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PREFACE
In
TO
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"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
the
and
introductory
numerous
theories
the
sketch
of
Author
of
this
-^
()
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,
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
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
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
in
consult
to
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
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
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
the French
those from
and
from
IX
have
Englishsources
original.
the
the German
been
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
to
and
America, and
in
England is to
hold her
there
is little doubt
that,
in
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
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-
....
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
,.
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
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
and
calcium-extraction
Stockem's
,,
,,
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
120
furnace,
ore-smelting
smeltingfurnace,
72. Siemens'
electric furnace,
73.
modified
121
121
123
electric furnace,
,,
124
Willson
H^roult
81.
The
82.
Modified
Hall
furnace,American
"
"
"
"
"
"
furnace,
(Minet) aluminium
Apparatus used at Neuhausen,
.
Aluminium
92.
Borchers' aluminium
extraction
Borchers' aluminium
apparatus,
furnace,
smeltingfurnace,
132
133
134
135
137
143
145
146
147
150
151
.....
aluminium
130
138
reduction.
91.
93. Modified
and
128
97-101.
section
longitudinal
furnace
apparatus. Hall
87.
in
......
86.
The
126
furnace
aluminium
aluminium
125
furnace,
H6roult
plan,
80.
102.
103
HI
reducing aluminium,
vessel,
electrolysing
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
64
.
duction,
88.
62
63
alloys,
plant,
sodium-extraction
electrolytic
53-55. Becker's
68.
61
,,
52. Castner's
66.
60
.....
56.
58
experimentalwork,
48.
67
.....
furnace,
152
172
XXI
ILLUSTRATIONS.
OP
LIST
PAGE
no.
103.
Weiss's
172
176
179
furnace
107. Borchers'
of cerium
for extraction
furnace,
metals,
productionof cerium
for
furnace
180
alloys,
201
122.
217
""
""
""
""
(Siemens),
Section of
of copper
131. Siemens-Borchers'
iofact
136a.
141.
Stalmann's
"
143-146.
Moulds
of
of
of
Plan
with
anode-strip
248
Casarza,
conductor
at
dJasarza, 249
249
(Casarza,
161.
Arrangement
251
251
depositing-room,
depositing-room,
of anode
252
253
process,
259
.
" 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
168. 169.
250
electrolyte
of the Marchese
" Halske
Siemens
the
circulating
of the Casarza
scheme
160.
of
installation,
Newer
main
238
,,
250
form
at
at
....
Cross-section
166.
of matte
250
155.
New
vat,
Hayden's
.......
165.
237
237
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,
"
of Thofehm's
of electrical connections
Scheme
142.
copper
222
electrode connections,
Stalmann's
221
to/oce
Thofehm
Anaconda
221
Plate XL,
(Siemens),
(cross-section),
electrical connections
The
vats
section),
(longitudinal
"
"
The
in copper
vats
copper
132.
220
of electrical connections
130. Scheme
218
219
(Siemens),showing cathode,
vat (Siemens),
vat
of copper
Longitudinalsection
136.
215
"
"
"
125. Cross-section
126.
213
216
Walker's
1*"*
124.
212
at
the anode
295
.....
ILLUSTRATIONS.
OP
LIST
XXll
PAGE
no.
174. Dietzers
175. The
Moebius
.....
apparatus, showing
Moebius
178.
apparatus
section
"
"
"
"
,,
,,
,,
Moebius
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
.318
plan.
scheme
179.
in half
.......
section
177.
anode
318
section,
176. The
304
vat,
alloy-separating
.337
192.
modified
"
340
apparatus,
.....
of wooden
341
separatingvats,
346
iron
196, 197.
""
"
plan of vat,
and
showing
",
Butters
and
Mein's
tributors,
dis347
.......
200-203.
Bottom
204-210.
Details of side
211-213.
Illustration of
348
....
349
.
Siemens-Halske
'
355
cyanide process,
214.
Cowles*
zinc retort,
electrically-heated
385
....
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,
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
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
See
MAGNESIUM.
Magnesia, like
held
all other
to be unreducible
oxides
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
Experiments
"
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
which
metallic
or
"
"
it in
short
time
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
IIPogg.
8MELTINO
ELECTRIC
to
the
AND
bottom
RBFINIKO.
; in
of these
one
hberated
the
access
and
the
from
pole
the
in
the
of
form
would
there
be
the
experiment
the
it,are
to
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
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 4*7 amperes.
arrangement of the
current
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
of
of this
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
uselessness.
effect
Apparatus.
has
been
"
A very
described
See Alumimum,
t Lehrhtich der
anorganischenChenu,
(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
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
wires
might
The
asbestos,and
be
cover,
had
an
steadilyand
g?,was
that
from
the
hot
*
gases
uniformlyraised
also coated
on
the
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
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
kept
were
in
batterycell),
porous
bored.
were
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
thick,served
combined
with
as
litmus
small
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
"
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.
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
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
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
MgO
the
temperature
higherthan
of the
is desirable
desired
C +
CLj
MgClj
would
have
bath
in the
inconvenience
the
reaction,as
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
cathode chamber
and
lithium.
of his
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
therefore,necessary
immersed
this
on
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
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
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
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
be
be at
once
solidified.
Graetzel
Napier's
with
in contact
crystallised
with
the comparativelycool walls,
yet any thin layer of fused salt that
upper
air
the
if the
^^ the fused
electrolytic should
reduction.
his
it
the formation
fused
with
The
even
9.
support
The
to
crucible
crucible
only
the crucible
within, and
2 to
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
indeed, originallyintended
find combined
in it,even
we
for
the
at
in
extraction
may
1844.
of
most
be
given
It
was,
copper,
but
important
elements
such
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
+ Cj\ GraetzePs
Patent
cxxv.,
684, 1845.
p. 376.
15
MAGNESIUM.
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.
"
"
electrolysis
fused
salts.
Within
cathode, is suspended
the
the
iron
carbon
*
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.
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
meltingvessels,however,
generator.
The
is best built
in
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
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
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
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
also have
been
of
heated
then
beforehand, are
introduced,and
the
is started.
electrolysis
process
If all the
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
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
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.
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
melted
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
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
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
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
led to
with
as
its introduction
industries
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.
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,
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
the
"
many
togetherwith
at
protectedfrom
It melts
clear red
at
180"
heat
C,
and
(about 1,000'C).
At
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
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
alkaline-earth metals,which
the
are
are
The
always present,must
separationof these
and
great difficulties,
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.
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
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.
*
de Chim,
et de
Phys.,
^'l :
LITHIUM.
According
author's
the
to
experiencewith
just described,lithium
kind
in them
electrolysed
for
and
other
short
so
with
time.
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
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.
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
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
the
Apparatus.
productionof
extraction
In
is
strontium
from
of lithium
Fig 14, t
"
that
is
an
apparatus for
well adapted
especially
to
its chloride.
porcelaincrucible
which
contains
the
fused
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.
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
of liihium.
sunk
is disconnected
which
would
the inner
The
with
from
dilute
painted
over
the
to the
solution
of
is coated
into
thick
of the metal
a
thin
with
layerof
silicon,
graphite.
lithium
with
26
SMELTING
ELECTRIC
the
by
alkali
silicates
metals, in
AND
REFINING.
of the
consequence
reduction
the
of
them.
by
notable
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,
and
liquid,
The
wide.
ram.
meter,
dia-
in
mm.
glasstube
level of
is raised out
rod
3 to 4
tube
glass
in the
carbon
an
of 20 volts and
current
will be found
there
of
consists
which
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
the
treatment
which
contains
alkaline-earth
This
metals.
of
only
soln-
little sal-ammoniac
and
the
is fused
mass
may,
if
above
the
is
now
for
added
neutralise
to
in
electrolysis
an
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
27
LITHIUM.
continued
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
metallic
porcelainsheath
the
be
not
descriptionof Troost's
the
quantityof
sufficient
the
otherwise
must
electrolysis
forms
explained in
were
a
carbon,
The
In
magnesium.
order
to
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
by Kahlenberg,*
owing to the
use,
practical
unsuitable propertiesof the solvent employed for the electrolyte.
Lascynski and Gorskif had already,in their determinations
of
it
has been
of lithium
that
found
conductivity,
be
to
scarcelyprove
can
discovered
of
chloride
lithium
was
soluble with
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
subsequent
difficulty,
little
so
use
use
in the
lithium
production
for
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
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,
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
3H.
caustic soda
an
upright
EIiECTBOLYSIS.
Davy's
the
Experiments.
hydroxidesof
"
The
potassium and
electrolytic
decomposition of
sodium
led,as
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
apparatus
an
of
process
^e
on
type
used
"
solution.
OF
EL.ECTROLYSIS
SODIUM
CHLORIDE.
The
"
ran
patent specification
second part of my
or
obtainingthe
united
action
follows
as
The
metals
of
"
invention
consists of
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
metals
attachments,
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
suppliedby
Fig. 17.
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.
The
Daniell's
cells of
ten
the
the
be
[ihe
eliminated
eliminated,the
that
oxidised.
be
to
the
so
line
also excludes
the metal
the
between
be used
to
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.
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
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
"
"
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
perature
the chloride
after
at the bottom
remains
current
of its
of the crucible."
short
ascertained
with
and
quantities,
in
so
other
be
metal
dissolved
the
re-depositedat
coherent
slightly
at
the
cathode
condition,that,
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
36
the
be
ELECTRIC
details
of
SMELTING
AND
its oonstructioii.
expected that
Nevertheless, it
advantageouslyused
be
it could
REFINING.
the material
; and
is
scarcelyto
of which
it is made
is
Fig. 19.
"
F'
x_ir
rp
Fig. 20.
Rogers'apparatus
after
hours.
few
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
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
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
renewal
or
of broken
half retorts
without
damaging
the
electrodes
alteringtheir position.
"The
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,
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
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
A:^ to the
halogensproduced
the fore-
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
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
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
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
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
it,and
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
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
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
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
Fig.2S.
"
Grabau's
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
of the FranJdin
Patent
October 8, 1889].
15,792,
44
SMELTING
ELECTRIC
REFINING.
AND
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
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.
SS.
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
chlorides,and
to
add
produced
contains
no
retain
,3 per
cent,
of
potassium. Trans.]
"
4"
SODIUM.
weeks
; but
the
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
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
in
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
:
"
preferablythe
better
sorts
be used
as
the material
"
of iron.
alkali metal
must
into contact
4. The
47
SODIUM.
conditions
These
of
apparatus;
one
improvement
in the
that
at
were
time
that introduced
was
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
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
high
bell
sufficiently
prevent solidification on
mous
walls,owing to the enor-
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
about
It consists of
two
togetherby
chambers
a
are
size.
nected
con-
specialjoint.
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
collection
Borehers, Alkalimetalle,"in
**
which
be
"if^,30."
tube-
metal,
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
50
ELECrKIC
SMELTING
"
Danckwardt's
AND
REFINING.
