THE

OF

HANDBOOK

SOAP

MANUFACTURE

W.

H.

B.Sc.

SIMMONS,

H.

APPLETON

A.

TWENTY-SEVEN

WITH

(LOND.),F.C.S.

ILLUSTRATIONS

LONDON

GREENWOOD

SCOTT,
"THE

OIL

AND

COLOUR

8 BROADWAY,

"
TRADES

LUDGATE

JOURNAL"
HILL,

\AlLrights reserved']

SON
OFFICES

E.G.

PREFACE

generaladvance

of technical

knowledge and research

Soap Industry has not remained
not perhaps been
anything of a
revolutionarycharacter, steady progress has still been
all branches, and the aim of the present
in practically

the

IN

last decade, the

during
stationary.While there has
the

very
made
work

is to describe

the manufacture

carried out

Soaps as
factory.

to-day in

an

of Household

up-to-dateand

and

Toilet

well-equipped

scientificportionsof the book, an acquaintance

In the more
of elementary chemistry is assumed, and in
with the principles
this we feel justified,
as in these
competition,
days of strenuous
no

hope

soap-maker can

unless he has

of the

of the nature

takingplacein
We

with this

to

with
compete successfully

or

hope

and

as

materials

raw

the pan,

also venture
Chemists
Works'

to

theoretical

sound

at other

he

as

his rivals

practical
knowledge

uses,

and

the

reactions

stages of the manufacture.

useful to
may
prove
consulted
in
connection
Analysts

that

other

well

the

work

Industry.

greater part of the book no

is
knowledge necessary, the subjectbeing treated in
not directlyengaged
such a way that it is hoped those who
are
desire
but
who
in the manufacture
of soap,
a generalidea of the
At

the

same

time, in the

chemical

will
subject,

find it of value.

dealingwith the composition and analysisof

materials,temperatures are expressed in degrees Centigrade,
these being now
almost
invariablyused in scientific work.
grees
In the rest of the book, however, they are
given in dein
also
added
Fahrenheit
(the degrees Centigrade being
factories
used.
of
these
still
in the majority
are
as
brackets),
of
factories the use
As regardsstrengthsof solution,in some
in
others
Twaddell
w
hilst
Baum6
is
degrees
degrees preferred,
therefore given the two
have
the custom, and we
are
figures
In the sections

in all cases.
m

"

iv

PBEFACE.

In
tion

the

Equivalents

Values,
our

results

Organic

figures
For

E.

Co.,

as

Forshaw

it

been

has

in

this

the

chief

the

oils

illustrations,
"

Son,

as

way,

all

Ltd.,

in

our

and

records,

H.

for

are

from

taken,

D.

Morgan,

are

Saponifica-

Saponificatiou

to

some

by

authors

their

Fats,

suggested

fats

the

and

preference

practice

onr

and

Analysis,
for

given

are

Oils

with

dealing

chapter

to

years

Allen

in

which
are

of

most
so

Messrs.

to

W.

J.

Fraser

Ltd.

W.
H.
LONDON,

September,

1908.

the

stated.

indebted
and

express

Commercial

H.
A.

S.
A.

"

CONTENTS

PAGE

CHAPTER

I.
.1

INTRODUCTION
Definition

of

Soap

Properties

"

Hydrolysis

"

CHAPTER

CONSTITUTION

OILS

OF

Researches

FATS,

AND

II.

AND

Berthelot

Mixed

Theories

Saponification

of

CHEMICAL

(3)

Acid,

by

Sulphuric

HEAT

(1)

OB

Emul-

Twitchell's

Acid,

Zinc

Magnesia,

Lime,

"

Steapsin,

Ferment,

REAGENTS,

Hydrochloric

Reagent,

accelerated

Castor-seed

(2) FERMENTS,

and

sin,

Hydrolysis

"

Modern

Glycerides

"

ELECTRICITY,

SAPONIFICATION

THEIR

...

and

Chevreul

of

Action.

Detergent

"

and

Soda

Oxide,

Potash.

CHAPTER
MATERIALS

RAW

and

Fats

USED

Oils

Limited

"

Use

Rosin

Fats

Alkali
"

Acids

Fatty

"

Various

"

.24

SOAP-MAKING

IN

Waste

"

III.

Oils

Less-known

and

of

Fats

"

New

Fats

(Caustic

and

and

Oils

Carbonated)

Soap-making

for

Suggested

Salt

Water

Soap-

"

"

"

stock.

IV.

CHAPTER

BLEACHING

TREATMENT

AND

Palm

Cotton-seed

Oil

RAW

OF

Oil"

MATERIALS

Cotton-seed

"Foots"

"

Animal

Bone

Fats

Fat

"

SOAP-MAKIKG

FOR

INTENDED

"

41

Oils

Vegetable

"

Rosin.
"

CHAPTER

V.

SOAP-MAKING

.45

Classification
Cold

of

Process

Pressure-"

Soaps
Soaps

Soft

Marbled
"

Direct

Saponification

"

Soap"Marine.

Pasting

combination

of

"

or

Soap"

Saponification

under

Fatty

Graining

with

Alkali
"

Increased

Hydrated
"

Acids

Diminished

or

Smooth

Soaps,
Out
"

Boiling

and
on

CONTENTS.

vi

I"AUK

Pans

Utilisation of

Settlingof Soap"

and

"

"

Colouring and Perfuming

and

"Barring" Open

of

Soaps

"

Milled

Drying

Soaps

Perfume

"

SuperfattingMaterial
cated

Soaps"

Slabbing

VII.
SOAPS

77

......

Colouring

"

Compressing

"

"

Cutting

Stamping"

"

Soap" Floating Soaps"Shaving

Ether

Soaps

""

Soaps
Soaps

Miscellaneous

"

Soap*

NwitraliHing and

matter"

Soaps for Woollen, Cotton and Silk IncUwtritsH -Patent

"

MtuliToxtil*!

'IVxtilo

Soaps.
VIII.

CHAPTER
SOAP

"

Millingand IncorporatingColour,IVrfuwo,

"

"

Medicament

or

Neutralising,

Pilling

"

Cold Process Soaps" Settled Boiled Soaps" Komoltwl

Toilet Soaps
"

Soap.

Close Piling" Drying" Stamping" Cooling.

MISCELLANEOUS

AND

of

Disinfectant Soaps--Framing"

"

CHAPTER

TOILET, TEXTILE

Nigrcs" TnniHpart"ntSoups

GO

Liquoring

Orutching

Cleansing

of

SOAP

SETTLED

OF

Oroy

VI.

CHAPTER
TREATMENT

and

Soaps" Ruling

Oil" Electrical Production

Mineral

"Saponifying

Household

Yellow

Base"

Soaps" Milling

Mottled

Mottled ~F"luo

Soaps"Curd

Strength" Fitting"Curd

PERFUMES

95

Oils

Essential

"

Source

and

Preparation" Properties-Artificial and

SyntheticPerfumes.
CHAPTER
GLYCERINE

MANUFACTUEE

Treatment

of

AND

Lyes

PURIFICATION

Evaporation to

"

IX.

