively
of the arc
is approached and the thickness
heated as the zone
of the charge diminishes, until the maximum
temperature is
the attenuated
attained
of which
in the arc itself,
layer of the
constitutes
one
pole.
charge
of

ConBiimption

Power.

in carbide

of energy

furnaces

The

"

vary

reports

the

kilowatt-hours

on

the

consumption

those
considerably,
especially

publishedby optimisticpatentees.
by Eer8haw,t

near

According
between

figures range
kilogramme of calcium

to

and

carbide.

per
it should
be remembered

statement

3*576

5-960

In this

nection
con-

that in the earlydays of the


all gradesof product that would
carbide industry,
yieldacetylene
Some
of them
at all were
probablyconsisted
put on the market.
carbide very poor in the latter,
of masses
of lime and calcium
will fuse
since both these substances
mutual
without
reaction.
the earliest and

When

publbhed

at

the

end

rather

of

1894,

togetherin

incredible
the

almost

any

estimates

of cost
the
determined

author

of energy

as 4 to 4*3 kilowatt-hours
per kilo, of
the experimentsbeing made
on
a small scal"J

reports subsequently published show

Reliable
values

correspondcloselyto the results of

working

were
sumption
con-

carbide,

that
on

portions,
pro-

the

these

large

scale,the probableexplanationbeing that the experiment lasted


lost by
therefore little heat was
only a few minutes, and
radiation.
A

study on
highlyinteresting
and

the

different conditions

of

of energy

output

the ratio between


of

carbide

manufacture, was

or

laid before the

Third
Keller (of

Paris

International

the tion
consumpacetylene,under

Acetylene Congress at
(1900)by
Keller,Leleux k Oie.). The strength
Electro-Thermique,
observed in the furnace
and Milan
of current
plant at Meran
In
the curves
at 30 volts tension.
averaged 7,500 amperes
the Cie.

*German
Patent

Patent

115,742 (1898); EoglishPatent

6,C61 of 1899; U.S.A.

660,043 (1900).

t Electrician,
London, 1900, pp. 46, 164, and 245.
2nd Ed., 1895, p. 90.
4:BorcherB, Elektrometailurgte,

METALLIC

COMPOUNDS

CARBIDES

AND

SILICIDES.

543

(Fig.255)plottedfrom these observations,the weight of carbide


while on th6
per twenty-fourkilowatt^hours is given on the left,
rightis the volume of acetylenein litres (at 15*'C. and 750 mm.)
furnished per 1 kilo, of product. The charge consisted of lime,
and the various percentages of carbon were
indicated along
as
the bottom
that

of the

mixture

table.

6*2 kilos, of calcium

acetyleneobtained
mixture
calcium

An

examination

of 100 kilos, of lime

only yielded290

of these

data

shows

65 kilos, of carbon

gave
the volume
of
per kilowatt-day,
300
litres.
the other hand, a
On

carbide

being

of 100 kilos, of lime


carbide

and

gave 7*0 kilos, of


of
but this
same
consumption
energy,
Of these two best
litres of acetyleneper kilo.
and

60 of carbon

for the

Fig. 255.
be most

advantageous to the carbide maker if


with
content
were
a
consumers
yield of 290 litres of gas per
kilo.,the electrical energy being most economicallyutilised in
the productionof this grade of carbide.
There
is little need to go closely
into the proposalsthat have
the productionof carbide and reducing
for accelerating
been made
the cost, by briquetting
the charge,adding fluxes,or readily
oxides
reducible
capable of forming carbides,since all these
have
Mention
methods
should, however, be
proved worthless.
* for the utilisation of
made
Rathenau
of a method
proposed by
results

it would

Eng.

Pat. Na

6,033 of 1900.

544

BLECTBIC

REFINING.

AND

8XELTIKO

vith silica or silicates. It


highly contaminated
sufficient
the
to
a
adding
charge
quantityof iron
whole of the silica
oxide
with
the
combine
to
ore
preferablyas
during the fusingprocess, the proportionsbeing selected so as
than 20 to 25 per cent.
to produce a silicide containingnot more
materials

raw

consists

in

"

"

silica.

of

Iron

The

iron

or

ferro-silicon

oxide

may

oxide, manganese

copper
like.

its

or

Alkali
The

only alkali

the

carbide.

brass, bronze,
oxide, or the

copper,

oxide, chromium

Carbides.

that

carbide

underneath

collects

replacedby

be

can

be

prepared,in anything like

the same
lines as the alkaline-earth carbides,
pure state, on
is lithium carbide,Li^Og,and this is devoid of any technical

importance.
Carbides
The

general method

direct union
oxides
also'

other

of

or

of the

carbonates

preparing

in the presence

there

is

no

carbides

need

carbide

by the

reduction

of the

calcium
and

carbon,

with

all other

applicableto
Hence

of

metal

Metals.

Important

of

an

excess

prepared at

of carbon, is

high temperatures.

in detail the carbides

to describe

important metals, and the author will therefore


few of their special
characteristics revealed
a
merely mention
the reader
For
further
publishedexperiments.
particulars,
by
this
is referred to Moissan's*
work,
authorityhaving made the
with
carbides and
most
important discoveries in connection
other simplemetallic compounds.
The
followingtable contains a list of the carbides arrangedin
the order of their atomic weights.
of the

other

3 belong also the carbides


of the most
important
group
with metallurgy,viz..Si, Ti, V, Zr.
metalloids connected
To

of

Behaviour
The
presence

carbides
of

of

watei*, to

acetylene,
e.^. :
*

towards

Water.

alkaline-earth metals

form

the

decompose in
correspondinghydrates and

"

CaCj
Paris

the

Carbides

2HaO

Ca(H0)2

CJI^.

Mektriache
Moissan, Der
0/en, Paris and Berlin, 1897, supplemts.
and Berlin, 1900.
German
edition edited by Th. Zettel.

METALLIC

It

COMPOUNDS

is from

this

'. CARBIDBB

that

property

AND

545

SILICIDES.

calcium

carbide

derives

its

importance.
the other

On

though
earfch

their

hand, the

carbon

metals,

According
variable

ratio

cerite group

of the

is the

same

that

as

carbides,

of the alkaline-

be

expressed by a single equation.


temperature employed, the reaction furnishes
of
acetylene, ethylene, methane, and

cannot

the

to

reaction

mixtures

hydrogen.
XTranium

carbide

rich

in methane.

and

solid

gives with water,


Only about one-third

hydrocarbons
gaseous
of the carbon
ever,
is,how-

combined

in this way, the remainder


going to form liquid
and
of
hydrocarbons,
compounds
carbon, hydrogen,

and

oxygen.
Almniniiun

methane

only

hydrocarbon,

one

"

AlA

equal volume

of

Mn,C

12HaO

3CH4

4A1(H0)8.

also

yieldsmethane, but associated


hydrogen

carbide

Manganese
an

furnishes

carbide

with

"

6HjO

3Mn(HO)2

The

followingcarbides are
carbide,and those given under

CH4

H^.

decomposed by

not

water

Iron

4, 6, 7, and 9 in the table.


carbides of groups 6-9,and also WC, in presence
of the
of their own
and
certain other
version
metals, undergo conand carbon
On the other hand,
into metal
monoxide.