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
in
of the water
been
attained
stopped,the
is
and
B,
into
tapping.
the
cocks
flow
temperature
blast
pipe,a\
escape-pipe,
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
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
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
^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
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
"
"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
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
bath are
of this is that in the lower
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
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
completely fluid
of sodium
of the surface
REFINING.
be
to
to include
as
The
area.
the
at
far immersed
so
AND
the
through practically
of a sleeve
by means
the
was
so
should
SMELTING
considerable
proportion
of the
bell
was
Fig. 41.
"
Fischer's
sodium-chloride
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
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-
that the
of
larger
apparatus might
use
placed over
the
hood
or
cathode
of
be
bell
that
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
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
had
REFINING.
AND
SMELTING
ELECTRIC
to the
portionunder
compartments, just
compartment
the
as
the
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-
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
have
time
for the
constructed
so
it
as
to increase
gained by
was
in
loss of
unnecessary
this form of
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
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
for
for
described
above
chloride
"
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
and
does
not
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.
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
104 grms.
cathode, connection
crucible.
end of two
cooled and
of
Each
The
hours
broken
rod
made
open,
force
used
the
bottom
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-
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."
"
Aluminium.
t Journal
of the Franklin
Hist,
Soc., 1889
(from Richards*
60
ELECTRIC
The
AND
SMELTING
REFINING.
had
again become
hindrance
led Vautin
to progress,
to
thus
forward
put
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
Fig.48. The
short cylinderterminating
a
wall of the conical portion
of
inner
shown
in
terraced
formed
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
it would
"
vessel
in
nally
exter-
an
be
It may
material
Fig. 47.
with
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
to
the
be
und
61
SODIUM.
in the melted
used
condition.
The
carbon
anodes, A,
with
their
V, which
with
the
to make
positiveleads,P;
of the
in the bottom
Fig. 48.
loss
"
operation had,
overflowed
by
the
The
pipe,X.
Borchers'
of salt which
cone
was
of course,
of the
to
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
""2
to
KLKCTHIC
catx:h any
SMELTING
that
matter
channel, S,
collecting
from
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
either of
one
thick
63
SODIUM.
size of the
of 300
amperes,
If
volts.
be
sodium
correspondsto
which
5000
amperes
The
surface.
illustration,is adapted
ahove
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
circumstance
of lower
stream
of lead
flowing beneath
them,
so
that
alloyscontaining
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
so
SEPARATION
The
OF
Castner
Prooess.
above
As
"
of caustic soda
electrolysis
for the
is
process
HYDROXIDE.
THE
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.
none
may
ring,a^.
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
D, insulated from
the
apparatus, is
suspended
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
at the anode
D,
must
the
not
be
height of
immersed
the
in the
rim, dy so
so
the
generated
collector,
bath
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
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
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,
be attacked
anode
fitted with
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
68
ELECTRIC
REFINING.
AND
SMELTING
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-
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
as
was
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
of
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
100
was
EngUsh
on
of the
the middle
Patent
6,808,
SODIUM.
of this
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
The
sodium
is ladled
the anode.
anode gases are collected and converted
at
"
of the
vessel,and
the
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
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
hours.
SODIUM.
of sodium
sodium
an
only
at
lasting
diaphragin.
furnace
pressure
within
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,
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
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
salt of
potassium
therefore,
suffice,
especially
proposed for
the
extraction
potassium.
Matthiessen's
the
observation*
of
electrolysis
"
mixture
that
of
72
ELECTRIC
was
interesting
; but
in the
SMELTING
salt
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
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
are
"
On
hitherto
account
of the considerable
dangerous
method
of
violence
production,
the applications
of potassium
highpriceof potassiumsalts,
remained
to be written
*
Joum.
416.
74
ELECTRIC
SMELTING
BEFININO.
AND
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
nitrogen,calcium
but
fluorides,
or
alkali
metals
their iodides.
from
not
is formed.
nitride
heated
in
an
phere
atmos-
Calcium,
at
their chlorides
from
It reduces
the
calcium
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
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
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
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
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
76
ELKCTRIC
to obtain
it from
SMBLTING
the reduced
the fused
REFINING.
AND
met"al in coherent
The
substance.
masses,
and
to
separate
depositedmetals
part rise
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
CALCIUM,
with
the
fused mixture
same
salt,and
of
77
BARIUM.
STRONTIUM,
for the
serves
tion
recep-
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
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
and
crust
metal
be reduced
*"'The metal
in
may
surface of the melted
upper
for from one
to two minutes, that
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
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
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
Strontium.
of
Extraotion
accounts'*^ the
difficult.
ammoniac,
so
by
positivepole,and
into
the
that
Matthiessen's
to
with
touching the
side
Matthiessen
had
are
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
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
According
a
strontium
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
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
without
Chemie
f that
The
of
sources
metallic
barium
in
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
Liebig-Kopp'sJahresberieht,1855, p.
1856,
Society,
berieht,1855, p. 320.
79
BARIUK.
8TK0KTIUM,
CALCIUM,
become
been
used.
high current-density
necessarily
The method
originatedby A. Feldmann*
either to mix
He
retrograde.
proposes
the
haloid
of
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
[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
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
problem
Matthiessen,
necessary
per
:
"
sq. metre
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
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.
the
frequently. The
beneath
the
stronglyheated
the second
way
by
"
other
been
of
it has
hand,
in
this
On
the
frequently
maintained
low
at a temperature so
a solid crust
that,if possible,
be formed
may
The
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
area,
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
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
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
at
in which
made
he, with
his
in Borchers'
pupil,L.
tories
labora-
Stockem,
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
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
The
amount
largest
proved by
was
calcium
experiments,when electrically-fused
red heat, under which
at a moderate
electrolysed
later
chloride
waa
the
conditions
metal
sponge
the cathode.
and
anode.
the
bottom
fluor
of
which
spar,
is
fironk
prevented
this
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
was
With
the current.
Figs. 60 and
made
any
convenient
most
it into
mains
current
than
more
was
found
was
"
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
chloride
carbon
as
now
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
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
the fused
from
was
separated as
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
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
per
pure
found
Stockem
vessels.
that,
the
on
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,
not
be
low
maintained
the
so
metal
could
somewhat
be
should
62.
floated to
be
surface
speciflcgravity
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
86
ELICTBIO
that
the
SHSLTIMO
coUecta
metal
on
bottom
to
minimise
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
the
by
part of
carbon
the
cylinder.
metal
chlorine
bottom, rested
as
salt,the
strontium
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
in the
calcium
BEFIKING.
the
anode
AKD
evolved
the
at
was
anode, and,
on
chloride.
the
obtained
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
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
hydrogen
when
thrown
it,for
in constant
the
evolves
readily
flattened
made
found
was
softness; for,
were
by
mass
was
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
is much
Beduotion
of
metals, like
the
Oxide.
The
"
oxides
of
the
alkali-earth
only carbide
no
more
in this way.
Even
if a mixture
be used
carbon than is requiredby the equation
CaO
Ca
containlDg
CO,
leadingto
the
separationof
the metal.
87
BEBTLLIUH.
If the carbide
long time
and
the
be
kind
it is often
hydroxide as
or
obtained.
that
the
soon
residue
of the
Metals.
air
as
In
been
finely-divided
rapidproductionof calcium
gainsaccess to it.
of at the end
It is obvious
"
that
of the
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
"
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
"
-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
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
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
barium
these
addition
chloride
The
barium.
of
by
with
or
of
means
either
alkali-metal
an
of
or
some
solution
of
chloride
of
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
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
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
Liebmann,t
in
his
patent
for
the
production of
be^llium
method
Chemical
t German
News,
Patent
91
BERYLLIUM.
Lebeau's
Experiments.
to the treatment
of
"
beryl
confirm
intimate
an
beryllium,together with
which
carbide,from
and
beryllium,
If
and
for
and
dilute
acid
hydrofluoric
of 100
mixture
50
ferro-silicon
the aluminium
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
Calcium
carbide
is found
to
be
convenient
reducingagent.
On
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
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
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
will be volatilised.
It
p. 1203.
is,therefore.
92
SMBLTING
ELBCTBIO
AND
BBFININO.
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,
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-
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
structure
crystalline
by
the
years.
these
and
metallurgical
chemicallypure,
obtainable
other
aluminium.
of pure
last few
(Al'";atomic
Aluminium
"
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
rapidlyloses
its
[11*4tons
mm.
per square
from
reducing the area
20
1,
to
[14-9tons
mm.
inch];after
per square
the tensile
per
strength is
inch];
square
so
23*5
or
to
[17*7tons
mm.
inch].
per square
electrical
conductivity of
The
Richards
100),is
t (copper
For metal
,,
),
"
"
"
"
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
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
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.
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
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
96
ELECTRIC
in
cryolite,
of
order
to
SMELTING
The
RBFINIXO.
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
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
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
"
the
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
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,
chieflyin
resistance,or
Previous
this
thus
"U.S.A.
Patent
319,796.
99
ALUMINIUM.
These
circumstances, however,
detract from
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
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
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
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
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
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
the
to
mouth
keep
of
the
the
rod,
place.
Theory
of
inspectionof
the
Cowles
"
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
"
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
by carbon, because
rods
of the screw,
means
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
The
author
contrary,as
cannot
a
of the alumina
if^fluence
of
agree
of his
result
in the Gowles
the heat
this
is attributable
furnace
generatedby
the current
sdely to the
in tfieresistcmce that.
is introduced
the range
Deville's furnace
completion
such
an
of
beyond
of the
should
reaction.
apparatus
to
that
possibility
It is not
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
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 carbon
and
of 35 to 40 amperes
is
for from two to three minutes.
current
on
proportionof
been
having
experiment,and,
arc
the
formed
The
is excluded
in the absence
of any
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
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
such
alumina,
equivalentto
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
as
be denied
*
the evidence
as
to
the
advanced
from
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
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.
the moderate
current
of 6 to
7 volts and
with
the
circumstances
"
solution
is
by
4 amperes.
of aluminium
nitrate
is to
be
so
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
(From
15, 1883.
Richards'
Aluminium, 1890.)
107
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
process
had
be
to
been
not
for the
however, be
taken
beginningof
this section.
R. de
as
Monteglas,!in
from
lytically
solution
of aluminium
to
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
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,
EnglishPatent
t German
" German
Patent
liGerman
Patent
Patent
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
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
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
deposition
producing this
the
usingplatinum
subjectedto strong pressure, and
is to be
metal
into
be cast
to
treated
The
of
manner
REFINING.
AND
SMELTING
success.
"
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
an
alu-
sodium
and
stannate
bath
was
in
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
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.
DeTille's
text-books
of these
acconnt
As
statements
Process.
to the effect that Deville
"
process
to his
with
exf"eriments"
which
adduces
French.