Crude

Pure
Dynamite Glycerine"Chemically

Charcoal

for Decolorisation

of

Yield
Saponification
"

of

Glycerinefrom

ANALYSIS

RAW

OF

Fats and

MATERIALS, SOAP,

Oils" Alkalies and

Crude

Alkali

AND

Giln,

GLYCERINE

Oils"

,117

OF

THE

SOAP

OF

OF

XI.

INDUSTRY

DEGREES, TWADDELL

DIFFERENT

Soap" Ly OH"

lf

140

AND

APPENDIX
COMPARISON

Glycerine.

APPENDIX
COMPARISON

by other methods

and

I "ii*-

X.

Salts" Essential

CHAPTER
STATISTICS

Fats

.111

Glyr.erino"Animal

Glycerine obtained

CHAPTER

Glycerine" DiHtillation"

tilled and

"

THERMOMETRIC

A.

BAUMI", WITH

ACTUAL

DENBITXKH

147

B.

SCALES

,148

CONTENTS.

Vll

PAGE

APPENDIX

TABLE

OF

THE

GBAVITIES

SPECIFIC

C.

OP

APPENDIX

TABLE

OF

STRENGTH

OF

CAUSTIC

POTASH

SOLUTIONS

CAUSTIC

OF

SODA

149

D.

SOLUTIONS

AT

60"

F.

151

153

r!
I.

CHAPTEE

INTRODUCTION.

Definition of Soap
IT

has

of

been

nation,

correct

been

first

was

soap

discovered

mixing

In

Fanti

race,

and

have

Africa,

at

five

to

and

Marseilles

this

the

soap

-thumb

at

once

the

Latin

product

chemical

bases,

sense
a

obtained
it

"

until

flourished

have

introduced

was

factories

olive-oil

banana

established

were

does

Soap

soap.

fourteenth

the

London

is in

nineteenth

classic

From

the

facture
manu-

scientific

by
the

on

basis,

commercial

salt, the production of soap

common

bounds

on

of Chevreul

for the

not

century,

1524.

century

researches

"!"i

into

slowly, being essentially earned

The

until

word

it

is

now

definition

to

which

palmitate, which

also

the

of

form

(Latin sapo,

soap

one

the

of

most

tallow

combinations
includes
the

not

bulk

of

the

soaps

etc., used

lead, manganese,

which

is

cognate

been

originallyapplied to
with
ashes.
In its strictly
with
of fatty acids
metallic
stearate, oleate
only sodium

have

to

appears

by treating

refers

and

linoleates

the

from

and

tallow)

sebum,

Spain,

in

to

seems

and

pared
pre-

soap
of

industries.

important
Definition of Soap.
with

of soap

with
ashes

the

placed the industry upon

discovery of a process

soda

by leaps

of British

with

of

of

the

but

Germany, having
by
product obtained
the
to
giving a bright hue
the natives, especially the
themselves

manufacture

beginning
developed very

of caustic

advanced

measure

from

wash

England

in

of soap

by Leblanc's

manufacture
has

made

been

of fats

stimulated

civilisation

the

great

water

and

manufacture

methods,

constitution

Action.

the

later, when

years

till the

of

and

the

first record

time

rule-of

for

have

to

appear
and

oil

hundred

for

moreover,

accustomed

been

by mixing
palm
and
manufacture
plantain skins. ^The
the
during
eighth century in Italy
some

in

be

Eome
used

ash

beech

Central

West

into
who

Gauls,

crude

France

of

gauge

perhaps

may

introduced

the

by

goats' tallow

hair.

this

is

soap

Detergent

"

has
of soap
not
existent
coalways been
present day, the use
civilisation, for according to Pliny (Nat. Hist., xxviii.,

with

12, 51)

Hydrolysis

"

of

use

though

but

the

at

the

that

said

Properties

"

as

of

commerce,

driers, and

but
various

oleate
olea(Hydrargyri
pharmaceutical preparations, e.g., mercury
oleate
and
lead
of other
tum), zinc
plaster,together with a number
metallic
salts of fatty acids.
the
Technically speaking, however,
of
the
term
is
restricted,
considerably
meaning
being generally
soap

fK

MANUFACTURE.

SOAP

limited

combinations

the

to

animal

treatingvarious

or

alkalies,obtained by

fatty matters,
vegetable

derived therefrom, with soda

the latter soft soaps.
The
of ammonia
use

and

fattyacids

of

potash,the

or

'as

alkali for

an

former

givinghard soaps,

attempted,but owing to the ease with which

decomposed,it can scarcelybe looked upon as

is

has, however,

Jackson
the

use
1906)
is prepared in

and

Neither
constituents

recentlypatented (Eng. Pat. 6,712,

This detergent
laundry work.
and

of use,
merely immersing them

the wash-tub

by
rinsingin

of the
salts of

potassium

oleate for

of ammonium

cleansed

goods are
short time

resultant
product of

the

value.

commercial

H.

has

soap-making purposes

often been
soap
much

fattyacids

the

or

at the time

it is claimed

in this

solution

that
for

fresh water.

given above
rosin,commonly called

definitions

of rosin have

shown

been

to

includes
rosin

the

and

sodium

soap, for

be aromatic, but

the

acid

in view

of

of these resinates to true

analogousproperties
soap, they are
of
constituents
generallyregarded as legitimate
soap, having been
used in Great Britain since 1827, and receiving
sanction in
legislative
the

Holland

in 1875.

Other

of

definitions

have

soap

given,based

been

not

upon

its

which may
be mentioned
but upon its properties,
composition,
among
that of Kingzett,
who says that
considered
Soap,
commercially,is a
that of
with water
liberates alkali,"and
body which on treatment
"

Nuttall,who
in

washing

defines soap as "an

".
and cleansing
"

in either alcohol

slowly,and

or

or

used

substance

unctuous

soda and

Both

Propertiesof Soap.

alkaline

hot water.

ble
potash soaps are readilysoluIn cold water they dissolve more

due to hydrolysis(vide
slightdecomposition,
turbid.
Sodium
oleate is
infra),the solution becomes
distinctly
in
in
dilute
solution
not
peculiar
undergoing hydrolysisexcept
very
,^nd at a low temperature. On cooling
hot soap solution,a jellyof
a
less
firm
consistence
or
results,a propertypossessedby colloidal
:more
in contradistinction to substances
ibodies,such as starch and gelatine,
"which under
the same
conditions depositcrystals,
due to diminished
of
the
salt
lower
at
a
-solubility
temperature.
Krafft (Journ.Soc. Chem.
Znd.,-1896,206, 601; 1899, 691; and
1902, 1301) and his collaborators,
Wiglow, Strutz and Funcke, have
this
solutions
of
the researches
-investigated property
soap
very fully,
In the light
of their more
recent
extendingover several years.
work,

owing

to

"

the

molecules,or

become

definite

gelatinouson

molecules

coolingmove

in the formation

althougharranged

aggregatesof molecules,of
of

much

but
crystal,

to that
differently

of

more

solutions

slowly

which

than

the

there is a definite structure,

a
of
crystal. In the case

soda

soaps the colloidal character increases with the molecular

weight
of the fattyacids.
Soda soaps are insoluble in concentrated caustic lyes,and, for the
most

part,in strong solutions

of sodium

chloride,hence

the

addition

INTRODUCTION.