The
oxides

of groups
1 and 2 will fuse along with their own
in
oxides,
any proportion,to perfectlyhomogeneous mixtures
carbides
without
will even
decomposition. These
exchange
carbides

the

their

for the

carbon

in oxides

oxygen

of other

carbide-forming

metals.

Magnesiiini
pure state,and
from

the metal
heated

when

has

prepared,but

been

at low

in

not

It is formed

compositionis unknown.

carbon
that

temperature

rises

heat,
also

and

This

"

temperatures,but decomposes

further.

carbides

Other
the

carbide.
its exact

also
are

decompose
:

the

more

carbides

or

of

less

readilyas

aluminium,

ganese,
man-

and iron ; whilst under


prolonged applicationof great
alkaline-earth
metals
the carbides of the cerite and
are

decomposed.

The

carbon

remains

behind

form

in the

of

graphite.
can
quantitiesof carbon
graphite*by comparativelysmall amounts
be heated along with
metal
its oxide
or

be

Considerable

of
a

converted

aluminium,

large

into
if this
of the

excess

carbon.
*

Borchers

and

Mogenburg, Oraphit

Institutf"rMetallhiUUnwesen

und

aus

amorpherKoMe

Halle
ElektrometcUlurgie,

a.

in Borchers

S., 1902.
35

546

BBFININO.

AHD

SMBLTUra

ELBCTBIC

sniiciDss.

beat methods

The

in which

those

of

preparing silicides

oxide

the

mixtures

in the electric furnace.


de
Moissan, Yigouroux, and

advised

the

sulphur
methods
With

decompositionof

regard

silica

Iron, nickel,cobalt,chromium,

"

generalformula
W^Sij.
tungsten silicide,
with

the

since
80 per cent,
furnace.

the

on

an

former

iron

in

to.

reaction,
the

been

author's

definitely

manganese,

copper,

FeSi
silicide,

; and

to

seems

also the siliddes

Whether

sulphidesinto

alloyitself with silica in all proportions,


ferro-silicon with
it is possibleto obtain
over
a
the
under
acid
in
electric
of silica,
a
slag
strongly

silioide

Iron

M^Si ;

bj

pursuedby

book, already referred

in progress
experiments are now
laboratory.
Up to the present the followingsilicides have

are

Aschermann

whereas

extensive

isolated:

are

metallic

by

reduced

were

Information

in Moissan's

largescale

of Aschermann's
practicability

the

to

methods

Ohalmot,

silicides.

and
dioxide
will be found

silicates

or

These

carbon

the

on

FcgSio and

FeSi,,mentioned

by

or
Chalmot,"^ should be considered true silicides,
merely
alloysof the other silicidesand silica,has not yet been settled.

de

The

suitable
(seep. 521) is particularly
and nearlyall the tap furnaces
preparationof silicides,
carbide
making and metal smelting can be employed

for the

used

in

for the
Of
iron

H^roult

new

same

the

furnace

purpose.

silicides those

industry,and

(siliconbronze).
laboratory,have
with

those
The

of iron

shown

metallic

used in the
are
(ferro-silicon)
in the production of alloys

of copper
researches

manganese
oxides and

of

the

Oroll, in
silicide to

be

author's
an

active

this silicide

sulphides. Since
easilyprepared and no dearer than the iron compound, and as
there are
plenty of ores available for its production that are
nearly useless for other purposes, this silicide may probably
the refiningof copper
to the front for accelerating
and
come
reagent
is

other

metals.
"

/. AfMT,

Chem. Soe,,1899, vol. xxi.,p. 59.

"

[" f

548

ELECTRIC

BMJBLTINQ

TABLE
COMPARISOK

or

CCNTIORADB

AKD

AND

REFINING.

U.
FaHRRMUKIT

ThRRIIOMETBR

ScALKS.

649

INDEX.

Aluminium,

Extraction

of, (Berg),

119.

Yield

AcETYLBNB,

of,542.
metals, 74.

Alkaline-earth
"

"
,,

extraction, 74.

,,

Alloys,Aluminium, 98, 163, 164.

,,
"

arski,115.

Antimony, 474.
470, 474.

Bismuth,

Cadmium,
Cerium,

446.
181.

Chromium,
Copper, 273, 288.
Gold, 329, 368.
Lead, 59, 461, 470.

"
"

re-

"
"

of,

of, 104.
bronze (Cowles), 100.
carbide,545.
Extraction of,95.

"
,,

119.

"

"

(Graetzel),10, 114,

153.
119.

"

116.
(Grousilliers),
(Hall,C. M.), 131.
(Hall, J. K), 153.
(Haurd), 106.
(Henderson), 127.
127.
(ffiroult),
(Hunt), 108.
(Jeanson),106.
(Johnson), 119.

"

(Kagenbusch),114.

"

at

Froges, 145,

at

Garaaune,

161.

161.

Praz, 161.
Lend, 161.
Neuhausen, 145,

"
"

at La

"

at

,,

at

161.

"

Niagara, 139, 162.


Rheingelden,161.

"

95.
(Beketoff)"

(Farmer), 116.
(Faure),114, 119.
(Feldmann), 118.
(Gaudin), 114.
(Gooch- Waldo),
(Gore),106.
(Grabau), 95, 116,

"

Foyers,

162.

"

107.
(Falk-Schaag),

"

98, 164.
trolysis
aqueous solutions. Elec-

"

"

"

alloys. Production

"

"

,,

93.

Falls of

of, 139,

(CorbeUi),105.
(Cowles),98.
(Daniel),118.
(Davy), 109.
(De\nUe), 109, 113.
(Diehl),118,119.
(Dixon), 119.

"

,,

at

(Case),119.
Conditions
160.

anodes, 10, 113.

"

ing),
(BurgluurdtTwin-

"

Kupferhiltte(copper

"

"

"

211.
finins),
Alum
shale,93.

"

"

(Braun), 106.
(Bucherer),154.
(Bunsen), 109, 113.
"

Zinc, 383, 395.

"

148.
(Bradley),

107.

Mercury, 447.
Nickel, 288.
Silver, 303, 329.
Sodium, 58, 60.
Tin, 59, 449, 460.
Tungsten, 504.