*'
Up
obtain
"
his
given in the
here
of
crept
into
left
intentionally
has
many
Bunsen's
reference
Bunsen's
reasons
form
have
||
to
impossibleto
of the gal-
aluminium
PhQ.
original
paper.
"
Translator.]
110
ELECTRIC
AND
SMELTING
RBFININO.
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
'"
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
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
centimetres
from
crucible.
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-
with
for
small
are
(two are actuallysufficient)
required
which
feeble
ance
resistchloride,
presents only a
of elements
number
to
aluminium.
decompose
to
the
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
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
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-
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.
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
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,
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
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
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
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-
(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
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
in
Grousilliers,t
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
117
ALUMINIUM.
producedby
this
the
solidifies over
portion
circulation,a
of
the
surface
cooled
the
of
whole
melted
of
salt
the
cell,
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
to come
appears to be
it is shown
in
Grabau
whether, by
the
be
of
aluminium
Further,it
contact.
use
nature
of the anode
cell
as
removed.
efficiently
with
iron, to
aside,the
introduce
author
has
mixtures of aluminium
salts
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'*'
alone
used
of
want
BBFININO.
AND
processes.
the present
has
time, patented
to
up
electrolytic
separation of
aluminium
pure
and
from
the
aluminium
silicates.
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
the
plant for
his
zinc,with
or
afterwards
;||and
latter metals
The
of
nature
did
the
fluoride
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
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.
by
excess
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
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
itself;and, in
has been
heated,
as
by includingthe electrolyte
or
in the
resistance
electric circuit.
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
arc
in the
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
tem|"erature obtainable
The
source
Siemens
in the
electric
arc
seems
to
have
first utilised in
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
patent
was
for the
real
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
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
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
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
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
melting would
the other
sudden
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
quarter of
half
consumption
an
stream
*
hour, and
from
was
be translated
the
the
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
author
be melted
To
Translatok.]
quantity ;
in the above
pl"oe
123
ALUMINIUM.
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
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
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-
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
"
EnglishPatent
4,208, 1878.
124
ELECTRIC
SMELTING
AND
REPINING.
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
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
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
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
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,
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
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
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
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.
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
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
to
cover
the
the
openings,n, during
the
130
ELECTRIC
SMELTING
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
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'
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
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
States
the
divided,and formed
400,664 of April 2,
July 9, 1886 ;
patents 400,766
of America
on
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
132
ELECTRIC
SMELTING
alumina,
and
the
electric
or
is
other
solution.
preferablyhas
oxygen
released
at
fv?ien it
electrode
18
of aliiminium, in sufficient
D,
suitable
the
By
connected
of
source
bath
fused
an
force
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
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
other
or
mV^y
p
Pig. 81."
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
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
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
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
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
"
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,
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
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
be
may
can
lower
be
picked out."
patent^external firingis expresslyprescribed
in this
Clearly,
heating of
for the
cathodes
claims
are
make
stillfar from
any
it
and
its contents,
of work.
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
fusible
and
its
Fig. 85.
400,664.
and
potassium
capacityfor dissolving
'^
"
135
ALUMINIUM.
the
bath
"
and
D, having
machine, or other
suitable
with
connections
suitable
electric
of
source
inserted
therein.
action
electric
the
of
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
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
when
in
some
of
efficient after
separated; but a
the bath, apparentlyfrom
(!),which interferes with
increases
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
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
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
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
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
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
owners
of the
Company)
has
Hall
more
patents
in
common
"
139
ALUMINIUM.
wiUi
above
in the
patents
or
with
that
of H^roult.
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
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.
and
"
bath.
2. The
at
sol vent
must
be able to
and
dissolve,
to retain in
solution,
be
auch
the
"
be
more
readilydecomposedthan
dissolved ore.t
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
conductor
of
7. The
good
electricity.
solvent
have
munt
corroding action
no
nascent
on
aluminium
of aluminium
of sodium
251
fluoride,
and
fluoride,
of calcium
234
fluoride.
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
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
bath
supply
that
so
deposited,
It is necessary
should
be as pure
foreignsubstances
will for the
the
the
about
to withdraw
taken
and
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.
information
satisfactory
to the
actual
is
on
the
is
current
from
alumina
is about
assumption that
746
5 H.P.
ampere
hours.
hours
This, of
yield0*554
141
ALUMINIUM.
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
"
subjectedto
which
might
standiugs,
which
was
similar
prevent misunder-
To
criticism.
in
in
England
plete
sought ; the comprovisionalprotectionwas
in
with
was
January,
drawings
presented
specification
July,1887, when
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,
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
"
noxious
vapours, hence
extraction of aluminium
therefrom
commerciallyfor the
by electrolysis
; in all cases
used
occasioned.
be
it cannot
It has been
sought to
"
render
it still more
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
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
nature
most
salt of sodium
there
different
in
the aluminium
aluminium,
that
"
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
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
former,
in the form of
being employed,accordingto their
singlesalt
the
and
has,therefore,been
aluminium
tised
of
and
fixed
more
bath
"A
sodium,
and
(?).
current
of
REFIXING.
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
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,
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.
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
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 :
upon
largescale
of the current.
influence
*'
2. The
avoid
**
of aluminium
of
use
brick
coveringfor the
tank
metallic
as
so
to
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
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.*
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
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
REFINING.
Since
was
the
clear
extraction
material
same
of
source
that, at
heat
certain
apparatus.
fusion,the coolingaction
of the
air
"
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
narrow
of
the
aluminium
lining of
the
top
as
an
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
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
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
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
follows
:"
''Hitherto
by subjectingthe
on
a
before
(i.6.,
other
fused
or
crucible,
the temperature
condition
gas)attacks
of the
it has
is
is that the
the consequence
destructive fluxingaction takes
treatingalmost
'
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
preventingthe
working the process, for
which
especially,
cryolite
and that the
of the
action
is
; but
destruction
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.
"
main
"
ore
and
the
gas
*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
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
truncated
and
cone,
Fig
Fig.95.
94.-
Bradley'saluminium
smeltingfurnace.
heat
of the
and
arc
becomes
conductingelectrolyte,
through
"
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
apart,in
not
attacked
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
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
says
of the cathode.
The
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
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.
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
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
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
for the
granted
was
the
the
in 1890
use
AktiengeselUchafi
state
which
of
case
heating,when
current.
electrolysing
similar
fusion,either by
an
E.M.F.
of 5
means
volts ia
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
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
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
eondition after
other
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
separatedfrom
hydroxide by
pure
REFINING.
AND
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
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
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
is carried
*
material
in trucks
away
Transacttoji
Inst,
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.
Etigineering,
157
ALUMINIUM.
The
bauxite
solution
so
of 1*45
prepared is now
speciticgravity at
treated
a
with
pressure
caustic
of from
soda
to
The
clear
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
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
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
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.
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
[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/
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
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
1,500 H.P.
to
vary
between
1,400 and
^Joum.
1,600 E.H.P.
Soc, Chem.
would
in
necessary
twenty-fourhours,
from
for the
be
same
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
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
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 dense
Indeed,with
carbon
of
from
the
of air around
high
thermal
the
apparatus.
conductance
now
walls and
the
carbon
of the smaller
use
to
this account
ing
in describ-
of the
furnace
of the
out
plant,it
then
cool,and
solidified
mass.
It
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
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
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
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
or
carbon
either
materials
blocks
there
are
on
the outside.
available
"
For the
ccUhodcy
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
162
ELECTRIC
AND
SMELTING
REFINING.
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
treatment
6,000 H.P.
remain
for
in
electrolysis.
Finally,the British
"
which
aluminium
Qould
proportionsgiven in the
Aluminium
substitute
in the
in
one
way
or
other
be
substituted,the
form
of sheet
for copper,
wire
and
tube
"
is used
as
the like.
ALUMINIUM.
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
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
sides of
to be
are
heated,and
not
intended
as
to
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
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
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
or
refining,
compounds
oxygen
leads
the
to
i'ormation
and
solution
of these
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
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
200
to
ton.
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
case
and
of
by
in the
its
{cf,chromium,
means
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
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.
or
has
without
electrolysis
or
the
submitted
been
attempt
any
at
separationpreviously.
Cerium, Ce,
Cerium."
of
Properties
the
best-known
metal
than
about
800** C.
of this group,
6 '73.
It has
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
obtain
to
then
residue
dry
melt
tion
solu-
the
chloride may
didymium
or
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
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.]
as
thick
of
mixture
thick
of which
iron wire, the end
thinner,and round its end is twisted a
as
horse-hair,which
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
about
cm.
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
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'
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
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
found
They
in
aa
that
they
refer to the
must
form
of
which
experimental furnace
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
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
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,
safety.
Borchers
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
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
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
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
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
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
The
of
the
to
of ammonium
aboat
a
[approximately
further
be
carefully
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
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
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
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
furnace
was
cathode
the
cm.
or
was
the
anode.
at will.
ensure
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
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
were
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
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
current
as
the
and
as
decreased
to "0 amperes,
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
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
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
pieces.
found, a fact
to
Fig. 107.
"
Borchers'
furnace
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
experimentssach
as
those
types
justdescribed.
180
ELECTRIC
SMELTING
RRFININO.
AND
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
this work.
REDUCTION
2.
FBOCESS.
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.
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-
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
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
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
"
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
to
consideration
of
of the
metallurgical
:
processes by electrolysis
"
attempts, in
purely
many
chemical
or
186
ELECTRIC
SMELTING
BBFININ6.
AND
reduction
in
in
1
stage
the
furnace
Product,
"
of the
malleable
copper.
Black
"
"
"
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
noble
and
metals,
iron) are
"
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
combining
than
of the cuprous
sulphur it exhibits
mixture
with
heavy metals,and
with
this
the extraction
property
of copper
187
COPPER.
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
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
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
salts
Eleotrolytic Befining
has indicated
as
acids
of the oxygen
condition.
in the divalent
account
either
divalent
reason
was
of the
lost in
dynamo.
the
utilising
field of
metallurgy until
ever,
Following upon this,how-
in the
current
in
question.
to apply the current
constantlymade
and
the
t
o
treatment
especially
metallurgical
purposes,
Attempts, however,
to
were
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
"
^^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
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
"
'"
"
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,
tU.S.A.
by-
pure
the
189
COPPER.
in which
above
by
stated
ores
copper
w^ould
before
operate.
is not
part
This
process
for it has before
new,
bottom
to the
of the
generaloutline
in its
patented and
been
as
used
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
me.
of
combined
was
copper
vessel
present
such
silver is not
extraction,but
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
of
the
which
regulus,from
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
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
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
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
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
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
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
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
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
afterwards
from
The
may
the vats,
for
be worked
inconvenient
to the
advanced
work
to
it will take
but
pimple or
blister
iron) with
(exceptingthe
metals
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
be
treated
recovery
in
of the
separatedfrom
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
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
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.
pressure,
without
riightexcess
which
at
once
from
to
the
set in motion
anode
providedfor
as
the
the
of
largequantities
cathode, where
copper
on
their
path
to
an
they deposit.