of caustic soda

brine

or

out and
to separate

of

potashsoap,

the

on

soda

to

solution

of soda

rise to the surface.

other

and

soap

C17H35COOK

hand, merely

potassiumchloride
NaCl

potassium
stearate

Addition

soap causes
of brine to

results

"

KOI

sodium

potassium

chloride

stearate

chloride

chloride,sodium

it, and
precipitate

solution to

position,
decom-

sodium

the' different soaps in salt solution

is insoluble in a
stearate
.Whilst sodium
considerably.
solution of sodium

solution

being formed, thus

of
solubility

The

in double

C17H35COONa

the soap

laurate

sodium

varies very
5 per cent,

requiresa 17

cent,

per

thrown

caproate is not

of

out

by a saturated solution.
hydrolysis is appliedto any
Hydrolysisof Soap. The term
the decompositionis
resolution of a body into its constituents where
of
the
action
when
water, hence
brought about by
soap is treated
the reaction taking
with cold water, it is said to undergo hydrolysis,
placebeingrepresentedin its simplestform by the equation:
solution

even

"

"

"

"

'

2NaC18H3502

H20

sodium

NaOH

soda

arrived

which

actual reaction

by

Chevreul,

and fats,found

that

the

pioneerin

the

been

diverse

very

small amount

stearate

has

occurs

chemists, and

many

at.

acid sodium

caustic

water

stearate

The

HNa(C18H3502)2

the

of alkali

modern
was

with the formation

together
equation,

in the above

subjectof

conclusions

gation
investi-

have

been

chemistry of

oils

as
liberated,
appears
of an acid salt,
a very

fattyacid remaining in solution. Eotondi

Ind., 1885, 601),on the other hand, considered
that a neutral soap, on beingdissolved in water, was
resolved into a
basic and
acid salt,the former readilysoluble in both hot and
an
soluble
cold water, the latter insoluble in cold water, and onlyslightly
quantity of

minute

free

(Journ. Soc. Chewi.

appears, however, to have been misled

oleate is readilysoluble in cold water, and
He

in hot water.

that sodium

have been

shown

G-es.,
1894,

1747

and
palmitate

be incorrect

to

1755),who

and

stearate

by

from

Krafffc and

Stern

by

the

fact

his

views

(Ber.d.

Chem.

experimentswith

pure

sodium

conclusions

arrived at

by

a soap
occurringwhen
of the fatty
acids from

is dissolved

in

confirm the
entirely

Chevreul.
The
water

is

of dissociation

extent

the nature

depends upon

made,

and

also

on

the concentration

which

of the solution.

the soap
The sodium

caprylicacids)are
and the fatty
by
acids from
cotton-seed oil being dissociated more
readilythan those
of stearic acid and tallow fattyacids.
The decompositionincreases
with the amount
of water employed.
The hydrolytic
action of water on
soap is affected very considersalts of cocoa-nut
far the most

fattyacids

(capric,
caproicand

those
easilyhydrolysed,

of oleic acid

MANUFACTURE.

SOAP

the

in

water,

ably by the presence of certain substances dissolved

Caustic soda exerts a
and magnesium.
salts of calcium
particularly
do also ethyland amyl
as
marked
retardingeffect on the hydrolysis,

glycerol.

alcohols and

by
property possessed

The

DetergentAction of Soap."
removing dirt is one which it

is difficult to

^ot

soap

explain.
satisfactorily

but
been
have
suggested,
complicated,
be regardedas solved.
cannot
the question
now
even
The explanation
commonly acceptedis that the alkali liberated
attacks any greasy matter on the surface to be cleansed,
by hydrolysis
loosened and
of dirt are
and, as the fat is dissolved,the particles
the
easilywashed off. Berzelius held this view, and considered that
free
it
with which
yielded
value of a soap depended upon the ease

theories,more

Many

alkali

less

or

solution in water.

on

theoryis considered by Hillyer(Journ. Amer. Chem. Soc.,

for,as he points out, the
1903, 524),however, to be quite illogical,
with the
liberated
alkali would be far more
likelyto recornbine
This

acid
a

than
separated,
while, further,unsaponifiable
glyceride,
greasy
there
and
as
as
fat,
easily
saponifiable
by soap
which

acid salt from

or

neutral

removed

it has

been

saponify

to

is

matter

be

can

no

Yet

question of any chemical action of the free alkali in its case.

is greater in
argument against the theory is that hydrolysis

another
cold

dilute solutions, whereas

and

Eotondi

(Journ. Soc. Chem.

basic soap, which

that

the

was

alone

responsiblefor
fattymatter
dissolving

soap

out, his

theoryof

and
incorrect,

Several

the best

having

regardedas
generally

are

Ind., 1885, 601)

he

of the

was

believed to be formed

detergentaction of soap, this basic

by saponification,
but, as alreadypointed

the formation

of

are

have
explanations

basic soap

is

Jevons
**

in 1878

in
"

or

"pedesis

been

suggested,based

solutions.

will be found

Most

to

other factors not

researches

some

of small

to be

known

now

therefore invalid.
on

of these

the

are

at any
rate in parfc,
be little doubt
correct, and there can
ultimate solution of the problem lies in this direction,
and

detergentaction of soap
with
properties,
together

opinion

by hydrolysis,

the

his conclusions

of soap
physicalproperties

solutions
soap
detergentaction.

concentrated

hot

a
particles,

depend

on

many

purely
probably,
that

the

that

the

of these

yet known.
on

the

movement

"Brownian

ment
move-

of the

particles
clay,iron oxide,or other finely
divided insoluble matter is suspended in
water, found that the pedetic
actoin was
increasedby soap and sodium silicate,
considerably
and
suggestedthat to this action of soap" might be attributed much of its
cleansingpower.
Alder Wright considered that the alkali liberated
in
by hydrolysis
which

some

is observed

way

to take

promoted

placewhen

contact

of the water

with

the substance
to be
of
themproperty
soap solutions selves
to facilitatecontact of the water
with the dirt,
of
as
the
one
chief causes
of the efficacy
of soap as a detergent.

cleansed,and Knapp regarded

the

INTRODUCTION.

Another

in which

way
is that

cleanser
as

serves

the

has

it

itself

soap

the

or

the

lubricant, making

that

suggested

been

alkali

as

by hydrolysis
thus

and

adherent,

less

dirt

acts

soap

free

set

moting
pro-

its removal.