Aluminium,

"

"

Magnesium, 20.
Manganese, 507, 511.

Alumina-carbon

"

(Borchers),145.

"

491.

Altenauer

(Bernard),141.
(Berthaut),114.
(Bertram), 106.
(Boeuski-Zdzi*

"
"
"

550

IKDBX.

Alumimom,

Extraction of (Kiliani), Anglesite,


460.
190.
Anhydrite,73.
273.
Annaberffite,
(Kleiner
Fiertz),
"
Anode
123.
cells,432.
(LeChatelier),113.
reactions. Use of (nickel),
"
"
294.
(LoMier),118.
,.
slime
141.
131,
(Minet),
(copper),244.
"
,.
"7.
254, 432.
(Monckton),
Anodes,
211-220,
"
Castingof matte, 248.
(Monteglas, de),
"
"
107.
Antimonial
nickel,273.
(Nahnsen-Pfleger).
glance,273.
"
"
107.
pyrites,273.
"
102.
474.
(Oentedt),
Antimonite,
"
(Overbeck-NieAntimony, 474.
"
487.
werth), 106.
Applications,
"
in copper
Behaviour
120.
re(Pichou),
"
"
R
tion
educ195.
(Pittfiburg
finins,
"
479.
Co.),138.
ElectrcHjrsis,
,,
Conditions for,
(Reinbold),107.
"
"
"
"

"

"
"

"
,,

"

M
"

,"

M
"

,.

"

"

(Richards),118.
(Rietz-Herold),

484.
,,

107.
,.

.1

"

"

"

"
"

(Tacony
Metal

"

,,

"

119.
(Itoger),
(Rogers),118.

(Rose),96.
(Senet),106.

"

Extraction,475.

"

,,

"

105.
(Tilley),

precipitation
process,475.
reduction

,,

and
Co.), 108.

(Thomas),

process,

486.

cess,
pro-

,,

Iron

"

Kopp's

,,

"

475.
Sanderson's process,
486.

105.
"

"

Siemens

-Halske

, ,

(Walter), 106.
process,487.
Solution and pre(Willson).125.
(Winkler), lia
487.
(Wohler), 95.
glance,474.
yieldof metal, 144.
Occnrrence of,93.
474.
(gray).
of crude, 475.
Treatment
oxide, Reducibiiity
of,
of,ores, 475.
by carbon, 96, 103.
Price of, 165.
Arsenic, 194.
Specific
gravityof fused, Arsenical nickel,273.

"

159.
273.
Arsenopyrite,
of, Asbestos, 1.
sulphide,
Electrolysis

"

"

"

,,

"

"

"

cipitat

"

"

,,

"

"

"

"

"

,,

"

"

Ashcroft

414.
(zinc),
546.
silicides,
495.
(chromium),
process
303.
Alunite, 93.
Augustin process (silver),
Azurite, 184.
Amalgam, Sodium, by electrolysis,
154.

Uses
"
Alums, 71, 93.

of,162.

process

Aschermann,

on

, ,

31.

of ores, 302, 331, 343.


See also Electric amalgamation.

Amalgamation

Amalgams,447, 448.
American

Bailby

fining),Balbach
Smelting Co. (copper re-

process

336.
(gold),

210.
(copper refining),
210.
327.
(silver),
Baltimore
Ammonium
407.
fining),
persulphate,
Smelting Co. (copper reAmperes, Table of,547.
210, 244.
Anaconda
finery), Barium, 74.
Mining Co. (copper re210, 227, 231-233.
carbide,530.
Andre's process (Nickel),275.
extraction, 86.
(silveralloys),
333.
Barker's process (gold),
307.
"

,,

,,

"f

""

551

IKDBX.

Basae-Selve

279.
(nickel),

process

Borchers-Stockem

Beatson

Boston

(tin),454.

process

Becquerelprocess (lead),462.
317.
(silver),
(aluminium), 95.
Berg process (aluminium), 119.
Bernard
process (aluminium), 141.
Berthaut process (aluminium), 114.
(magnesium), 4.
Bertolus (iron),
517.
Bertram
process (aluminium), 106.
Beryl,87, 88, 91.
"

"

Beketoff

process

"

"

(calcium),

process

83.

Bauxite, 93, 155.

and

Montana

Mining

t process (gold),
333.
Breakell-Haycraf
273.
Breithauptite,
Bromargyrite,300.

Brunner
508.
(manra"nese),
Beryllium,87.
compounds. ElectrolysisBrunner, Mond " Go.*8 works
,,

of, 88.

"

"

"

"

(Lebeau), 89.
(Liebmann), 89.
(Warren), 90.

273.
Beyrichite,

Bucherer process (aluminium), 154.


Buff process (magnesium),3.
Bullier (calcium carbide),529, 532,
540.

Bischoff-Tiemann's

experiments

Bunsen's

-earth
experiments (alkali

282.
(nickel),

metals),75.

Bismuth

ochre, 470.
Bismuthine, 470.
Bias (zinc),389.
Bock

"

,,

,,

"

,,

,,

(aluminium),
109.

electrolyticgold, 359,

on

(cerium),168.
(chromium),

368.

496.

experiments (gold),340.

Bodlander's

Body

(zinc),

440.

extraction

,,

Co.

210.
(copper refining),
Bradley process (aluminium), 148.
Bradlv (movable hearth),538.
Brand (electric
furnace),540.
453.
Brandenburg, Dr., process (tin),
Braun process (aluminium), 106.
Braunite, 507.

process

259.
(copper),
339.
(goU),

,,

"

"

,,

22.
(lithium),
(magnesium),

3,33.

nium), Burghardt (zinc),409.


(alumi115.
Burghardt-Twining(aluminium),107*
Bohm, R. (neodidymium),174.
Bussy process (magnesium), 3.
Bohne's process (tin),452.
Butters and Mein's distributor,
347.
210.
Bolton " Son (copper refining),
Bonnet, see Placet- Bonnet,
Borax, 29.
Borchers' electric furnace, 58, 171,
process
Bog[U8ki-Zdziarski

172, 177, 180, 491.


,,

process (alkalimetals),79.

,,

"

"

"

"

"

(aluminium),103, 145.
530.
(carbides),
(chromium), 494, 497.
(magnesium), 13.

,,

"

"

,,

(maneanese), 509, 510.

,,

,,

503.
(molybdenite),

, ,

"

"

"

,,

"

of iron and
(separation
nickel),293.
(sodium),45, 47.
60.
(sodium allo^^s),
454, 459.
(tin),
(tungsten),505.