Theory
and
practicealike
teach
that
only a
very small
electro-
194
SMBLTING
ELECTRIC
REFINING.
AND
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
on
liquid.The
in
weaker
but
slightly,
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,
suitingsolution.
the
doubt, arose
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.
acid, and
antimonic
tend
so
the
is saturated
solution
precipitatedin
at the
cathode
so
long
an
removed
with
the
neutralisation
the bath.
from
antimony,
of the
least marked
and
when
Even
when
coming
salt is be-
basic
proportionsof
the normal
towards
electrolyte
; but, of course,
the slime is the most
often
acid
and
copper
; at the
worst,
some
case
*^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
are
chemical
solution of such
metallic
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
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
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.
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
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
cent,
after ten
even
days
in
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
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
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
"
[1*8to
sq. metre
"
The
operation
of the various
detrimental
In the
influence
above
reactions
whole
the
on
the
solution,producedby
alluded
course
is greatly
place,the conductivityof the electrolyte
the
and
the
difference
of
between
Kiiminished,
potentialrequired
first
electrodes,under
5
otherwise
0*25
have
of this
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
so
and
is
electrolyte
also
an
essential,
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
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
[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
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
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
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
of
[25lbs.]
hour, or 272*26
the steam
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,
determination
accurate
an
"
From
privatecommunication.
200
ELECTRIC
8HBLTIKQ
REFINING.
AMD
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
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
effects
the
that is
copper
least,as
mud
of the
action
current, but
lying immediately beneath
and,
is
from
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
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
vol.
ccxlii.,
p.
286.
202
SMELTING
ELICTRIC
anode
BEFININO.
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.
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
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
presence
furnishes
the
copper
anodes
constituents
difficultly-soluble
"The
mud
copper
protectiveaction
the
sulphateand
explanationof
decrease
the
gradual increase
in the
of
baths
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.
of
use
baths.
the
would
anode
formation
the
to
in
as
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
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
free from
chlorine
Hence,
originallypresent
is used
to
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
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
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
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
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
other
On
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
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.
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,
"
the
of great interest to
Miigge,formerly of
!206
SMELTING
ELECTRIC
AND
REFINING.
played an
It
found
was
chlorine
reached
in the water
its
and
maximum,
all the
anodes
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
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
intermission
introduction
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
*'
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
"
current-densities
1. At
of less than
001
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
Cu
This
reaction
saturated
in the
with
continues
cuprous
until
Cu
the
sulphate.
2Cu.
sulphate solution is
cupric
It is difficult to decide off-
Wiedemann,
((j/l
without
inflaenoe
208
ELECTRIC
hand
far the
bow
SMELTING
of
REFINING.
of cuprous
sulphate solutions
formation
of copper
electrolysis
process
AND
solution,or, indeed,whether
is
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
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
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
be
observations
The
Seidel
will's
Von
first
are,
in
at
receive
cupricions,so
the
anode
Hiibl's
published
industrial
des k.
u,
1886,
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
of
perties
pro-
always distinctlyinferior to
has
which
been
mechanicaUy worked.
to it,however, as already shown, when
are
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
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
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.
fonud
General
the crude
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
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,
Electrodes
are
in
the
Baths.
suspended, anodes
of from
20
in agreement;
in the
are
is the
it is
objections,
Arrangement
all
in
of the electrodes.
electrodes
the
PARALLEL
THE
system
and
use
the
electrodes
all similar
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
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
so
well
known
and
are
which
distant
be
most
unusual.
direct
from
the
date
that,under
obtained
Hence, it
existingcircumstances,the anode
reverberatoryfurnace
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
made
so
be considered
may
material is usually
Nord-
of the
and
simplesttype,
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.
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.
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
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
[1in.}.The
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
frames
run
are
to the
up
On
converter.
the
under
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
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
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.
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,
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-
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),
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
~=dtiii!^
Fig. 126.
"
Longitudinalseclion
of copper-vat (Siemens).
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
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.
Siemens-Borchers'
fitted with
132.
seen
of
soon
Borchers, of the
this invention,it
The
Fig.
that the
Borchers'
copper-
vats
section).
(longitudinal
is shown
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
surface, lowers
tube, 6, and causes
of the
contents
the
the
to
of
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.*
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
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
at
In the
Installation."
and dischargingof the
the filling
SiemenB-Borohers'
effected
by
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^
-^^".
__^wt^'
'^*^';:'"''^'^"?**^^^P!J^^^p^
226
ELBGTRIC
''
From
new
sunk
the actual
that
of
cost
refining
reduced
has been
of the
REFINING.
AND
SMELTING
in
about
appear
"In
introduce
to
the
works, either
have
the
improved
into
process
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
themselves
recognised
system, and
that
they
originaldesignersof
did
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,
Patent
663,093, June
30, 1896.]
228
ELECTRIC
farther
SMELTING
from
removed
the
vertical
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
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
however, afford
Revue
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
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
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
lined with
the lead
from
connected
lead
on
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.
15
Two
Btrip-electrodes.
of 10
AND
in all
coupled in
are
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
from
set
every
of five tanks
to
measuring apparatus
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
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
and
the
Anaconda
Copper
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
"
"
costs
of
cost
per
ton
of refined
metal.
There
are
120
men
employed
in
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
"
"
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
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
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
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
200
passes through
facilitate the circulation
tanks
in
tanks
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
Iihs 8 small
tanks
lead
doing
anodes
serve
there
so
must
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
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
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
whole
series.
The
connected
immediately
joined up in series
are
The
"
to
139.
In
the
with
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
in contact
plate comes
Fig. 140.
"
Stalmann's
with
the solution.
last*
(cross-section).
vat
copper
The
The
named
made
is
of
wooden
walls
to
of the
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
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,
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
.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
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.
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
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,
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
only
different tanks
system
"
of Siemens-
must
names
Beflning.
those
the
dispositionof
any
Series
in
are
belonging to
Hayden and
pairs within
the
the
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
240
BLECTRIC
8MELTINO
AND
REFINING.
of the
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
over
superiority
TREATMENT
the
From
IMPURE
OF
the
descriptionof
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
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
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
much
as
as
possiblebefore
of
Treatment
In
Impure
the
clear
Solutions
in the
Chicago
Copper
"
the
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
small
the treatment
the impurities(chieflj
arsenic
and
antimony) are
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
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
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
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.
244
ELECTBIC
According
in the
to T.
8M"LTING
RBFIRiyO.
AKD
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
latter
allowed
to
settle,after which
now
mud, which
the
clear
solution
is drawn
ofiT.
residual
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
obtained
in tellurium
this
as
been
the
drawn
with-
above-described,nitre
slag thus
The
if there
were
duced
prosale for
any
would
works
one
for
furnace
metal.
that
After
blast
the
of the
surface
[6-6lbs.]
daily.
been
in
After
yield 3
grammes
kilo-
for the
lytically
crude
ProoesB
Baritan
copper.
used
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
245
COPPER.
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
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
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
"
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
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
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
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
remains
that
of
account
it
which
course
has to be
material
prepared
from
anodes
are
the
kind
of metallurgical
ores
or
formed
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
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
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.
"
"
the baths,
through
with the
about
brought
circulation
uniform
arranged in
aid of leaden
the vats.
The
channels
through a
on
the
bottoms
installation.
depositing-room.
stood at the
^hole
of
the
in
The
of the installation is
Figs.152 and 153.
arrangement
illustratedin the accompanying three drawings,of which
Fig.
154 is the
a
generalview
With
anodes
of the interior of
of such
complex
the
one
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
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.
after
short
Chemialfyfm
time
of action.
/Residue
Solution
plates.
eoniaininq
Sulphur.
h^cipitMle
of
Copper
Cu
S.
mTOKSSKifihU
"
"
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
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
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
with
other
about
to
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
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
[O'Sin.]wide
cm.
be attached
to
cross
riveted
to
stripswhich
slats
stripswith
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
by allowing
large iron
ground
otherwise
[2 fbb
ladles and
iron
in
thick
cm.
made
strip,outside
the
by
sunk
were
They
AT
USED
wide, 4
cm.
of the
out
ANODES
OP
was
electrolyte
made
by extractingthe
richest mattes
256
SMELTING
BLGCTRIC
50
when
ready
for
contained
use
phuric
dilute sul-
copper) with
of
cent,
per
REFINING.
AND
about
27
of
terrace
form,
bottom
of
Two
and
vats
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
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
(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
Halske
"
to
tate
facili-
other
the
diameter
of
ozs.
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
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,
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
Fr.
was
32,000.
so
small
The
that it
this calculation
was
is that
an
in the solution
itself
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
separatedthere,and
39
so
form
grms.
3*9 grms.
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
in this direction,which
of the whole
plant. The use
the removal
of the
providethe
to
process by
of the work
and
from
the muffles
from
Siemens
new
as
that
gases
to
found
were
those
the copper
mattes
salts
in the
of
crystallisation
arranged on
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
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
t German
Patent
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
outside the
338,150,Jan. 5, 188G.
S.
partitions,
260
ELECTRIC
solution
solution,and
similar
REFINING.
AND
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.
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
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
and
salt,
it is first
that it may
so
peroxidised,
another chargeof ore.
from
and
owing
ferric
to
the
the
same
solution
absorptionof
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
[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
over
of the
bottom
this
liquidescapingfrom
vessel.
The
\^
compartment,
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.
2Fej(S04)8+ XH5SO4
2CUSO4 + 4FeS04 + S + xUfiO^
CUSO4 + HjO
3CUSO4 +FesO,
CUSO4 + (Fe,Os+ SOj) + Hj
2Cu
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
the
that the
position
electro-chemical
series
force.
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
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
poorer
lieu
in
if the copper
evident
from
in the
is used
lost,by
the
for
former
other
alternative
of this nature.
of
liquidthrough the
is necessary
for satisfactory
work, the cells are placed
form (Fig.161),and
all the cathode
compartments,
connected
are
26a
COPPER.
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.
be
must
The
[English
concluded
that
cells
electrolytic
Patent
3,533,Feb. 27,
264
ELECTRIC
SMELTING
AND
REFINING.
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
anode
electrical
with
the necessary
with a layerof
covered
electrical
connections,and
is
K,
which
quite covered
are
maintained
in slow
cylinders may
made
be
other
by
of
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
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
the
through
but
the cathode
from
mixture
the solution
compartment
upper
slow
to
the anode
Here
compartment.
the
ferrous
into ferric
the ferric
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
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.
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-
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-
"
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
Siemen^Bche
in
cells
placed
anodes,
the
of cuprous
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
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
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
CuClj
So
ft.]capacityare
should
acts
of these
ores
m.
to extract
CuS
CujCla.
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
shown
is present in
in the
following
dissolves
is formed
in the
"
Ag^S
2CuCla
CujCl,
2AgCl
S.
described
Cheniie,1890,
XeitMhrift/iir
angeiaandte
p. 622.
ii68
REFINING.