-theory yet advanced

J^hejnost -likely
power

soap
oils
with

emulsions

form

has

is

long

been

based

that

fact

The

solutions.

of

that

will
the

and

known,

attributed

sifying
emul-

the

on

these

readily

detergent

i]

it, the

explanation
the fatty
emulsifies
given being that the alkali set free by the water
in
matter
suspension
always adhering to dirt, and carries it away
the other impurities. Experiments
with
by Hillyer (loc. cil.} show,
will readily emulsify a
that
of alkali
while
however,
N/10 solution
emulsion
is produced with
oil containing free acidity,no
cotton-seed
with
from
oil
which
the
has
been
all
removed,
kerosene,
or
an
acidity
emulsion
oleate will readilygive an
of sodium
whereas
solution
a N/10
with
to the soap
is due
either, thus proving that the emulsification
of

action

has

not

to the

itself,and

35, 592) have

foaming

considers

made
of

that

141, 44) and

very

complete

liquidsand
there

are

on

similar

considers

cohesion
its

is also very

small

emulsifying power

this

have

can

oleate,

which

water,

is

an

but

the

is

excellent

it

must

former

play

an

considerable

have

40
and

low.

per

cent,

second
of

it is doubtless

chiefly due.
for

So
a

far
1

reference

has

per

as

of

to

its

property

its

that

soap

solution

and

oil.

of

detergent

cent,

different

already

action

'

*?l

i|

^ 1

viscosityis concerned,
solution
from

been

of sodium

that

made,

of

pure

gated
investi-

exhaustively, and,
the result
that
of a very
of experiments, concludes
as
large number
the cleansing
of soap
is largely or entirely to be explained by
power
the
which
it has
of wetting
of emulsifying oily substances,
power
and
of
and
into
and
texture
lubricating
penetrating
oily textures,
is
It
that
be removed
impurities so that these may
easily.
thought
all these
the low
be explained by taking into account
properties may
cohesion
of the soap
their strong attraction
solutions, and
or
affinity
to oily matter, which
tension
between
the low surface
together cause
question

sur-

while-

water,

this

If*

^ If

foam.

condition,

that

holds

Quincke

liquid will

no
pure
fulfils Plateau's

work

be

must

viscosity very little

emulsifying agent.

whose

whole

tension

little influence,

has

Hillyer, to

The
which

liquid

of

Ann.,

nisi fication

em

of bubbles.

formation

that

admirably
being only about

tension

the

on

solution

Soap
face

the

the

(Wiedmanns

Quincke

properties
(1)
phenomenon,

its surface

views,

to

researches

two

important part in
viscosity,and
(2)
but

been

alkali.

(Pogg. Ann.,

Plateau

and

frequently

soap

very

t.

'if
;

CHAPTEE

CONSTITUTION

OF

II

OILS

AND

THEIR

AND

FATS,

SAPONIFICATION.

Researches

Chevreul

of

Saponification
Castor-seed

phwric
Oxide,

THE

Theories
of
G-lycerides Modern
;
by (1) Heat or Electricity,(2) Ferments
and
Steapsin,
Emulsin,
Reagents ; Sul(3) Chemical
Magnesia, Zinc
Reagent, Hydrochloric
Acid, Lime,

and

Ferment,
TwitchelVs

Acid,
Soda

and

Mixed

"

"

accelerated

Potash.

oil is of very

term

Berthelot

Hydrolysis

"

significance,
being applied

wide

of

vastly different natures, both

organic
materials
are
soap-making
concerned, it
the

to

though
also

many

utilise

become

oils

frozen

Scheele

oil

with

or

tallow

of
fat

and

of

melting

vegetable

the

during

preparation

their

1779

in
is

oils)

other

or

The

are

acid

and

tirely
en-

to

years

readily

Fats

soap.

as

sources,

few

last

points,

as

and

to

withwith
:

that

time

be

may

garded
re-

form

stearin
olein

fats

showed

that

chemical

the

was

fatty acid
soap,

and

(found

and

SNaOH

3NaOOC18H3S

largely

olive

CHOH

CH2OH
"

hydroxide

glycerol

stearate

CH2OOCWH31
CHOOC16H31

in

sodium

stearin

CBLOH

SNaOH

3NaOOClfHsl

CH2OOC16H31

CHOH

CH2OH
sodium

palmitin
hydroxide

sodium

palmitate

of

which

(of

CH20001SH35
sodium

the

glycerol

palmitin

"

as

combining
the

CE..OH

+.

of

was

decomposition

CH2OOC18H35
CH00018HS3

preparation
regarded

of oils and
who

glycerol, the

base,

follows

in

constitution

definite

and

the

that

Chevreul

was

reactions

at

soap

the

It

fatty

free.

and

involved

soap

into

discovered

liberated,

chiefly consists)

cotton-seed

made

the

mixture,

soda, potash,

remaining

for

understood.

properly

manufacture

been

restricted

be

may

animal

far

so

almost

oils.

mechanical

not

from

heating beyond

plaster glycerol

mere

the

have

on

Although
lead

attempts
mineral

oils
as

products

derived

but

inorganic,

and

substances

to

glycerol

and

OILS

OF

CONSTITUTION

PATS.

AND

CH.2OH

CH2OOC18H38
CHOOC1SH,,
I
CH,OOC18H33

3NaOH

3NaOOC18H,3

CHOH

I
CH",OH

"olein .8fitu?, S"?T

oleate

glvcerol
"

hydroxide

Berthelot

Chevreul's

investigations
by
t
and
glycerol,he
fatty
method
he adopted consistingin heatingthe fattyacids with glycerol
sealed
in
tubes.
Thus, for example :
08Hfi(018H3602)3
3C18H3503H + G3H5(OH)3
tristearin
stearic acid
glycerol

subsequentlyconfirmed
fats

directlysynthesisingthe

acids

from

"

three hydroxyl
is a trihydricalcohol,i.e.,contains
glycerol
are
(OH) groups, the hydrogen atoms of which
displaceable
by acid
three
in
t
he
above reaction may
be supposed to take place
radicles,
Since

stages. Thus,

we

(1) 018H85OaH

have

may

"

03H5(OH)3

C8H5(OH)L"018H3502+

H2O

monostearin

(2) C18H3AH

OsHB(OH)3C18HMOa

+ H2O
C3H,(OH) (ClsH3r,0.2)o

distearin

(3) 018HM02H

C3H5(OH) (G,^,.^,),

+
H20
C3H,(C]SH3r,02):j

tristearin

diglyceride,
being
according to the relative
and representedby the following
termed alpha and beta respectively,
There

are

possible forms

two

of

monoglyceride and

positionof the

formulae,where

E denotes

the acid radicle

acid

radicle,these

"

Monoglyceride:
"

CILOH

GH.OR
and

CHOH

(alpha)

(beta)

OHOB

CH2OH

CHaOH

OHaOB

CH.OE

Diglyceride
:

"

and

CHOH

(alpha)

(beta)

CH,OH

CH2OE

Accordingto
used, and

the

in

the relative

temperature to

preparingmono-,

CHOE

proportionsof fattyacid and glycerol

which
ceeded
heated, Berthelot sucthey were
of
various
di- and
fatty
triglycerides

acids.
all
Practically
mixtures

of these

variably

occur

the

oils and

compounds

in nature

of

soap-making consist of
fattyacids,which intriglycerides.

fats used

in

glycerolwith

in the form

of

MAJXU^AUTUKK.

formerlyconsidered that the three acid radicles in any

to the
were
identical,
corresponding
occurringglyceride
naturally
It

was

formula

"

CH2OE
CHOE

CH2OE
where E denotes the acid radicle. Eecent work,however,has shown
in which the
the existence of several so-called mixed glycerides,
of
the
of
molecule
same
are
hydroxyls
by two or
displaced
glycerol
sometimes three different acid radicles.
The

first mixed

to
glyceride

be discovered

obtained
C3H5(OC18H350)
(OC1SH350).2,
fat.