"

,
"

"

(uranium), 506.
"
387, 392, 441.
(zinc),
"
Brothers
(copper refining),

"
"

Borchers

"

,,
-

Siemens

(strontium),85.
-

Halske

221,
(copper refining),

224.

331.
(gold),
446.

,,

446.
electrolysis,
extraction,446.

,,

uses, 447.

"

Calamine, 382.
Calcium, 73.
carbide,530.
,,

extraction, 76.

"
,,

"

(BorchersStockem), 83.

,,

,,

"

(Bunsen), 75.

"

(Davy),74.

,,

(Matthiessen),76.

iodide (Moissan),83.

"
,,

oxide,534.

"

uses, 87.

Calc spar, 73.

211.

Borchers

Cable

Cadmium,

process

Calomel, 447.
Carbide, Aluminium, 545.
Lithium, 544.
"

552

INDBX.

Carbide, Magnesiam,

Manganese,

"

electrolysis,Glaser's

Chromium,

545.

experiments,

545.

501.

Production
of,386.
silicon,
"
Uraninm, 545.
Production
Carbides, alkaline-earth,
of,86, 590.
Carbon electrodes (Bunsen's),3.

Krupp*s

,,

Reduction

"

by, 86,

experiments,

535.

Placet-Bonnet

,,

alumina

of

process, 498.

by,

extraction, 491.

96, 103.
Carbon-alumina

anodes, 4, 10, 113.

Aschermann's
495.

"

Carborundum, see Silicon carbide,


CamaUite, 1, 4, 6, 16, 17, 18, 71.
Casarza, Copper extraction at, 248.
Case process (aluminium), 110.
Cassei Gold Extractins Co. 338, 341.

Srocess,
nace,
aplet's fur492.

Goldschmidt's

,,

338.
(gold),

Heibling's

"

449.
C}a8siterite,

cess,
pro-

494.

process (soda),49.

Castner

495.

process,

Cassel process

Street's

MoUerA

of alkaline-earths

Reduction

"

process,

502.

nace,
fur-

Moissan's

,,

(sodium),31, 64.
Cathodes, 211, 212, 218, 219, 220,
249, 255, 435.
Caustic soda, Electrolysis
of, 31.
73.
Celestite,
Cerite,166.
metals, 166.
"
of, 167.
Electrolysis
Uses of, 182.
Cerium, 167.
extraction
(Bunsen), 168.
(Muthmann-HoferWeiss), 171, 175
(Stockem), 170,182.

492.

,,

"

"

,,

"

"

,,

"

"

"

allojrs

"

carbide
oxide

"
"

181.

,,

180.
,,

180.

"

Cerussite,460.
184.
Chalcopyrite,

Chalmot,

de

process,

546.
(silicides),

495.

reduction

,,

cess,
pro-

491.

493.
refining,

,,

490.

occurrence,

properties,490.
uses, 502.

Cinnabar, 447.
Clarke electric furnace,537" 540.
Classen's experiments (nickel),
277.

Clay, 93.
Clerici process

326.
(gold),

Cobalt, 282, 283, 285.


nickel pyrites,273.
pyrites,273.
separation,285.
,,
(Vortmann), 285.
Coehn process (copper),271.
(zinc),412, 416, 417.
,,
"

"

Chalk, 73.

precipitation

,,

"

Chaplet'selectric furnace,492.
Chatard*s experiments(gold),
337.
Chicago Copper Refinery (copper),

Coleman
process (tin),455, 459.
CommunionHuttenwerk
fining),
(copper re-

242.
Chili saltpetre,
29, 68.
Chloanthite,273.
Chlorination of gold ores, 338.
Chlorine in copper refining,
203.
409.
Choate (zinc),
iron ore, 490.
Chrome
Chromium, 490.
495.
electrolysis,
"

Compagnie

,,

JBorcher's
"

ments,
experi497.

tt

"t

Bunsen's

i"

Feree's
ments,

Electro

metallurgique,

Congo red, 399.


Copper, 186.
alloys,273, 288.
anodes, Behaviour
"

,,

,,
"
"

of

purities
im-

in, 193.
anode mud, 199, 244.
Black, 184, 185, 186.
extraction

tf

"

"

at
at

ments,
experi496.

""

211.

Casarza, 248.

Schwarzenberg,
269, 270.

experi- I

at

Stolberg, 254,
257.

501.
"

(Body),259.

553

INDEX.

Copper, extraotion (Coehn), 271.


(Hoepfner),266-

Copper,Refining of, Electrolytic


"

(Siemens-Halske),260-266.
270.
(Smith), 238.
(Marchese), 247(Stalmann), 236.
254,256.
Theory of, 192.
(cost of),
(Thofehm), 228-234.
256.
(Von Hubrs experiments, 208.
(Napier),12.
Copper, Refiningof,smelting, 185.
(Roessler),196.
184,193,246.
sulphides,
,,

"

"

glance,184.
matto
refining (SiemensHalske), 260-266.
Native, 184.
ores,

184.

uses, 272.

"

Corbelli process (aluminium), 105.


Corundum, 93.
Cost of copper refining,
225-227,232.
Siemens-Halske
cyanideprocess
"

352.
oxides, 184.
(gold),
184.
pjrrites,
Crocoisite,460, 490.
409.
210, Croselmire (zinc),
refinery.Anaconda,
Cowles electric furnace, 102, 120.
227, 231, 233.
furnace, 120.
Refiningof, 185.
smelting
(aluminium
Electrolytic,187, 210.
alloys),
process
tric
(zinc),384.
(Baltimore ElecRefining Cowper-Coles process (lead),465.
Co.),244.
(vanadium),
489.
mens
(Borchers- Sie412.
Halske),
(zinc),
459.
221-224.
Cruickshank
455,
process (tin),
Chicago Copper Cruikshank, Copper deposited by,
"

"

"

"

"

"

"

,,

"

"

"

"

"

"

"

Refinery,242.
,,

,.
"

Conditions,244.
Cost of 225, 227,

148, 150, 155, 160.

232.
current
,,

187.

Cryolite,29, 93, 114, 115, 131, 145-

,,

,,

required,

Specificgravity of fused,
160.

198, 227.

,,

,.

,,

,,

"

"

"

"

"

"

"

"

,,

,,

Cupric compounds, 187.


108, Cuprite,184.
(Elkington),
210.
Cuprous compounds, 187.
and
Currie (zinc),409.
Seidel's ments),
34, et acq.
experi- Cyanide process (gold),
341.
207.
on,
Cyanides,Christy
Radziszewski
(Graham), 233.
on, 341.
"

(Forster

(Hayden),238.
(Kiliani's experimente), 193.
multiple system,
Danckwardt
239.
process (sodium),49.
(Oettel'sexperiments, Daniel process(aluminium), 118.
tin ore
Danneers
experiments on
copper

tion),
sulphate solu"

,,

"

Parallel
211.

system,

(Patera),

smelting,450.
Darlins

210.

process (sodium),68.
Davies" apparatus (tin),
458.
Davy's experiments (alkalineearths),

187,

74, 530.
"

,,

(aluminium), 109.