AND
8MBLTINO
ELECTRIC
*"
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
to solutions
copper
with
an
baths,
volt,is equivalentto
0-8
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
"
greater depositing
power
affordingtwice
one
under
this amount.
contributingto
causes
1. The
**
would,
double
much
so
that
copper
half.
The
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
contain
and
with
the
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
1.
2.
3. Constant
movement
of the slimes
while
and
being leached.
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,
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.
"
and
of copper,
finelythat on
per cent,
so
pass
through
34*5 to 32*6 of
pass
100 sieve.
The
revolvingwooden
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
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;
would
per cent,
from
were
also
to dissolve
necessary
that a large excess
of
because,at
iron
271
COPPER*
disintegrated,as
did
tbey
fragments
at
slightestprovocation,*the
the
collected
of the anode
the bottom
at
of the bath
and,
"
"
chloride
Ooehn
with
the other.
on
chloride was
electrolysed
cuprous
formed
the
at the
chloride
current-density, cupric
observed
low
when
that
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
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
solution,which
*
streams
[It is claimed
downward
from
the
anode, is withdrawn
ampere
per
to
eleotricAlly
"Translatob.
graphite.
25.
272
ELECTRIC
SMELTING
With
of cathode
of copper
the
the erection
several
laboratory,
gave
of
of ultimate
been
have
of the kind
and
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
of
of the
deepest part
of
current-density
and
Since
REFINING.
AND
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
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
not
favourable
especially
conditions,such
chlorides,
except
as
are
able
only attain-
solutions
obtained, there
so
the
treatment
of
process
is
cupricor
yieldedin
Denkschrift der
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
The
are
towards
end
the
of the
removed
acid and
sulphate,slightly
the
with
of copper
In
and
of copper
nickel
last trace
anode
treatment.
traces
are
short
solution
or
time
is
speise
the
contains
last
pure
little iron.
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
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
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
or
On
zincthe
double
in order
still better
attained
from
of iron-
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
*'
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
charac*
277
NICKEL.
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
*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
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).
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.
279
NICKBL.
and
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
which
is to
be
in the
obtained
rarelypresent) cannot
are
least,if
at
means,
in the
condition
metallic
Basse-Selve
patenteda
Process.
process
in a
of
firm
Tbe
"
Basse
the
also
Selve*
separationof nickel
for the
the
same
from
iron,
cobalt, and
zinc
solution
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
the
carbonate,and
zinc
have
carbonate
sufficient ammonium
it is then
alkaline
been
moved,
re-
to convert
electrolysed.
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
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
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
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
ammonium
made
was
follows
as
up
100
:
"
cobalt
c.c.
30 grms.
30 grms.
500
cathode
The
wide,
and
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.
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.
side
the
on
long by
the cathode
in the
grms. separated from
The
metal
and
was
fairlystrong plate.
dull
was
similar
ammonia
water.
c.c.
was
sulphatesolution.
sulphate.
ammonium
7*6
cms.
The
used
wide, was
current-strength
and
cobaltic
whole
of the
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-
after very
heating in
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
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
,1
Enginetring and
"ilicuUs.
Patent
112,890.
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
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
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
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,
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
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
in
solution.
The
the
cathode
takes
small
cent,
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
nickel
should
cobalt^or
from
the
is
cobaltic
i^ould be
oxide
free
of that
trace
metal.
account*
An
that Vortmann's
made
there
to
was
from
the
electrolytically
the form of peroxide,
but
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
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
smeltingand
tops-and-bottoms
of nickel
tion
by reducchloridising
roastingfrom
"
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
; copper,
traces of
"
O'l to 0*2 j
platinum.
For
followingmethod
the
on
and
mattes
nickel-copper
Anodes
"
average,
an
of
210
grms.
cast from
UJke
mends
recom-
(containing
matte
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
densities
solutions
normal
the
of
had
from
to
50
"
to
contain
300
from
amperes,
50
to
with
120
chlorides
grms.
of
the
nickel
per
litre,and
"
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,
is also
at densities
of 200
account
edition
of this work
With
Alloys.
Niokel-Oopper
Dr.
".
kind,
the
supplied by
was
about
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
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
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
"
considerable
anodes.
soluble
Lead
"
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
only a
Review
of
will have
methods
of
of art,
or
indeed, even
the
As
from
FrooeBses
Industrial
Standpoint.
"
It
been
determined
is
from
seen
the
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
silicate
withdrawn
from
the action
it has
present known,
With
of the solvent.
found
been
all the
ores
that
per cent
has
ore
reduce
little nickel
much
crushed
fine
as
in
as
speise.
than
it is
surprisingwhen it is remembered
matte, which, in comparison with ore, contains
in the form
of
at
the
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"
,,
,,
"
"
to
concentrations.
For
materials
Stated
in round
t Engineeringand
numbers
per
cent.
9.
292
ELECTRIC
BMELTINa
REFINING.
AND
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.
It
that
is true
the
bulk
of the
iron
be
can
removed
from
within
But
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,
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
nickel, were
Such
as
far
by Borchersf
in the
certain
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-
the
the
proportion of
and
by weight.
"
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
has
reduction
recommended
the
in the
of
amount
addition
of copper
of iron
nickel,the
residue
of copper
of iron
be
present may
most
The
method
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
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
The
above.
author,
in
the
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,
295
NICKEL.
lead chlorate
over
could
by
in the
anode
cathode
into
the
then
be obtained
treatingthe
cells without
solution.
of
The
resultingsolutions
outside
good coveringpower
cells.
electrolysis
the
lead
Again,
form
of
felt like
Fig. 170.
Fig 172.
Fig.171.
Fig. 173.
Apparatus
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
been
used
for the
diaphragms; they
Royal
525
mm.
Porcelain
were
coll.
and
173
show
form
above
Clay
purpose.
obtained
of suitable
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
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.
"
"
"
(2) Arsenic,
various
(3)
arsenical
which
of
is available
be
may
under
stances
circum-
some
sulphuricacid.
utilised
for
the
preparationof
compounds.
Tfie roasted
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.
wind-furnaces
of either
form
with
fused
which
oxides,the
the addition
is
specially
applicableto
mixture
of acid
oxides
of
fluxes,either
is reduced
in crucibles
or
in blast furnaces.
be worked
!17)
lead and
bismuth
(20) Anode
worked
II.
(5)will
slimes
up
in
Frocesses
during
This
which
the
in the
be found
which
and
Copper
Boasting
and
Nickel
Separated
are
Smelting
are
Stages.
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.,
+ German
29^
NICKEL.
(3) Slags,which
(4) Crude
thrown
are
matter which,
and
away,
the method
departingfrom
employed
in the
(5)Mixed
matie^ which
separates into
in
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
(13) Concentrated
rich in nickel
of the
to
bottoms
warrant
are
their
in copper and
extraction
the
latter metal.
The
Leaching
of the
Concentrated
(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
Copper, by
(16) Copper containingpreciousmetals,which
Electrolysis, yieldingfinally
(17) Electrolytic
copper.
(18) Silver,and
Smelting
for
water
compounds,
with
Tops
are
separatedby
300
ELECTRIC
SMELTING
Chloridifling Roasting
of
REFININO.
AND
the
reverberatoryfurnaces,followed
Concentrated
in
Bottoms
by
with
cop|)er, there
obtained
are
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
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.
low
Of
of
of those metals
one
soluble
are
made
which
be oxidised
cannot
high
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
are
with
trated
concen-
render
it soluble
haloid
Eztraotion.
"
waste
following
processes
salts;and
in other
formed
by
double
the action of
are
metallic
cyanideson
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
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.
(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
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
from
by mercury
productsin which it is present as a haloid salt.
working conditions,free silver sulphide also
it
the
not
the
can
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
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
"
"
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
ores, to which
The
Solution
the
a
of
"
the
preciousmetals
part of the
the
and
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.
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.
sabmitted
S^iss
Processes.
"
The
ores
are
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
"
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
supportingthe
hard
the cathode
material
to
current.
be
treated,S, and
or
rubber, celluloid,
glassplatesset
is
loose
bottom
for
is constructed of
in wooden
frames.
If
be
B06
SMELTING
ELECTRIC
AKD
REFINING.
be demonstrated
deposited
This
can
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
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
of the
raw
material
it is
supportedby a
beingfreelysuspended. Odd piecesof thick imperfectly-corroded
alloyare included in the succeedingcharge. The sediment also
contains
lead
acid),whilst
where
they mostly
recovered
in
remain
pure state
acid, dissolvingthe residue
a
in
nitro-hydrochloricadd, filtering
stannic acid,and finally
precipitatingthe
thrown
down
with
metal
by
iron
in
the
chloride.
ferrous
of
process
Platinum
recuperatingthe
is
iron
solution.
of separationis
difficulty
increased in
are
not
at
predpitable
anode.
fraction
Of
of
of associated
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
presence
nitrate retards
the reduction
of nitric acid
to
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
better
Andre
power.
the
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
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
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
membranes
Here
modified
be
may
membrane
with
of low
a
small
"
the
on
come
of the
bottom
the
of this second
porosity,or
anodes
(in
vessel is
preferablyby
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
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
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
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
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
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
covered
of
it
sm^ German
namely, the
"c.
^was, at
"
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
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
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
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
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
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
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.
At
*^
I,* at
the
deuUche
the solution
of
fresh batch
as
before,and
electrolysed
way, to be
showed
that in
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
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
silver
"
fiummer
From
personal comniunication
of 1901.
from
Wohlwill
to
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
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
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
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
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
the
smaller
the anode
from
many
be
to
and
found
time,
became
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
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
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
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
;
"
the two
copper
and
silver
"
are
togetherwould
317
SILVER.
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
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,,
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
scrapers
the surface of the cathode, so
serve
tanks
of
pitch
(inside
width
contains
are
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
^18
KLKCTRIC
SMBLTIliO
AND
[Fig.175.
"
The
Moebius
REFINING.
Under
of each
and
the electrodes,
section of the vat,
compartment
in half
section.
Fig. 176.
"
The
Moebius
apparatus
"
section
showing cathode^
319
8ILVBR.
is
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
the
the
woven
cathodes, the
anodes
frame,
are
and
are
enclosed
stretched
this
in
turn
on
is
(Fig.178).
anodes
in the
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.
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
cathode-plate.They
cathodes
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
REFIMINa
be lowered
should
currenirdensity
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
be
dissolved
from
anode-plate
every
silver within
small
area
whole
the
; moreover,
the
metal
only locked
very important
is
The
cost
of
[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
account
used
current-density
p. 356.]
"
constant
with
Plant.
Company's
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.
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,
far
so
impurities)was
when
crystals,
999|
ozs.
in all of
2 per cent,
that the
process
999 to
33,000
words,
into
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
work.
"
was
Translator.]