Hansen

has

since found

from

1 to 2 per cent, of

that

by

was

oleodistearin,

Heise in 1896 from Mkani

tallow contains

oleodipalmitin,
C3H5(OC1SH350)(OC16H31O),stearodipalmitin,
C3
(O016H310), oleopalmitostearin,
C3H5(OC18H330)
the
(OC1SH350)and palmitodistearin,
CH(OC16H310)'
(OC18H3flO)2,
latterof which has also been obtained by Kreis and Haf ner from
lard, while Holde and Stange have shown that olive oil contains
oleodidaturin,
(OC17H330).,
03H5(0018H380)

and Hehner

and Mitchell have obtained indicationsof mixed glycerides

in linseed oil (which theyconsider contains a compound 'of glycerol
radicles of linolenic acid and

with two

radicle of oleic acid),

also
one
and shark oils.
In some
the fatty
acids are combined with other bases than
cases
glycerol.As examplesmay be cited beeswax,containing
myricinor
and spermaceti,
of
cetin
or cetyl
myricylpalmitate,
consisting
chiefly

in

cod-liver,
cod, whale

and
palmitate,
waxes,

but

sometimes
do not
The

herein lies the essential differencebetween fats and

as these substances are
not soap-making
materials,
though
admixed with soap to accomplish
some
object,
special
they

requirefurther consideration.

principal
pure

triglycerides,
with

their formulae and

table :
constants,are givenin the following
"

chief

**::
10
and

MANUFACTURE.

SOAP

washing free from

blue

litmus

paper.
those insoluble

rather

caproic, caprylicand
soluble

mineral

This

in water,

acid,is

soluble in alcohol and

oilylayer consists of the

reddens,

"fattyacids

"

or

in water, acids like acetic,propionic,

butyric,
less readily
or
capric, which are all more

remainingfor

part dissolved in the aqueous

the most

portion. All the acids naturallypresent in oils and fats,whether

free or combined, are
monobasic
in character,that is to say, contain
OH
The more
.CO
only one carboxyl
important fattyacids,
group.
"

be classified accordingto their chemical

may

homologous series,having the generalformulae

I. Stearic series

constitution

into five

"

CJS9n+1COOH

II. Oleic series

III. Linolic series
IV.
V.

Linolenic

I. Stearic Series.
their
table

series

Eicinoleic series
"

The

meltingpoints and
:

acids
principal
chief sources,

of this
are

with
series,
together

given in

the

following

"

Medullic

and

this series,have
and
and palmitic,

margaric acids,which
now

been

shown

to

were

consist

formerlyincluded
of mixtures

in

of stearic

and oleic acids respectively.

stearic,palmitic

CONSTITUTION

acids

The

of this group
directlywith iodine

combine
at

in all
and

OILS

AND

saturated

are
or

proportions;

distil

does also lauric acid, which

11

FATS.

compounds, and

bromine.

The

distil without

ordinary temperatures,

miscible with water

less soluble in water
as

OP

first

two

decomposition,and
the

unchanged

four

next

are

solid,and

are

II.

Oleic Series

in the presence

The

unsaturated

is almost

of these

nature

Thus, they readilycombine

on

and

the lower

apply

acids

with
members

from

attempts
De

to the

with

with

been

and

precedingseries.

or

iodine to form

of the series

at

are

addition

reduced,

once

higheracids

such

point of
made

view

Keychler

oleic

matter

of the

to effect this

have

as

acid,but

of

by

the

technical

some

candle-maker,

shown

as

number

that

by heating oleic

1 per cent, of iodine in autoclaves

up to 270"-280"
Ziirer has devised
into
and
stearic
is
converted
cent,
acid,

62,407) a

the

action

nascent

hydrogen.

(EnglishPatent

More

1,515,1903)

which
dichloride,

recentlyNorman

with

hydrogen

nickel, cobalt

or

or

iron.

conversion

for the

acids of Series II. into the saturated

water-gas

compounds

in

It is claimed

portance
imof

acid
70

(German

the oleic acid is first converted

whereby

process
of chlorine into the

version
con-

other methods.

C., about

per
Patent

by

the

Wilde

their behaviour

renders

that of the

bromine

of the latter into solid acids is

have

solid

sponding
amalgam in alkaline solution,to the correthis reaction
acids of Series I.
Unfortunately,

saturated
does not

with

sodium

with

treatment

All these

"

different from
with various reagentsentirely

compounds,

or

of water,

are

are

more

by
completelyinsoluble in water.
acids are
soluble in warm
alcohol,and on being heated
caustic alkali undergo no change.
only

liquid

are

insoluble in cold water, and

The
boilingwater.
higher acids of the

slightlydissolved

series

will not

the
that

has

is then

secured

reduced
a

patent

of unsaturated
of Series
of

fatty

tion
reduc-

I.,by
finelydivided

presence
by this method

oleic acid

completelytransformed into stearic acid,and that the melting point

of tallow fattyacids is raised therebyabout 12" C.
has been
which
method
Another
proposed is to run the liquid

is

12

SOAP

olein

over

series of

MANUFACTURE.

which
electrically
chargedplates,

effects its reduction

to stearin.

Stearic acid is also formed

oleic acid with fuming hyby treating

of phosphorus,while other solid acids are
acid or zinc chloride on oleic acid.
obtained by the action of sulphuric
Acids of Series II. may
also be converted into saturated acids by
with
solid
300"
C.
caustic potash,which decomposes them
to
heating
into acids of the stearic series with liberation of hydrogen. This reaction,
the
with oleic acid,for example,is generally
representedby
equation
K010H8102
KC,H30,
C1SH3402 2KOH

driodic acid in the presence

be

more
really
complex than
oxalic
acid is also
pointedout,

though

it must

Edmed

has

The

quantity.

of the

One

on

process

commercial

this indicates,for,as
in considerable

formed

scale has

of
important properties

most

acids of

of isomeric

doned.
aban-

been

now

of acids is

this group

the

formation

with

termed the elaidin reaction.

Oleic acid,
acid,generally
acted
by nitrous acid, yieldselaidic acid,melting
example,
upon

for
at

treatment

nitrous

45",and

being

occurs

converted

into

elaidin,which

lead salts of the acids

The

ether, and

of the

action
givesbrassic acid,meltingat 60" C. This rewith the neutral glycerides
of these acids,olein

erucic acid

also

in

highermeltingpoint on

the lithium

melts

at 32" C.

of this series

salts

more

soluble

are

in

much

soluble

more

alcohol than

those

both of which
stearic series,upon
properties
processes have
for the separation
of the solid from the liquid
fattyacids.

based

been

III. Linolic Series

These

They

acids

"

readilycombine with bromine, iodine,or

by nitrous acid,and their lead salts are

unaffected

are

in ether.
IV.

Linolenic Series :

"

oxygen.
soluble

CONSTITUTION
acids

These

OF

similar in

are

with

six atoms

combine

with

only four

of

acid combines

converted
melts

at

two

acid into

52"-53" C.

those

of Class

iodine,whereas

or

III.,but

the

latter

"

with

nitrous

by

bromine

FATS.

atoms.

V. Eicinoleic Series :

This

AND

propertiesto

combine

OILS

Pure

of bromine

atoms

the isomeric

or

ricinoleic acid, obtained

active,its rotation
optically

being [a]d+

iodine,and ia
acid, which
castor oil,is.

ricinelaidic
from

6" 25'.