,,

"

(ma^esium),3.

188.
,,

(Randolf),238.
Haritan

"

"

"

,,

,,

,,

Copper

Works, 234, 244.


(Schneider -Szon-

tagh),227.
Series

system,
236, 239.

(sodium), 30.
Defacqz (tungsten),505.
De Laval furnace,519.
deposition,
Depolarisersin copper
,,

,,

257.

Depretz electric furnace,97, 119.

554

INDEX.

nnd 8ilber-Scheide
397.
AnfiUlt,317,
Deville prooMS
(aluminium),95, 109.
607.
Dialogite,
Diaphimgms, 434.
DiasDore, 93.
Dienl prooeas (aluminium), 119.
Dietsel prooees (silveralloys),
303.
Diaohargedoors, 348-350.
Distributor (Buttersand Mein), 347.
Dixon process (aluminium), 119.
Deutache

Gold-

Electric furnace

(Mnthmann-HoferWeiss), 171, 172,


175.

.,

(Pichou,

"

ing),
smelt-

ore

120.

.,

,,

"

"

(Price),640.
(Rathenau), 540.
(Schindler),152.
(Siemens),119, 120.
(Stassano),627.
(Stockem), 181.
(WiUson), 125.

"

Dolomite, 1.
Dor^ silver,
Refiningof,311.

"

Electrode,214.
tracting
carbon. Bunsen's, 3.
Dorsemagen'a experiments in excell,Grabau's, 25.
zinc,
,,
"

386,389.
red lead,419.

"

"

machine,
Dyblie-Hixonanode-casting

of berylliumcompounds,
Electrolysis
88.
255.
Electrolyte,

214.

of,250.

Circulation

"

Electro-magnetictreatment
E
Eldridoe
Electric

513.
Electro-thermal

furnace),540.
(electric
336.
amalgamation (Baile}'),
"
"
"
"
"
"
"
"

,,

(Barker),333.
(BreakeU), 333.
(Hannay), 334.
(Haycraft),333.
(Jorv),338.
332.
(Mofloy),

,,
"

(Rae),'336.

reduction

of

nesium,
mag-

19.

Elkington process

(copper refining),

188.

Elliott's Met"l

Co. (copper refining),

210.

Elmore

Metall

Aktiengesellschaft

210.
refining),
(copper

Eisners

Emerald
(Motz),336.
(Pelatan-Clerici), EmeiT,
336.

"

of iron

ores,

340.
experiments (gold),

nickel, 273.
93.

Engefhardt
(mercunr),
English

Electro

448.

MetallurgicalCo.

210.
calamine, 382.
(copperrefining),
412.
furnace (Borchers),58, 171, Eschelimann's
process (zinc),

172. 179, 180, 492.


"

"

(Borchers-Stockem),
82, S3, 85.

"

,,

"

"

"

,,

"

(Bradley).150.
(Chaplet),492.
(Clarke),637.

Faulerz, 300.
Falk-Schaag process

(CompagnieElectro- 107.
539. Faraday'slaw
Metallurgique,
(Cowles),102.
ing),
(Cowles, ore smelt-

,,

,,

,,

Farmer

(aluminium), 116.
277.
(nickel),
Faure
(Dorsemaffen),386.
process (aluminium), 114, 119.
79.
(Gerard Lescuyer), Feldmann
process (alkalineearth),
125.
(aluminium), 118.
(Grabau), 125.
Felspar.29, 71, 93.
(H^roult),128. 535. Feree's experiments (chromium), 501.
ing),
Ferro-aluminium, ICJO.
(Johnson,ore smelt120.
chrome, 491.
5
41.
507, 508.
(Keller),
manganese.
151.
387, 546.
silicon,
(Kiliaui),
Fischer process (ma^esium),
6.
(Kleiner-Fiertz),
123.
(sodium),40, 52.
Fluor spar, 73.
(Moissan),492.
process
"

"

"

,,

,.

"

,,

,.

"

,,

"

"

,,

.,

"

,,

,,

,,

electro-deposition,

371.

120.

"

of

(aluminium),

.,

556

IHDEZ.

Hammond

409.
(zinc),
experiments

Hampe,
"

beryllium

88.
lODABOYBITB, 300.
eomponnas,
reduction of aluminium,Iron, 195,511.
102.
Cast, 512.
"

"

Hannay

in

334.
(gold),

process

Crude,

"

Harmet
516.
process (iron),
Hasse (unc), 390.
Hauerite, 507.
Haurd
process (aluminium), 106.

"

"

,,

,,

513.

Production, 513.
Harmet
"

"

"

H^roult

"

Hausmamiite, 507.
"

,,

"

"

"

"

Keller
517.
Stassano

Heath

(movable hearth),538.
96, 119,
Heating by electricity,
126.
73.

"

"

Heibfingprocess (chromium),

494.

284.
(nickel),
409.
Heinzerling(zinc),
Hemelingen Magnesium Work, 20.
Henderson
(aluminium),
process
,,

127.
Herold-Rietz
(aluminium),
process
107.
He'roult electric furnace, 128, 5Sn.
process (aluminium), 127.
"
"

"

(chromium,)
(iron),515, 521.

"

"

manganese,

494.

"

510.

Hilbers

(magnesium), 127.
210.
Hill.W. A. (copper refining),
o
f
Hillebrandt, electrolysis cerite
metals, 168.
23.
Hiller process (lithium),
(strontium),78.
machine,
Hixon-Dyblieanode -casting

,,

"

515.

"

"

,,

515.

333.
Haycraft process (gold),
Hayden process (copper refining),

Hearyspar,

process^

515.

"

glance,511.
Grey, 512.
Ingot, 513.
Malleable,512.
"

cast, 513.

"

"

Production, 519.

"

"

"

"

,,

"

"

,,

"

"

"

Meteoric, 273.

"

ores.

"

511.
Pij;,

"
"

Wrought,

"
"

cess,
pro519.

H^roult

cess,
pro521.

Siemens' furnace,
519.

Preparationof,513.

546.
silicides,
Telluric,273.
Weld. 513.
White, 512.

"

De Laval

513.

"

214.

Hoepfner process

(copper),266-270.
280.
(nickel),

"

(sodium), 34.
(zinc),419, et eeq.

,,
,,

Jabixk:hkoff
Jeanson
Johnson

process (sodium),33.