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
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
The
the aid of the scraper, S.
pulley outside the vat and the chain-
belt,n
are
O.
actuated
Within
by
the frame, E,
are
the
anodes, G, of gold-
1895.]
532,209, Jan. 8,
324
ELECTRIC
silver
bearing
SMELTING
placed
filter cloth,or
woven
AND
REFINING.
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
contains
[The
Perth-Amboy
Company
account
(ofwhose
has
been
Perth
it
"
New
to
from
erected
that
Jersey.
that
little silver.
too
given above)
Amboy,
be
must
copper nor
The Guggenheim Smelting
Installation.
installation of the Thofehm
copper process an
anode
(new form).
the
of
account
improved Moebius
an
were
each.
in the
48
Each
Mineral
works
electrolytic
tank
was
Industry,1895,
325
SILVER.
about
14 ft. 3 ins.
made
of
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
were
1 in.,with muslin
to hold four anodes
as
by
requiringthe
1^ lbs. of
copper
found
was
normal
tank
in
of
divided
most
for
the
maintain
to
it
necessary
enrichment
time
to
which
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
|c.
and
326
SMELTING
ELECTRIC
REFINING.
AND
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
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
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
been introduced
"
"
EnglishPatent
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.
filtering-cloth,
Cp
arranged the metal bars,S, which are
again,at rightangles there is rested
whilst
contact-block,D,
the
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
be overlooked
with
used
tank.
electrolysis
are
removing
a
very
brisk
devices
ment
move-
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*
very
act
as
acid and
an
form
aurates, with
salts,termed
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
it, may
As
Metal.
of
few
metals, it is usual
EXTRACTION
A.
OF
GOLD.
CRUDE
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
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
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
ores, in which
and
is then
means,
contained
amalgam
in the
appaitktus.
same
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
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
that it forms
by
means
mentioned,
apparatus
the mercuiy
solutions of
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
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
of the mercury
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
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
serving the
the
The
In
anodes.
as
converted
These
SMELTING
of substances
and
volving
in-
salts to
available
be
must
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
"
335
GOLD.
out
his
anodes
in
kept
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
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
solution.
5. In
for
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.
amalgamator
true, shows
with
of the Utah
the Works
and
sluice for
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
from
Imttery slimes
amalgamating
of
treatment
other
apparatus.
7. A
of Jor^B/
ProceSB
above,
has
author
has
given
results
on
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
in the
PROCESSES.
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
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
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
Gold
of
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
Exhibition,London,
1886.
339
GOLD.
dram
of
or
cylindrical
mounted
material,and
some
less than
hundredth
or
thousandth
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,
part of 1 per
this process
for the
year.
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
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
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
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^,
observed
research
exhaustive
the
into
electromotive
of
Deyelopment
the
then
made
of
metals
Bodlander's
Frooess.
very
has
force
and
an
in
views
on
tion
In the introduc-
"
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
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
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.]
p. 864.
342
ELECTRIC
In
SMELTIHO
AMD
RBFINIKO.
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
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
the minimum
consume
to the
electricity
leachingprocess
complicationsof plant and precautionsin working
than outweigh the benefit accruing
most
cases, more
its use.
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
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
"
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.
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.
sluices
"
with
action of the
cyanide.
^The
344
ELECTRIC
SMELTING
AKD
REFIMINO.
Frue
"
be
treated
of solution
in different
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
formed
about
of the vat.
thick
grooved joints.
made
are
[4f to
mte.
thick, the
bolts
the
arrangements.
The
about
REFINING.
AND
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
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.
to 210.
series with
or
without
difference of level,
in
one
case
even
with
the
follows
:
"
Preliminarywashing with
ores
water
or
alkaline
solutions
if acid
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
of
This
further
the
storage, and
form
must
part of the
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
works
in
Plant
second
in the Transvaal
Worcester
Band
Rand
Central
:
"
Central
Beduo-
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
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
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
gold, which
lead
a
cost
of the
separatedby cupellation.The
is
of about
gold,the
solution
amounts
about
to
is retumetl
make
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
The
instance
one
of
gold
in
per ton,
"
installation
an
would
there
for the
The
the
be
stirringmechanism.
of
oost
necessary
diftei'ent in different
obviouslybe
very
be estimated
to
accoixiing
treated.
with
It
its full
be
may
the
assumed
that
and
charge of tailings,
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
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
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
economy
and
difficulty
of the
Arthur-Forres^
process
in other
chemical
sitates
reagents neces-
acid.
as
compared
electrolytic,
is clearlyshown
by the
with
Fig. 21a.
nioBtration
of
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
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
stimulated
*
M.
that
the
further
success
of the
Siemens
experiments in the
Eissler, The
same
(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
be
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
or
operation,this
with
the
Siemens
process.
The foregoingtable,suppliedby the office of the South
African
general
method
scarcelycompete
the
survey
Witwatersrand
of
can
PREPARATION
OF
FINE
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
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
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
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
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
addition
of alkali-metal
hydrochloricacid,and
potassium,or ammonium
the
density,to cause
without
of the
remarked
strong solution
very
absence
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-
Without
escape
region of actual
"
affectingit.
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
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
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
t A
only
can
acid
quantity of hydrochloric
the
hypothesisthat
above
the
from
the
solution
hydrochloricacid
the
place,taking
not
in
Batisfactory
mixture
cause.
of chlorineand
The
that
the
platinum
hydrochloric
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
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
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.
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
acid
only, or
the
the
principal,
resistance
of the
solution.
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
must
formation
equation
AUCI4H
In
increased
an
two
substances
4Ha.
that
chlorine
low
temperatures,
in the solution
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.
be observed
should
than
same
chlorine.
that
the observation
considerabljgreater
time by the anode
The
following table
in the
experiments
with
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
(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
lost 0*06
gramme*
the solution
in the
the current
is used.
cathode
in
for the
course
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
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.].
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
current-densities
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
to
its
all the
the
other
constituents
gold,but, by
reason
of the
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
the anodes
in
goes
into
becomes
graduafly
solution,and
concen-
'*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
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
("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
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
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
alterations
hour.
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
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
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
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
kind
smoothness
of cement
or
anode, so that,from
portionof the
that moment
separates at the
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
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.
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
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
"
*'
if the
375
GOLD.
In
both
and
series,
agree
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
quantityof depositwhich
correspondsto
which
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-
was
appear
to
be
time,
same
found
in the
it will
serve
case
confirm
to
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
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
"
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
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
8, and
in bath
numbers
of the above
The
The
results
the
were
same
bath
as
in
was
"
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.
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.
"
was
mean
was
current-density
therefore
raised
to
about
1,500 am-
379
GOLD.
[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
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
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
**
understood
that
under
electrolysis
these
conditions
afifords a
remarkable
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
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
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
"
"
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
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
of the
"
United
States,New South Wales, Western
Australia,South
Africa,Belgium, France, Germany, and Russia.
Large plants
the
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
ZnO
[or zincite],
aluminium
in
carbonate,calamine,ZnC03, and
zinc
bloom, a
basic
the
ore
and
the
carbonate
residual
copper
alloyingmetal
or
silver
"
be
383
ZINC.
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
crystalline
(hexagonal)Ktructure, and
specific
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.
of
the
of
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
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.
to obtain
pure
A.
zinc.
EXTRACTION
BOASTIira
1.
AHfB
ZINC.
CRUDE
OF
BEDnCTIOir
PBOOESS.
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-
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
German
1885.
Patent
34,730,June
10, 1885.
[EnglishPatent
6,994,June
9,
386
BLKCTRIC
SMBLTINQ
AND
REFINING.
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
that
furnace,and
to
at
silicon
entail
which
silica
would
can
be
certainly
complicationsin use
would
quire
re-
"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
to
of zinc oxide.
of
Treatment
It
Blende-bearing
is
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
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
sufficient
scarcelybe
provided in
is best
ferro-silicon is found
a
REFINING.
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
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
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
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
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.
has been
in the
written
chapteron
copper
concerning
the
use
of
anodes.
sulphideores as
Up to a few years
had
treatment
ore
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
:
"
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.
"
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
more
cylinderto
Chlorination
"
condition
coarser
complete conversion
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
at
the
present in
the zinc
blende.
392
ELECTRIC
SMELTING
AND
REFINING.
The
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
removal
was
ties
quanti-
of lead chloride
it had
after
separationand
lead
water.
be
it would
probably be
the
This
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
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.
which
the
available
is not
for
much
successful
the
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
even
author's
The
use.
largescale,and
zinc
solutions
"
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
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.
Ores
lead
it
would
treatment
simplifiedif the
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
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
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
known,
the
"
This
1
cm.
each.
crude
copper anodes,
90
amperes
*
German
were
[7*4to
8*4 amps,
per sq.
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,
that
REFINING.
was
quite unexceptionablezinc
view
volts
1*45
to
AKD
course
conducted
laboratoryunder
the most
of
frequentopportunities
with
insoluble anodes
in
his
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
bath, but
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
the
vat, and
the
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
tanks.
with
the
improved
and
air
this way
was
and
brought about,
such
introduction
of
by
even
the
the lowest
as
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
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
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
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
contained
Patent
J English
Patent
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
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-
xxvii., p. 630.
IT The
precipitatecontains
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
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
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
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
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
the
followingvolumes
of soda solution
for every
turbidity.The
Thus,
10 grms.
we
used
of zinc
"
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
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
result
would
the anode,
rough,
since
an
order
''In
be
a glasscell
of refining,
compartments by diaphragms of
the process
zinc
purified
into
cast
was
the
used, divided
was
into
form
cm.
[0*4in.]thick ; for the cathodes sheet zinc
correspondingwith the anodes in size and shape. The
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
neutralised
itsell
For
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
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^
of
hydrogen
cathode,although more
solutions. As
these
appear
in
considerable
sparinglyin
bubbles
adhere
the
for
some
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.
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
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
be
employed
refiningof zinc, a
take
chloride
made
The
test
made
was
would
less pure
metal
were
2*5 litres [| gall.]
with
solution
of the
zinc
proportionsof
which
linen
area
of 300
and
the
free acid
sq.
chlorine
and
cm.
current-density
was,
current
therefore,1-8
operation in
one
to foretell what
edges
cathodes,and
of the
showed
zinc
removed
excellent
an
on
these
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
as
to
detection
case
the
there
in which
action
The
be
be
no
need
of any
device
other
for
so
stirring
strongly
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
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
which
solution
is
flowing
at
REFINING.
the
flow of the
rapidityof
The
in
direction
process.
the cathodes
is, however,
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
be
to
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
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.
"
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
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
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
"The
"
with
Marshall
Hugh
"
at
that
have
we
the
the formation
found
"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
of
nitrate
its reduction
resultingfrom
the
kind
ammonium
to
the cathode.
at
they reallypromoted
and Giinther)
have
(Forster
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
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
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
it
in actual
was
in zinc works.
use
For
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
(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
Patent
71,155.