The decomposition
Hydrolysisor Sapouification
of Oils and Fats.
of a triglyceride,
broughtabout by caustic alkalies in the formation of
soap, though generallyrepresentedby the equation already given
(pp.6 and 7)"
"

C,H,(OB) +

3NaOH

C,H5(OH)3

such a simple reaction.

any means
In the first place,though in this equationno

is not

by

of the latter is found

presence
to take

place; in
the oil or

radicles to

supposed

since

in

appears,

the

for saponification
indispensable

glyceridesthere are three

their saponificationcan
glycerol,

formation

of

successive
and

mono-

from
triglycerides
fatty acids
be
regarded as a
equation may

of
above

water

the

separatedfrom
take place in three

of the

converse

to

be
to

be

fact,the water must be regardedas actuallydecomposing

fat,caustic soda or potash merely actingas a catalytic

agent. Further,

three

3BONa,

stages, which

in
diglycerides

are

the

acid
be

the
thesis
syn-

and

glycerine. Thus, the

of the following
summary

"

fOH

fOB

O,HP^
(i.)

OB

NaOH

C.H^

OB

BONa

'

LOB

fOH
(ii.)
0.,H,^OB

fOH
NaOH

=
r

OB

BONa

BONa

'

LOB

fOH

fOH
(iii.)
Geitel and

physicaland

OB

NaOH

Lewkowitsch,
chemical

who

OH

have

pointof view

studied this

questionfrom the
of opinionthat
are
respectively,

]
1

I
II

14

these three reactions do actually

saponified,
time unsaside by side,the soap-pan
containingat the same
occur
and
diglyceride,
monoglyceride,glycerol
soap.
ponifiedtriglyceride,
This theoryis not accepted,
however, by all investigators.Balof Lewkowitsch's
doubt the validity
conclusions,
foiano and Marcusson
of olive oil with
the saponification
and Fanto, experimentingon
of any
formation
caustic potash,is unable to detect the intermediate
solution
that in homogeneous
and concludes
monoor
diglyceride,
the
on
the saponification
is practically
Kreeman,
quadrimolecular.
when

oil

an

fat is

or

*
"

|
'

",j

evidence
as

"

Hydrolysiscan

practiceto

j
"I

'j
|
j
1

|
!

''j
j

to favour

seems

is

(,

and
is bimolecular,
saponification
this theory,the matter cannot

that

of Geitel

view

though the
regarded

be

settled.
yet definitely

',

*i|
j

data,supportsthe
physico-chemical

other hand, from

and Lewkowitsch

"|

.'}

MANUFACTUBE.

SOAP

allowed,but

as

be
the

broughtabout by water alone, if sufficienttime

process is extremelyslow, it is customary in
reaction

accelerate the

the

by

use

methods,

of various

action of
(ii.)
electricity,
with
effect
chemicals
the
and
treatment
(iii.)
accelerating
;
enzymes,
due
is
their
methods
to
latter
of the two
emulsifyingpower.
of soap is to
The most usual method adoptedin the manufacture
soda
the
oil
caustic
fat
the
or
or
by
fattyacids
potash,
hydroiyse
the
with
the
time
liberated at
same
combining
catalyst,i.e.,soda or
potash,to form soap. Hitherto the other processes of hydrolysis
for the preparationof material for candles,
have been employed chiefly
for which
complete separation of the glycerolin the first
purpose
since the fattymatter
is not essential,
is usuallysubjected
hydrolysis
with sulphuricacid to increase the proportion
to a second treatment
The colour of the resulting
of solid fattyacids.
fattyacids is also of
no
importance,as they are always subjectedto distillation.
During the last few years, however, there has been a growing
attempt to first separate the glycerolfrom the fattyacids,and then

which

include

or

the latter into soap by treatment

with the carbonates
of soda
of course
the
than
are
caustic
considerably
cheaper

convert
or

heat

of
the application
(i.)

potash,which

!i
"!

fat.

which

alkalies,but
The

cannot

be used

in the actual

used
processes chiefly
reaction is brought about

for this purpose

two

the

of
saponification

by

neutral
those

are

in

by Twitchell's

or

enzymes

reagent.
I.

Applicationof

150" C. the

Heat

or

effect of water

steam
passingsuperheated

Electricity.Up
"

to

temperatures

of

oils and

fats is very slight,

but by
heated
matter
300"
to
200"C.
through fatty
on

the neutral

are
glycerides
completelydecomposed
fattyacids accordingto the equation

into

glyceroland

"

C3H5(OE)3+
The

fattyacids and

steam, and
condense
aqueous

3H.OH

are
first,

of

C3H5(OH)8+

formed
glycerol

by arranginga

solution of

obtained

series of
almost

distil over

is

with

the

excess

of

condensers,the former, which

alone

in the later
glycerine

fattyacids

3EOH.

in the earlier ones,

This method
ones.

used
extensively

in France

for the

and

an

of preparation

produc-

CONSTITUTION

OILS

OF

AND

15

FATS.

of stearine for candle -manufacture, but the resulting

product is
To expose the
liable to be dark coloured,and to yielda dark soap.
tion

'

.acids to

heat for

Mannig

has

under

the

of time, and

minimum

patented (Germ.

pressure
mounted
in
plate
in

of

form

claimed, much

of 8 to 10
a

closed

Pat.

160,111)

whereby
projectedagainst a
a

atmospheres is
vessel,where

a
spray, the
increased.

rate

of

prevent discoloration,

so

process

it mixes

Simpson (Fr.Pat. 364,587) has attempted to

decompositionby subjectingoils or fats to
action of heat and electricity.
Superheated steam
are

immersed

the
battery,

the two

baffle
oil

or

hydrolysisbeing thereby,it

tne

oil,in which

the fat

with

steam

electrodes

accelerate
the
is

further

simultaneous

passed into

connected

allowed

is

with

to exceed

the

namo
dy-

270" C.

being
discovered
in 1871
of Enzymes. It was
by Muntz
de
t
hat
of
seeds a
castor
Chemie, xxii.)
^Annales
during germination
quantityof fattyacid was developedin the seeds,which he suggested
might be due to the decomposition of the oil by the embryo acting
or

II.

as

temperature not

Action

"

that when
castor
Schutzenbergerin 1876 showed
steepedin water, fattyacids and glycerolare liberated,and
this to the hydrolytic
action of an enzyme
present in the

ferment.

seeds

are

attributed
seeds.

No

evidence

of the existence

however, till 1890, when

Green

of such

ferment

was

adduced,

(Boy. Soc. Proc., 48, 370) definitely

capableof splitting
up

proved the presence in the seeds of a ferment

the oil into fattyacid and glycerol.
The

first

experimentersto suggest any industrial applicationof

this enzymic hydrolysiswere
Connstein, Hoyer and Wartenburg,
who
(Berichte,1902, 35, pp. 3988-4006) published the results of a
of the .whole subject. They found that tallow,
lengthyinvestigation
other oils,were
cotton-seed, palm, olive,almond, and many
readily
the
castor-seed
ferment
in
the
of
dilute
hydrolysedby
acid,
presence
but that cocoa-nut
and palm-kerneloils only decomposed with difficulty.
The presence of acidity
is essential for the hydrolysisto take
the
suitable
most
place,
strength being one-tenth normal, and the
to the quantity of ferment
degreeof hydrolysisis proportional
present.
Sulphuric,phosphoric,acetic or butyricacids,or sodium
bisulphate,
be used without much
influence on
the result.
Butyric acid is
may
stated to be the best, 'but in practiceis too expensive,and
acetic
acid is usuallyadopted. The emulsified
mixture
should be allowed
to stand for twenty-fourhours, and the temperature should
not exceed
40" C.