(aluminium), 106.

"
"

Jory

"

119.

338.
(gold),

"

Hofer

(cerium group), 171.


Horbachite, 273.
Horn
"

447.
quicksilver,

silver,300.

Hornung-Kasemeyer

process

(sodium),41.
Horry (movable hearth),538.
327.
House-Symon process (silver),
Hunt

on

the

PittsburgReduction

Kagenbuscu

process

(aluminium),

114.

Kahlenberg,27.
Kainite, 1.
Kandler
(movable hearth),538.
Kaolin, 93.

Co. 's Work, 108. 139.


Huntington- Heberlein process (lead) Kasemeyer-Hornung
process
462.
(sodium),41.
Keith process, 466.
Huntington (tungsten),505.
Huppertz, Experiments by (lead), Keller electric furnace,541.
462.
"

Hydrargillite,93.

Kellner

process,
process

517.
440.
(zinc),

557

INDEX.

Kempen

works

experiments (masnesium),
Liebig's

(tin),454.

Liebmann*8

Kieserite,1.
ing),
Kiliani's experiments (copper refin-

process

"

"

(beryllium),
(beryllium
oxide),

193.

fiimaoe, 151.

("luminium), 130.

process

"

90.

Limestone, 73.
Limonite, 511.

398.
(zinc),
"

Lindemann's

(Bunsen), 22.
(Guntz), 26.

(HiUer),23.

Kopp^sprocess
Kmpp

28.

extraction

"

413.
(zinc),

process

273.
Linnseite,
Lithium, 21, 26,

303.
Kiss process (silver),
Kjemn heating process, 523.
Kleiner- Fiertz furnace, 123.
Knofler process (maffnesium), 19.
Konieliche Friedricnshiitte,395.
Koemann

(antimony),486.
416.
process (zinc),
502.
(chromium),
process
(manganese),510.

"

,,

(Kahlenberg)^

,,

(Matthiessen),

27.
,,

21.

,,

"

(Troost),22.
experiments (cerite metals),

Kugelgen,y. (tin),450.
Kugel

process

3.

89.

Lorenz

284.
(nickel),

180.

Kupfemickel,273.

393, 443.
(zinc),
Lossier process (aluminium), 118.
Luckow
388, 413.
process (zinc),
4
64.
(lead),
Lyte'sprocess
"

"

416.
(zinc),
167.
Lea and Hammond
409.
(zinc),
Lead, 195, 460, 470.
Lakoe

process

Lanthanum,

H
MacAbthub-Foskest

59.
alloys,

,,
"

462.
leachingandprecipitation,

"
"

Cowper-Cbles
process,

,,

465.

"

"

462.
electrol3rsis,
Lyte*sprocess, 464.

,,

,,

Salom's process, 464.

,,

,,

ores,

"

Refiningof,466.
"

,,

Magnesite, 1.
Magnesium, 1.
"

20.
alloys,

"

carbide,545.

"

Keith's

process,

"

Electro-thermal

Tommasi
"

(Borchers),13.
(Buff),2.
(Bunsen),2.

process,

469.

smelting,461.

"
"

"

2.
(Bussy),

precipitation
process,

2.
(Davy),

462.
,,

"

6.
(Fischer),

roastingprocess,

"

461.

(v.

tion
reduc-

and
"

,,

process,

20.
(Hilberg),

-sodium

59, 63.
alloys,
Lebeau, experiments by (beryllium),
,,

Le

process

Chatelier

(Knofler),19.
19.
(Ledderboge),
2.
(Liebig),

89.
(beryllium),
process

(Matthiessen),3.
(Napier),12.

(aluminium),

113.

Melting

Ledderboge (magnesium),19.
21.
Lepidolite,

511.
Magnetite,

L^trange

Malachite, 184.

408.
process (zinc),
Le Yerrier process (nickel),
284.
Leyera (vanadium oxide),488.

Gorup-

Besanez),5.
7.
(Graetzel),

462.
"

tion,
reduc-

19.
extraction (Berthaut),
3.^

466.
"

(gold),.

Magnalium, 164.
Magnesia-carbonanodes, 4, 10, 113.

460.

"

process

341.

extraction, 461.

of

posited,
electro-de19.

Manganese, 507.
511.
application,
,,

558

IHDSX.

Monckton

fi09.
Manganese, electrolysis,
H"^roiilt'sprocess,

"

,,

510.

precipitation process,

,,

508.

(aluminium),97.
process (aluminium)

process

Monteglas,De,

107.
Morrow
213.
anode-plates),
(casting
Motz (gold),
336.
Mud, Anode- (copper),199.

Reduction
of,506.
"
540.
silicide,
Milgge(coppercathode-cry8tal8),205.
"
282.
Mtinzingprocess (nickel),
Manganite,507.
Mansfeld
fining),Muthmum
(cerium group), 171.
Copper Mines (copper re210.
(neodidymium),174.
"

(barium carbide),530.

Maquenne

Mylius (cadmium), 446.

Marble,73.
Marchese

(zincexperiments)396, 405.

,,

process (copper),248, 254,

256.

Matignon (neodidymium),174.
Matte-anodes, Castins of,248.

of, copper,

Mattes, Treatment

260-

Nahksbx

266.

(spongyzinc),398.

(zinc experiments),409.
Nahnsen
4
58.
Matthews*
(tin),
ium),
Pfleger process (aluminapparatus
107.
Matthiessen s experiments (alkalineearth metals), Napier'selectrolytic
vessel,12.
Nebel (silver),
326.
75.
22.
(lithium),
Neodidymium, 167, 174.
"
Nemst
4.
407.
(ammonium persulphate),
(magnesium),
"
"
(potassium),71. Nettel (mercury),448.
,,
"
Netto process (sodium),30.
Meerschaum,
1,
extraction
Aluminium
Neuhausen,
Memmo
(movable hearth),539.
,,

Menniche,

tin

smelting,454-458.

at, 145, 161.

Works,
Niagara Metallurgical

Mercury, 447.
extraction,447.

,,
"

"
"
"

"

uses,

"

Meyer

448.
(Engelhardt),

Niccolite,273.

(Nettel),448.
(Vortmann), 448.

Nicholas Chemical

Nickel, 273.

448.

454.
process (tin),

"
,,

diaphragms,434.

,,

, ,

288.
alloys,

concentrated

275.
"

(aluminium), 141.

process

"

282.

317-327.
Moebius process (silver),
Moissan's process (calcium),81.

"

carbide),

"

"

531,532.
(chromium), 492,

"

"

,,

"

"

"

"

503.
(molybdenite),

"

(uranium),506,507.
process

process

"

(electric
amalgamation),

332.