411
ZINC.
the
to
surface.
potash and
of
double
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
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-
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
very
the
that
Process.
rapid variations
be
may
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
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
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
to
has
with
connection
vat
be
may
"
not
speciallynoted
very
harmless
it
which
to
proposalsin
which
the
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
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
ziac
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
are
two
molecules
of zinc
Patent
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
means
ores
A.lthoughLuckow's
the largescale,it
on
anode
has
matte
Fromm
not
the
account
been
adopted
utilisation
deserves,and
in
some
of the
instances
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-
same
Kjellin,twhich
aimed
"
"
reacts
with
as
follows
FejCl" + 3HaO
"
3ZnCL,
FeoCOH)^.
tanks
with
iron anodes
2ZnCl,
and
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
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,
until
the
the
mass.
gangue
The
transformer
is
the
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
copper
zinc to
throw
to
filter-
and
silver
The
down
the
remove
and
filtrate
the residual
copper
next,
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
From
the bottom.
influence of small
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.
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
product
of red lead
provedthat
lithargeand
above, and
red
is about
250** 0.
very
than
fine red
from
that
^ven
compound
^vould
excess
wet
condition.
The
temperature
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
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
He
to
writes
as
follows
:
"
420
ELECTRIC
zinc
for
SMBLTUia
It is needless
here
obtaininga solution
alkali-
and
almost
of zinc
earth-alkali
or
lead
It will suffice to
has
worked
the
REFINING.
AND
the
exclusivelyin
of
direction
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
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
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
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
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
Stahl
*
has
(Niederfischbach)
made
series
351.
of careful
422
ELBCTBIC
SMELTING
AND
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
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
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
formed
to zinc extraction.
^*
to
be
Hoepfner cannot, therefore,
have
attempted the extraction
residues, and
*
therefore
the
credited
with
of the
zinc
the
residues
utilisation
of
ZtUung^ 1894,
p. 1.
them-
425
ZINC.
seWeM, but
he
has
of 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
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
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
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
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.
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
and
the frames
used
the membranes
by
which
divided
the whole
of the cathode
and
anode
frames
chamber
8 anode
The
frames
third side
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
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
on
is made
therefore,replaced by
arrangement, however,
baths.
the
cross
U-shaped glass
a
remedy
external
did
The
the
afford
not
difficult to
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
of bath
tear
the
of this
in Electric
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
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.
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
the
shows
bands, H.
sides
of the
The
frames,
supports, resting
as
100
about
are
carried
are
into
220
Fig.
metal
bars, P, which
iron
and
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
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
"
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
tanks
by
suggestionto
were
The
built
up
of broad
to
G.
bath
and
Throm,
apparatus
the enclosed
wooden
frames
wooden
held
day
with
in
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
mixture
whole
long edge
tank
turned
downwards, and
431
ZINC.
with
the
side
beingopen.
wide
and
The
inside
[75
one
(to
into
come
direct
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.
solutions,the
action
was
the
of the
but
pitch-pine
On
wood
the
very
The
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
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
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
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
ends
upper
small
wooden
two
the
inserting the
after
which,
the
and
sides
the
At
of the
boards
anodes,
is
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
year
durabilitywere
to
as
cost.
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
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
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
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
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
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
of
about
the other
on
is afterwards
pinch-cock,to
the chlorine
from
wood.
stripsof
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
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
passing from
until
cell itself.
the
first bath
out
anode
time
same
maintained
on
The
plant.
at
bath
the
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
"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
solution.
in
Each
both
was
between
system
was
The
difference
; both
Fiirfurt
supplying the
arranged terraceof
[4 ins.]lower
cm.
better
drawbacks.
baths
10
being
Hence, there
one.
their
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
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
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,
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
influence
an
not
successful.
least
at
than
of
system
proved
not
or
the
that
seen
conditions
series
Thus
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
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
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 remembered
large plant
are
insulated
are
on
ware
earthen-
a
precautions,
weather, but
impossible,
except with
cost, to
insulate
such
earth.
by connecting up
or
439
ZINC.
six baths
of
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
cent,
2 per
solution
not
yet spongy,
the
bath
do
tests
or
however.
The
controlled
are
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
become
and
Even
or
work,
ence
refer-
on
the
few
the
on
the
cause
in
needles
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
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
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
and
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
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
"
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
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
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
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
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
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
See
also
p.
for
17 of
44r"
ZINC.
the
of water
removal
dehydrated
the
oxychloridesfrom
or
zinc
zinc
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
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
stated.
above
in the manufacture
dehydration process
from
as
process does
likelyone, and the
Inst-named
The
author
of well-dried
current
of
suitable
the
with
the
to
when
of the
fused
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
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
11,190, May
5, 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
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
*
spongy
statement, made
to
deposit. Mylius
in
the
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
9*3 per
the author
"
of very
fusible
alloys. The
compounds
of cadmium
are
solution, 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.
"
but
at
300"
about
oxidised
0. it becomes
to
the
red
oxide.
Ozone
The
the
dissolves
metal
"
occurs
mercury
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
treating
AND
mercurial
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
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.
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.
removed.
is thus
tungsten
of the ore,
simple reduction
in blast
either
with
furnaces
carbon
the necessary
fluxes,
the
latter
reverberatories,
being
in
or
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
are
groups
"
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
[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
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
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
it
an
works,
metallurgical
exceedinglycheap rate.
statement
the
or
addition
other
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
mention
treatment
maximum
about
and
In
or
tin
process.
By the
3 tons
pletely
com-
Three
appear
makes
no
account
left unattacked.
handle
[0*0645
amp.
eight vats,
tin
readilyand
was
metre
of the
of 240
only
as
towards
1-2
whole
the
treated
those
current
and
was
was
gathered
be
high.
very
iron
being
tin
required to
were
was
the
where
residual
density used
then
dissolved,the
or
weeks
to dissolve
anode
as
iron and
of
seven
the
that
if it
iron
by electrolytic
latter metal
would
were
be
tended
insolved
disclusion
con-
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
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
German
t German
Patent
Patent
96,198, March
10, 1897.
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
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
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
cent.
Sn)
When
a
largerproportionof
stannic
up
acid
regenerationof
Menniche
the
among
pounds
com-
"
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-
"
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
These
bands
is the
are
is
The
matter
baskets
of
are
mesh,
bound
with
bent
into
hooks
above,
so
gripping them
that
the
456
811ELTING
ELECTRIC
It is made
so
auspended
"of the
to
as
REFINING.
AST)
exactlyfib the
capacityof
The
tank.
the
baskets
bath,
"electrodes to
prevent
resistance
the
of
the
formation
short
of
reduced
is thus
electrolyte
The
circuits.
to
minimum.
"
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
of holding back
purpose
tin.
Diaphragms are not
"The
the
suspended particlesof
spongy
used.
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
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
by coolingthe liquid
of tin
Menniche's
account
ore.
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
obviouslydiffer from
employed, must
scrap
the same
mechancial
found
been
components
for the
could
serve
as
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
baskets
of wire
mesh
with
an
met
so
much
receptaclesare
iron
between
with
framework,
the
sources
anode
favour
now
which
as
usually
complete
other
stances,
organicsubelectrolytes.
An
purpose
would
appear
to
be
sufficient
to
make
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.
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
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
from
of NaCl
KOI
mixed
with
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.
460
ELECTRIC
connection
which
with
melts
The
at
Uses
and
first
the
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
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
"
the
lead
forms
peroxide
Thus
first in the
named
ores
lead
ore
The
of the metal.
a
by
^are
"
maintain
to
radical
plant
above
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
where
be taken
containinglead,must
in connection
As
the
in sufficient
and
appliesspeciallyto
by-productsand
of
number
which
remark
are,
from
"
waste
derived
are
PbaPbO^.
The
white
acid
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.
Process.
"
462
ELECTRIC
Reduction
and
Boasting
AND
SMELTING
REFINING.
Frooess.
In this process,
"
ing
roast-
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
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
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,
463
LEAD.
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
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
Traiie d'ElectriciU
1855,
in
author
treated
beyond
at
the
et de
contained
called electro-chemical
be
the statement
contains
and
from
The
REFINING.
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
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
18.
466
SMELTING
ELECTRIC
REFINING.
AND
as
consists in
process
The
well-known
fusion
LEAD.
SOFT
LEAD"
PURE
OF
MANUFACTURE
but
littleof the
the
noble
metals
noble
metals, and
the
are
other
The
concentrated.
lead
latter
in which
alloyis finally
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
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
*
26.
467
LEAD.
cathodes
rods, 0, restingon
of
long side
one
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
[ 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
side
aa
to
is
well
second
a
as
from
copper
the vat
anodes
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
"
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
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
9,000 kgs.
sume
generator will con-
about
An
For
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
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
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
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
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-
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
seem
which
which,
form.
even
The
undoubtedly
under
these
circumstances,
results of short
been
successful
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.
of applying the
poftsibilitj
in
the manufacture
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-
accumulators.
CHAPTER
IX.
BISMUTH.
Properties
the oxide,
and
Bi^Oj,
bismuthine;
for
of
Ocouirenee
as
bismuth
work.
metallurgical
and
arsenical
sulphide
Bismuth
and
lustre
specific
gravityis 9*74
is
to 9-8.
has
not
1,100* and
metals,
The
copper,
alloysof bismuth
low
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
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
first-named
metals
are
metals.
guished
distin-
and
nickel
very
471
BISMUTH.
little action
ordinary
on
the
metal
when
even
it is red-hot.
the
Among
only in
hismuth
the
sulphur dioxide
several
oxidation
The
neutral
or
production of
products;
derived
compounds
soluble
and
salts
almost
but
sulphate.
It
forms
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
Preliminary
of the
Treatment
Ores
usual
^Liquation. Formerly it was
native
but
this
bismuth;
"
"
contained
on
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
then
in the
so
enriched
as
together with
to
contain
hearths
at
from
of bismuth
oxide,
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
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.
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
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
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
is
salts, and
the
in
derived
acid
So
antimonates.
of
compounds
known
the
the
mony
anti-
trioxide,
or
the
as
contain
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
"
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.
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
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
saved.
If
sodium
thio-antimonate
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
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
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
small
"
was
also mixed
salt.
of the
with
Adopting
experiment
the
are
478
SMELTING
ELECTRIC
REFINING.
AND
Here
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
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
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
"
trisulphide
; and
should
3 per
cent,
not
of
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
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
character
the variations
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
run
fresh sodium
sulphide liquor.
up with
is drawn
off exactlyas before,but instead
of
is then
into
boiled
one
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,
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
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
again used as
A plant such
valve, a,
which
accumulated
finally
are
of
are
of the
portionsof
rinsed
slimes
taining
con-
rate
ments,
483
ANTIMONY.
iron
tanks, B, hang
the
The
latter
of
Fig. 233."
iron
tank"
Antimony electrolytic
insulate
H,
iron
the
so
bars,J, are
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
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
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
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
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
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
the
that
acid
hydrochloric
facturers
manu-
for its
salt,coal,and
manufacture, common
be
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
Kopp*8
"
ores
antimonious
chloride,accordingto
6FeCl, + SbgS,
"
the
followingreaction
GFeCl,-h 2SbCl,+
"
Sa
The
electrode.
ferric chloride
latter
solution
is
regeneratedat
is then
used
the
once
positive
more
to
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.