; at

50" C. the action

is

weakened,

and

at

100" C.

ceases

altogether.
have
since examined
the hydrolysingpower
Several investigators
of various other seeds, notablyBraun
and Behrendt
(Berichte,
1903,
36, 1142-1145, 1900-1901, and 3003-3005),who, in addition to confirming
Connstein, Hoyer and Warfcenburg'swork with castor seeds,
have made similar experiments
with jequirity
seeds (Abrus peccatorius)
almonds, the
abrin, emulsin from crushed
containingthe enzyme
leaves of Arctostaphylos
Uva
Ursi,containingthe glucosidearbutin,

16

MANUFACTURE.

SOAP

myrosin
crotin

from

mustard-seed, gold lac (Gheirantuscheiri)and

black

from

seeds.

croton

Jequirityseeds

action

lanoline

were

and

found

carnauba

to

have
than

wax

the

on
strongerdecomposing
seed, but only caused decompositionof castor oil after the
with alkali. Neither emulsin,
first neutralised
initial aciditywas
action on castor oil,
marked
crotin have any
arbutin nor
hydrolytic
but myrosin is about half as active as castor seeds, except in the
occurs.
no
decomposition
presence of potassium myronate, when

castor

phy$. cliem. Ges., 35, 831-835, arid Chem. Eev.

the hydrolytic
Fett. u. Harz.
IncL, 1904, 30 et seq.)has examined
Eussian
to
of
thirty
seeds,belonging some
action of a largenumber
than half of these brought about
but althoughmore
different families,
of over
10 per cent, of fat, he considers that in only
the hydrolysis
two
vulgar-is,
cases, viz.,the seeds of GJielidonium majus and Linaria
these beingthe onlytwo seeds for which
is the action due to enzymes,
to the amount
of seed employed,
acids is proportional
the yield
of fatty
the seeds
not produced when
instances hydrolysis
while in many
was
have as
to
found
seeds of GJielidonium
old.
The
were
were
majus
than castor seeds, but
great,and possiblygreater,enzymic activity
those of Linaria are much
weaker, twenty to thirty
parts having only
four
seeds.
the same
five
to
castor
as
of
activity
lipolytic
parts
of free acids found in rice oil has led 0. A.
The high percentage
Brown, jun.(Journ.Amer. CJiem. Soc.,1903, 25, 948-954),to examine
and
the rice bran, which proves to have considerable enzymic activity,
rapidlyeffects the hydrolysisof glycerides.
The process for the utilisation of enzymic hydrolysis
in the separation
of fattyacids from glycerine
the industrial scale,as originally
on
devised by Gonnstein
and his collaborators,consisted in rubbing a
of
the
quantity
coarselycrushed castor seeds with part of the oil or
fat, then addingthe rest of the oil,
togetherwith acidified water (N/10
acetic acid). The quantities
6i parts of decorticated
employed were
S. Fokin

castor

beans

acetic acid.

(/.-mss.

for every 100 parts of oil or fat,and 50 to 60 parts of

After stirring
until an
emulsion
is formed, the mixture

is allowed to stand

-for

twenty-four hours, during which hydrolysis

takes place. The temperature is then raised to 70"-80" C., which
destroysthe enzyme, and a 25 per cent, solution of sulphuricacid,

equal in

taken, added
three

to one-fiftieth of the

amount
to

layersare

total

quantityof

fat

originally

separation of the fattyacids. In this way

the
at the top consisting
of the clear fatty
formed,
one
promote

acids,the middle

emulsion
one
an
containing
portionsof the seeds,
and the bottom
of the aquefattyacids and glycerine,
one
consisting
ous
The
intermediate layer is difficult to treat satisfactorily;
glycerine.
it is generallywashed
twice with water, the washings
being added to glycerine
and
water, and the fattymixture saponified
the

resultant soap utilised.

The
process has been the

numerous
investigation,

subjectof a
attempts having

considerable

amount

of
.

been

made

to

actually

constituent of the seeds,or to obtain

separate the active fat-splitting

*f

18

SOAP

stated that
or

be added at the beginningof the operation,

may
be made
of that formed
duringthe process, though

acetic acid

use

may

in the latter

hydrolysisis

case

have

Experiments
(Journ.SOG. Chem.
ferments

MANUFACTUKE.

derived

slower.

somewhat

carried out

been

by

and

Lewkowitsch

Macleod

Ind.,1903, 68, and Proc. Boy. Soc.,1903, 31) with

from animal
viz.,lipasefrom pig'sliver,
sources,

and

steapsin from the pig or

has been shown
by Kastle.and

The

ox

pancreas.
Loevenhart

former, althoughit

(Amer.Chem.

Journ., 1900,

49) to readilyhydrolyseethyl butyrate,is found to have very little

results have
favourable
fat-splitting
power, but with steapsinmore
is conbeen obtained, though the yield of fattyacids in this case
siderably
cotton-seed
inferior to that given by castor seeds.
With
after
liberated as a maximum
oil,83-86 per cent, of fattyacids were
fifty-six
produced in the.
days, but with lard only 46 per cent, were
Addition
time.
of dilute acid or alkali appeared to exert no
same
influence on the decompositionof the cotton-seed oil,but in the case
of the lard, dilute alkali seemed
at first to promote
hydrolysis,
though afterwards to retard it.
Fokin (Chem. Rev. Fett. u. Harz. Ind.,1904, 11S'-120 et seq.)has
attempted to utilise the pancreaticjuiceon a technical scale,but the
use.
process proved too slow and too costlyto have any practical
throws a good
Rancidity. The hydrolysingpower of enzymes
deal of lighton the development of rancidity
in oils and fats,which
is now
-generally
regarded as due to the oxidation by air in the presence
of light and moisture
of the free fattyacids contained by the
It has long been known
rendered
oil or fat.
that whilst recently
free
from
fats are
animal
acidity,freshlyprepared
comparatively
contain small quantities
of free fattyacid,
vegetable oils invariably
"

and

there

'of enzymes

can

be

doubt

no

contained

expressed,hence
albuminous

the

in

that this must

the seeds

necessityfor

or

be

attributed

fruit from

which

separatingoils and

to the action

the

oils

fats from

are

hering
ad-

as
quicklyas possible.
Decompositionof Fats by Bacteria.
Though this subjectis not
of fattyacids for -soapinterest in the preparation
.of any practical
bacteria readily
making, it may be mentioned, in passing,that some
fats.
Schriber
(Arch.f.
41,
Hyg.,
328-347) has shown that
;hydrolyse
of air many
bacteria promote hydrolysis,
in
the presence
under

matters

"

favourable

||,V

"!"j
','v

'}"

\\!j'
'

conditions

as

to

temperature and

access

of oxygen,

the

up into fatty acid and

process going beyond the simple splitting
dioxide and water
Under
carbon
anaerobic
being formed.
^glycerol,
found
to
conditions, however, only a slightprimary hydrolysiswas
take place,though accordingto Eideal (Journ. Soc. Chem.
Ind., 1903,
of free fatty
acids in a
69) there is a distinct increase in the amount
after passage through a septictank.
sewage
Experiments have also been made on this subject by Rahn
(Centralb.Bakteriol,1905, 422),who finds that Penicillium glaucum
have considerable
action on
and other penicillia
fats,attackingthe
oleic
acid.
not
A motile
and
lower
fatty acids, though
glycerol

CONSTITUTION

OF

OILS

AND

19

FATS.

bacillus,producing a green fluorescent colouringmatter, but not

identified,had a marked
action and decomposed oleic
hydrolytic
acid.