284.
(Hiibling),
284.
(Kugel),

"

"

(Le Verrier), 284.

"

"

282.
(Miinzing),

,,

,,

Monazite, 166.

uses,

604.

"
"

(Rickets),280.
(separationof iron),
293.

"

reduction of oxide,503.

,,

(Frasch),284.
(Hoepfner),280.

"

"

Molybdenite,502.
Molybdenum, 503.
503.
production,

(Farmer),277.
(Forster's experiments),

"

(chjfomium),

499.

Molloy

(Classen's experiments),

287.
"

"

Muller- Street

"

277.

493.
,,

279.
(Basse-Selve),
(Bischoff Tiemann),
-

"

Minctte, 511.

"

mattes, 291.

electrolytic
treatment( Andr^),

389.
(zinc),

Millerite,273.
Minet

Co. (copper refining),

210.

Mica, 71.
Miest

139,

162.

"
,,

"

"

"

280.
(Strap),

(summary), 290.
(Ulke'sexperiments),
286.

559

INDEX.

Nickel

(review of pro-

extraction

ceases),296.
-copper

,,

273.
glance,

,,

Plattner process (gold),


338.
Polydymite,273.
Potassium, 71.

pyrites,273.

iron

,,

272.
pyrites,

,,

273.
vitriol,

(chromium)

process

498.

288.
alloys,

"

Placet -Bonnet

cyanide,Electrolysisof,

"

72.

Niewerth-Overbeck
process (alnminiuro),106.
Nikolai (movable hearth),538.
Affinerie
Norddeatschen
(anode-

72.
,,

,,

(Matthiessen),

,,

71.

213.
plates),
,,

(Linnemann),

extraction
"

uses, 72.

"

(copper refin- Power, Consumption of, by carbide


ing),210,312. furnace,542.

368.
Praseodidymium,167.
(gold),
of cerite metals), Price electric furnace,540.
(electrolysis
"

Norton

Price

169.

Nothemann

455.
process (tin),

Prices

395.
(zinc),

process

(aluminium), 165.
Psilomelane,507.
Purple ore, 511.

Noumeite, 273.

507.
Pyrolusite,
Pyromorphite,460.
Oersted's

experiments(aluminium),
95.

Oettel's

(copper sulphate
210.
QuiKTAiNB
solution),
(magnesium),17,

,,

"

"

process

454.
(tin),

444.

Omholt process (sodium),36.


Overbeck
Niewerth
process
-

minium),
(aluRadziszewski

106.

Oxides, Reduction
3,86.

of

all,by carbon,

on

oxidation

of

cyanide,341.
Rae
process (gold),336.
Rand Central Keduction Co. (works),
351.

Randolph

process

(copper refining),

238.

Pateba
"

process (copper),187, 188.


303.
(silver),
"

Patin (movable hearth), 539.


302.
Pattinson process (silver),
Pelatan-Clerici process (gold),
336.
495.
Peligot(chromium),
(uranium),506.
,,
Lead Co. (silver),
322.
Pennsylvania
electrical heatingfurnace,97,
Pepys^
98.
Perrot

furnace,14.

413.
Pertsch process (zinc),
Pettenkofer (goldrefining),
359.

Raritan

Copper

Co.

ing),
(copper refin-

210, 234, 241, 244.


Rathenau

electric furnace,540.
and

Suter's

Works, 20.
(sodium),67.
Reduction, Electro-thermal,of magnesium,
,,
"

,,

Suther

19.

Reinbold

(aluminium),107.
Rhodochrosite,507.
Rhodonite, 507.
Richards (aluminium),94.
Rickets process (nickel),
280.
process

Rietz-Herold
process (aluminium),
107.
Pflegerprocess,
Roberts (movable hearth),538.
Pfleger-Nahnsenproce8s(alumimum),
Robertson " Bense works, 453.
Rock salt,22.
Phcenix process (zinc),415.
Rossler process (silver),
317.
Pichou furnace, 120.
119.
(aluminium),
Pitchblende,506.
Roger process
Reduction Co. (aluminium), Rogers process (aluminium),118.
Pittsburg
(sodium),35.
108, m.
"
"
442.

560

INDEX.

59.
Rogers process (sodium allovs),
RoQtschewsky (anode reaction),294.

(zinc),417.

"

Rose

Silver extraction

(by amalgama-

tion),
300.

(by copper),300.
(by lead),301.
(by mercury), 300.

"

"

(aluminium),95.
"

"
"

glance,300.

"

ores,

S
"

Salom's process (lead),


464.
Sanderson's process (antimony),
486.

107.
504.
Scheelite,
Schindler furnace,152.

Schmollnitz

(Kiss),303.
(Moebius),317-327.

"

(MoUoy), 332.

"

(aluminium),

process

(House-Symon),327-

, ,

"

Sapphire,93.
504.
Sargent (molybdenum alloys),
Schaag-Falk

300.

refining(Augustin), 303.
303.
(Dietzel),

"

"

"

"

"

"

(Patera),303.
317.
(Rossler),
(WohlwiU), 309-317.
303.
(Ziervogel),

waters. Treatment

187.
of, Smee (electrolvsis),
188.
of tin-plate
Smith, electrolysis
scrap,
451.
Schneider-Szontagh
process (copper),
227.
Soda, 22.
211.
Sohreiber,G. (copper refinins),
Sodium, 22.
Seidel (copper sulphate solution),
allovs,58, 60.
"

207.
,,

Senarmontite, 474.
Senet process (aluminium),106.

"
"

Separatingvats, 345.
1.
Serpentine,
Siemens

W.

Siemens

"

Y.

,,

,,

,,

"

(Castner),64.
(Danckwardt),

34 1
(cyanide
process),
Halske
(cyanideprocess),

49.

68.
(Darling),

341.
"

Cost of,353.
electric furnace,
540.

"

Siemens-Halske

"

30.
(Davy),

(cyanideprocess),

,,

,,

process (antimony),
487.

"

"

(anode-plates),
213.

,,

,,

"

(copper-matte),

,,

"

40, 52.
(Fischer),
(Grabau),42.
(Hoepfner),34.

,,

,,

(Homung-Kase-

"

"

"

"

"

"

,,

"

,,

"

Requirements

"

35.
(Rogers),

"

"

meyer), 41.
(Jablochkoff),33.
(Netto),30.
(Omholt), 36.
(Rathenau and
Suther),67.

260-266.
"

(Becker),65.
(Borchers), 45,
47, 68, 60.

electric furnace, 119, 519.

, ,

31.
amalgam (electrolytic),
extraction

"

"

ing),
(copper refin-

211, 219-

for,46.

221.
"

"

,,

Siemens

"

Halske

"

351-368.
(gold),

"

(tin),451, 452.