-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
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
less often
occurs
Properties.
form
buted
widely distrismall quantities.
Yanadiam
"
is
part in very
of free oxide
in that
than
of
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
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
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
*
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
first German
edition
of this
490
ELECTRIC
83IELTINO
AND
REFINING.
the
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
lead,PbCiO^.
used
Chrome
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
as
easily obtained.
is
carbon
chemical
oxide"
CrgOu,
comfiounds
with
being an
Prooess.
of iron
iron
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
"
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-
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
thus
The
passage of a powerful
of cross-sectional area
of
current
the
rod
small
raise the
oxide
The
it
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-
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.
more
evenly in the
"
furnace
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
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
serves
impurities. If the
this calcium
chromite
and
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
aluminium
means
chromite, the
edition
the greatest
of the
none
carbon.
in the
carbide,which
chromium
also of chromium
alone,
free from
formed, and,
is
is true
reduced
these
them
REFINING.
oxide is reduced
electric furnace.
carbide
the author
by
AMD
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
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
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
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
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
SU.S.A.
Patent
244.
13,
1895.
496
ELECTRIC
SMELTING
AND
REFINING.
His
current.
Bun8en*8
of his observations
account
Experiments.
"
"
The
ran
follows
as
densityof
"
the current
(that
the
on
important
for example, if a current
through a solution of chloride
most
Thus,
surface
the
upon
of
area
of
resultingchemical
the
reactions.
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
''As
which
The
and
(1)D
the
of
absolute
with
I is found
=-pr ;
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
then
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
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
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
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
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
;
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
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
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
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,
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
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
which
of
arms
which
contact
acid increases.
other
The
the normal
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
more
of the
circuit
provided
bell
"
is
arm
electric
an
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
"
Oesellschaftin
502
SMELTING
ELECTRIC
Under
form
AND
REFINING.
Alterations
followingtable
as
shown
in the
has
patented
"
Process.
Krupp's
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
"
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
cent.
has
and
molybdenum
conducted
were
air
Guichard^
"
as
carbide.
contains
Sulphides.
author
has
[Borchers]
shown
earlier
that
edition
both
the
of this
and
oxide
work
the
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
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.
"
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
Treatment
Preliminary
duots.
be
the
"
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
alloys,they, like
the
slags,must
be
treated
so
as
to
obtain
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
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],
all oxides
were
observations
reducible
He
had
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
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
The
so
obtained
contained
from
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
"
"
silver, and
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
(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
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
considered
that
he
fluoride
by fusing manganese
pure
manganese
in a Hessian
crucible. He
must, however, have
more
manganese
*
silicide than
metal, for,Wohler
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
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
"
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
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
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
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
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
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
manner
considerable
time.
same
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
"
very
to the
production
carbides,
metals, if
it is wished
to obtain
them
t La
Proc^4
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
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
""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
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-
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
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
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
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
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
"
515
ibon;
Italy),although
furnace
Better
work
who
those
would
have
have
had
experience
predicted the
in
failure of the
electric
process.
obtained
results,since
"
malleable
so
process,
"
direct
iron
modified,will
century,
be
from
dealt
productionof wrought
Towards
Prooess.
H^roult, whose
"
the
end
of
iron.
the
is identified with
name
nineteenth
the
modern
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
not
tried.
Harmet'8
Prooess.
H6roult's
"
Those
who
had
knowledge of
any
have
read with
some
M6
SMELTING
ELECTRIC
drawing
electric
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.
assist the
Fig. 239.
Fig. 239.
The
"
Drawing
of
an
coke-chargingof shaft K
metal
tapholesof the
is
slag and
from
the furnace
with
arranged
at
the
side of the
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
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
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
hearth
Beneath
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
has
accumulated
it is
which
on
must,
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
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,
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
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
in
the
two
eectioii.
longitudinal
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
as
the metal.
REFINING.
time
to act
electrolyte,
an
AND
SMELTING
all direct
he avoided
inevitable
the
electrodes.
carbon
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
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
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
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
....
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,
on
It
the
than
that neither
layers of
the
and
injuriousnor
in which
so
bath
the electrodes
between
regulated that
metal
be taken
must
between
between
respectively.Care
thence
was
kept
designedlyraised
below
this level
to
the
is shown
figures
by the
525
IRON.
"
and
0-89;
0-31.
C,
H^roult
The
also
can
process
scale ; and
small
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
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
end
the bath
bobbin
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,
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.
Fig. 246.
Fig. 247.
sary
was
once
to
construct
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.*
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
"
.......
5*70
used
the limestone
CaO,
3790
"
Moisture,
and
followingcomposition:
Carbon,
Ash,
51*21
MgO,
311
SiOj,
0*90
as
flux contained
percent.
,,
"
:"
F^O:}
"
43*43
"
addition
of
"
Fixed
carbon,
Hydrocarbons,
Ash,
*Lncchini, La
Chimica
528
ELECTRIC
The
made
charge was
of
up
"
Iron ore,
As
raw
125
Fitch
120
160
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
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,
Total,
Less
900
cb.
Actual
gas,
at
18*00
of iron,
Or
that
only conclusions
experiments that have
been
favourable
particularly
and
purity and
power,
of Heroult
94*00
approximately"3
The
the
22*80
3*00
112-00
m.
2oentesimi
3 60
12*00
Supplies,
processes
13*30
6*75
Consumption of
Whereas
11 '25
0'50
.,
Upkeep
24O0
4*80
at 5 lire
of limestone
4 cwts.
5 cwts.
420
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
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
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
known
for
free
simplecompounds
compounds can be
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
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
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
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
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
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
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
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
carbonates,"c.,of
the alkaline-earth
metals
with
carbon
electric furnace.''
into
in
30
CaCj
CO,
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
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.
"
and
sold
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
of the lime
the
evaporation,
indeed,proceed to
used, the whole of
been
the
being so
even
above
will allow.
case
by
and
of carbide
the fusion
more
over
an
the lime
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.
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,
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
opinionon
the
matter.
alreadybeen
which
dealt with
in the
and
conditions
of the
course
requirements
have
foregoingremarks,
been considerably
RAW
Caloium
introduced
from
Oxide.
in the
This
"
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-
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
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
"
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,
this
"
lined with
carbon.
"
"
536
ELECTRIC
SMELTING
AND
charging hole
REFINING.
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.
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
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
so
of
the
to
this there
methods
COMPOUNDS
the
wheeled
of
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
fittings.The
electrode.
one
second
The
was
crucible,the
portionof
reached
enable
furnace,in
iron
shaft, composed
this
core
cell.
carbon,
of the
sides
stopped,to
was
firebrick
of
block
iron
of the
the
bricked
suspended from
provided above
served
into
to
preserve
was
necessary
charge round the
this furnace
is full
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
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.
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
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
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
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
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
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-
the
same
purpose
of
solidified
of
in
masses
naces,
fur-
tap
and
of
high
Keller, however,
electrodes,or, for
either
only two
naces,
large fur-
uses
very
of electrodes.
two
rows
case
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.
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-
electrodes
"Nemst
and
Borchers, Jdhrb,
der
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-
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
Reliable
values
working
were
sumption
con-
carbide,
that
on
portions,
pro-
the
these
large
study on
highlyinteresting
and
the
different conditions
of
of energy
output
carbide
manufacture, was
or
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
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
of the
mixture
table.
acetyleneobtained
mixture
calcium
An
examination
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
and
60 of carbon
for the
Fig. 255.
be most
it would
Eng.
Pat. Na
6,033 of 1900.
544
BLECTBIC
REFINING.
AND
8XELTIKO
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
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.
to describe
other
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
cannot
the
to
reaction
mixtures
hydrogen.
XTranium
carbide
rich
in methane.
and
solid
hydrocarbons
gaseous
of the carbon
ever,
is,how-
combined
and
oxygen.
Almniniiun
methane
only
hydrocarbon,
one
"
AlA
equal volume
of
Mn,C
12HaO
3CH4
4A1(H0)8.
also
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
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-
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
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
Whether
sulphidesinto
silioide
Iron
M^Si ;
bj
pursuedby
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,
"
[" 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.
,,
,,
"
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.
"
"
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.
"
ing),
(BurgluurdtTwin-
"
Kupferhiltte(copper
"
"
"
211.
finins),
Alum
shale,93.
"
"
(Braun), 106.
(Bucherer),154.
(Bunsen), 109, 113.
"
"
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,
"
"
"
"
,,
"
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.
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.
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,
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.
process (alkalimetals),79.
,,
"
"
"
"
"
(aluminium),103, 145.
530.
(carbides),
(chromium), 494, 497.
(magnesium), 13.
,,
"
"
,,
,,
,,
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.
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
Aschermann's
495.
"
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),
"
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,
,,
,,
"
"
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.
(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.
"
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,
232.
current
,,
187.
,,
,,
required,
Specificgravity of fused,
160.
198, 227.
,,
,.
,,
,,
"
"
"
"
"
"
"
"
,,
,,
(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
tagh),227.
Series
system,
236, 239.
(sodium), 30.
Defacqz (tungsten),505.
De Laval furnace,519.
deposition,
Depolarisersin copper
,,
,,
257.
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
.,
(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
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),
"
(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
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.
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.
,,
,,
,,
,,
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
Marble,73.
Marchese
(zincexperiments)396, 405.
,,
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.
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),
"
"
"
"
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
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,
,,
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.
"
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.
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
"
furnace,14.
413.
Pertsch process (zinc),
Pettenkofer (goldrefining),
359.
Raritan
Copper
Co.
ing),
(copper refin-
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
"
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.
, ,
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.
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.
refining),
228-234.
Travers
em), 83.
,,
213.
(anode-plates),
(copper
chloride
105.
,,
"
process
Thorium,
Thromm,
"
Thofehm
zinc
electrolysing
Thomas-Tilleyprocess (aluminium),
73.
Strontianite,
Strontium, 74.
"
for
Phoenix
process
(zinc),415, 441.
"
treatment
"
Tungstic ochre,504.
of ores, 504.
Twinins-Burghardtprocess (aluminium,
Sylvine,71.
327.
Symon-House (silver),
107.
Ulke's
286.
experiments (nickel),
Ullmanite, 273.
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
"
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
"
Winkler
process
423,
(aluminium), 118.
Witherite, 73.
Wohler
(manganese),508.
experiments (aluminium),
Wohler's
bide),
(calcium car-
,,
530.
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.
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