"

413.
(zinc),

Borchers*

process

(copper),221-224.
SiUcides,546.
Silicon bronze, 546.
carbide.Production
Silver,300.
"

"

"

,,

"

-lead

59,
alloys,

-tin
,,

63.

59.

uses, 70.
Spathiciron ore, 511.
"

of fused aluminium
Specific
gravities
and electrolytes,
160.
507" 608.
of,386.
Spiegeleisen,
409.
Squire(zinc),
alloys,
Separationof (AndrS), StadtbergerHtitte (copper refining)^

303, 307.
"

(Watt), 31.
"

dor^. Refiningof,311.
extraction
(Balbach),327.
(Becquerel),317.
,,

211.

SUhl (zinc),
421.
Stalmann
(copper),236.
j^rocess
Stassano pig-ironprocess, 514, 527.

561

INDEX.

Steatite,1.

Talc, 1.

Steel,97, 98, 512.

Tanks

Stibnite,474.
Stockem, see Borchera,
StolbergCo. (copper),254, 256.
339.
Stolp process (gold),
460.
Stolzite,
280.
Strapp processes (nickel),

429.
solutions,
Tenorite,184.
Texasite,273.

Moller-Street,

Street, see

(Burchers),79.
(Borchers-Stock-

,,

Stutzel

"

(Feldmann), 79.
78.
(Hiller),

"

(Matthie8sen)78.

,,

"

(neodidymium),174.
(zinc),

415.
on

the

Tiemann
Tommasi

166.
6. (zinc),429.

282.
(nickel),
469.
(lead),
(calciumcarbide),531.
process

process

21.
Triphylite,

Trona, 29.
Troost

22.
process (lithium),

Tungsten,504.

Sulphide O}rporation Works


Swinburne

refining),

228-234.

Travers

em), 83.
,,

213.
(anode-plates),

(copper

chloride

105.

,,

"

process

Thorium,
Thromm,

extraction, 78, 85.

"

Thofehm

zinc
electrolysing

Thomas-Tilleyprocess (aluminium),

73.
Strontianite,
Strontium, 74.
"

for

Phoenix

process

(zinc),415, 441.

"

reduction process, 505.

treatment
"
Tungstic ochre,504.

of ores, 504.

Twinins-Burghardtprocess (aluminium,

Sylvine,71.
327.
Symon-House (silver),

107.

Ulke's

286.
experiments (nickel),

Ullmanite, 273.

scales. Comparison Uraninite,506.


Uranium, 506.

Thesmometer

of,548.
Tin, 449.

extraction, 449.
"

, ,

,,

(Beatson),454.
(Becker),459.
(Bohne), 452.
(Burchers' experi(ments, 454, 459.

,,

carbide, 545.

,,

507.
electrolysis,

"

precipitation
process,

506.

reduction

506.

,,
,,

"

507.

uses,

453.
(Brandenburg),

"

(Coleman), 455.
(Cruickshank),455.
(Divies),458.
(Gutensohn),451.
(Matthews), 458.

"

(Meyer),454.

489.
electrolysis,

,,

(Peetz*8

occurrence,

"
"

,,

Valentinite,

ments),
experi460.

"

474.

Vanadinite,460.
Vanadium, 488.
488.

properties,488.

455.
(Price),

reduction

454.
(Quintaine),
(Siemens " Halske),

uses,

process,

488.

490.

Vautin
process (sodium),60.
Vitriol,Blue, 184.
Vivian " Co. (copperrefining),
210.
(Weyland),453.
Vivianite,611.
of,450.
ore. Treatment
Voltmer (manganese),509.
uses, 460.
Von Hubl's experiments (copper sulphate
Tin-platescrap, Treatment of,450.
208.
Tinstone, 449.
solution),
Vortmann
285.
minium),
process (cobalt),
Tacony Iron and Metal Co. (alu108.
(mercury),448.
, ,

451.

"

"

36

INDEX.

562

Zinc, blende, 382.

"

bloom, 382.
chloride,420.

"

deposit.Cause

"

119.
prooess (alummiam)*
anode oastingmachine, 214-

Waldo

Walker
217.
Walter

106.
prooees (aluminiam),

Water-power (aluminium),161,
Wehner
(movable hearth), 528.
Weias, L. (oeriumgroup), 171.
"

Weyland

extraction,384.
(Ashcroft),414.
(Coehn), 412, 416,

"

162.

"

"

417.

174.
(neodidjrmium),
4
5SL
(tin),
prooess

"

"

"

"

(Cowles),384.
(Cowper-Coles),
412.

337.
Whitehead's
experiments(gold),
White lead ore, 460.

(Dorsemagen),386,

"

,,

389, 418.

Wilfleytable,344.
Willemite, 383.
Willflon (caloiumcarbide),529, 53^
Aluminium
Co., Furnace

(EschellmannX412,

"

"

419.

"

"

403.
(Forster),
(Giinther),403,4ia

"

,,

(Hoepfner), 419,

"

"

"

by, 537.

used

electric furnace, 125.

"

Winkler

process

423,

(aluminium), 118.

Witherite, 73.
Wohler
(manganese),508.
experiments (aluminium),
Wohler's
bide),
(calcium car-

,,

530.

Wohlwill, E., experiments (copper


mud),

anode
199.
,,

,,

(copper cathode
205.
crystals),

"

"

"

"

,,

"

(KoniglicheFried395.
richshiitte),
(Kosmann), 416.

359,
"

"

"

"

"

"

"

"

"

"

"

"

"

(Lindemann), 413.
(Lorenz),393, 443.
(Luckow), 389,413.

"

"

(Mylius

(Lange),416.
408.
(L^trange),

et

sea,

alloys,

,"

"

"

"

"

(Partsch),413.

"

442.
(Pfleger).
(Rontschewsky),

(Oettel),444.

288.
504.

Wolfram,
Wright (electricfurnace),540.
Wulfenite, 460, 502.

"

"

417.

Zaratite, 273.

"

"

"

"

,,

(uranium), 506.

"
"

of,395.

Treatment
alloys.

BBLL

AMD

BAIN,

ft
(Siemens
413.
Halske),
421.
(Stahl),
(Swinburne), 415,
441.

303.
Ziervogelprocess (silver),
Zimmermann
Zinc, 383.

and

Fromm), 398.
(Nahnsen), 409.
(Nothemann), 395.

(gold refining),

nickel- copper

ei seq.

440.
(Kellner),
39"
(Kiliani),

95.
"

396-

of spongy,

ores, 382.
Uses of,445.

Zincite,382.

LIMITED,

PRINTBKS,

QLA80OW.

J'

i6^

Potrebbero piacerti anche