"

The

lipobacter has been proposed by De Kruyff for

bacteria which hydrolysefats.
III. Use of Chemical
Reagents. Among the chief accelerators
the
in
hydrolysisof oils are sulphuricacid and TwitchelTs
employed
reagent (benzene- or naphthalene-stearosulphonic
periments
acid),while exhave
also been
with
made
BOG.
hydrochloric
acid (Joum.
Chem.
Ind., 1903, 67) with fairly
satisfactory
results,and the use of
sulphurous acid, or an alkaline bisulphiteas catalyst,
been
has
patented in Germany. To this class belong also the bases, lime,
magnesia, zinc oxide, ammonia, soda and potash,though these latter
differ from the former in that they
substances
combine
subsequently
with the fattyacids liberated to form soaps.
The
phuric
Sulphuric Acid.
hydrolysingaction of concentrated sul"

name

"

"

acid

upon

oils and

fats has

been

known

since the latter part

of the

eighteenthcentury, but was not applied on a practicalscale

till1840
when
Gwynne patenteda process in which sulphuricacid
used
to liberate the fattyacids,the latter being subsequently
was
distillation. By this method, sulpho-compounds
by
purified steam
first formed, which
of the glyceride
are
readilyemulsifywith water,
with steam, liberate fattyacids,the glycerol
treatment
and, on
maining
rethe
form
of
in
acid.
The
glycero-sulphuric
partly
process
has been investigated
by Fremy, Geitel,and more
recentlyby LewCantor Lectures," 1904, 795 et seq.},
who
kowitsch (/.Soc. of Arts,
series of experiments on
the hydrolysis
of tallow
has conducted
a
with 4 per cent, of sulphuricacid of varying strengths,
containing
from 58 to 90 per cent, sulphuric
acid, HoS04. Acid of 60 per cent.
useless as a hydrolysing
less appears to be practically
or
agent, while
acid
acids
cent,
47*7
were
with 70 per cent,
developed
fatty
only
per
"

after

maximum

after fourteen

steaming, and with 80 and 85 per cent,

of 89 '9 per cent, of fattyacids was
only reached
fifteen hours' steaming respectively.
Using 98

hours'

twenty-two

acid,the

and

obtained after nine

per cent, acid,93 per cent, of fattyacids were
hours' steaming,and after another
seven
hours, only 0'6 per cent,
more
produced. Further experimentshave shown
fattyacids were
that dilute

whale,

and

sulphuricacid
rape

owing

be

also

scarcelyany

Carpenter,some
obtained from tallow by

According to
acids may

has

action

on

cotton-seed,

oils.
Lant

to the conversion

of

75
the

per

cent,

of solid

process,
considerable quantity of oleic acid into

tion
(vide p. 12),but in the process a considerable proporC. Dreymann has recentlypatented
of black pitchis obtained.
(Eng. Pat. 10,466, 1904) two processes whereby the productionof
case, after
of hydrocarbonsis obviated. In the one
any largeamount
with sulphuric
acid,the liberated fattyacids are washed
saponificatiqn
with
with water
and treated
an
oxide,carbonate, or other acid-fixing
body, e.g., sodium carbonate, priorto distillation. In this way the

isoleic acid

Jp

fatty

sulphuricacid

MANUFACTURE.

SOAP

20

clearer than by the ordinary process, and is almost

is much
distillate
is only about
matter
of unsaponifiable
odourless,while the amount
The second method claimed consists in the conversion
cent.
1*2

per
with methyl
of the fattyacids into their methyl esters by treatment
of the esters by
acid gas, and purification
alcohol and hydrochloric

I
f

decomposed with
the pure esters being subsequently
distillation,
without
the addition of
with
or
in
an
autoclave,
steam,
superheated
facilitatetheir
to
zinc
oxide,
decomposition.
an
oxide,e.g.,0*1 per cent,
is made
of the
Twitckell'sReagent. In Twitchell's process use
steam

"

importantdiscoverythat aqueous solutions of fattyaromatic sulphuric

phonic acid,readily
acids,such as benzene- or naphthalene-stearosul
dissociation
into fatty
their
dissolve
bodies,thereby facilitating
fatty

glycerol.These

acids and

preparedby treatinga
acid with

an

of

excess

compounds

stable at 100" (1, and

are

of benzene

mixture

or

naphthaleneand

are

oleic

sulphuricacid,the following reaction taking

place:

"

+ c18H34(x+ H.,so4
oflHfl

C.HXBO.HJG^H^O

ILO.

two layersseparate,
the resultant product with water
boiling
solution of sulphuricacid
of a clear aqueous
lower one consisting
has
acid
been formed, while the
whatever benzene-sulphonic

On
the
and

layer,which is a viscous oil,contains the ben^ene-stearosulphonic acid. This, after washing first with hydrochloricacid and
then rapidlywith petroleum ether, and drying at 100" 0., is then
upper

quantityof this reagent to a

and water, agitatedby boiling
of fat (previously
mixture
purified)
of tho fattyacid
with open steam, effects almost completeseparation
from glycerol.
The process is generally
carried out in two wooden
vats, covered
with closely
lids,furnished with the necessary draw-off cocks,
fitting
the first vat containing
coil.
lead coil and the other a brass steam
a
In the firstvat, the fat or oil is preparedby boilingwith 1 or 2
acid (141"Tw. or 60" B.) for one or two hours
per cent, of sulphuric
and allowed to rest, preferably
the fat
overnight; by this treatment
is deprivedof any dirt,
lime or other impuritypresent. After withdrawing
the acid liquor,
fat
oil
is
other
the
transferred to the
or
vat,
readyfor

where

use

the addition of

it is mixed

with

and open
distilled),
the
a

amount
requisite

small

one-fifth of its bulk

steam

applied.

As

soon

of water
as

(condensedor

boilingtakes place,

into the vat by the aid of

reagent is washed
and
the whole is boiled cona
tinuously
through glassfunnel,
twelve or even
twenty-fourhours,until the free fatty
of

littlehot water
for

acids amount
with

the

to 85-90 per cent.

amount

grade of material,the smaller

efficientresults,
the

good

The

better the

colour

the

of reagent used varies

consistent with
amount

of the finished

product;

with

but for materials

-J to f per cent, is sufficient,
2
more
to
grade proportionately
up
per cent, is required.
The reaction appears to proceed better with materials
containinga
fair quantityof free acidity.

from
material,

of lower

"

CONSTITUTION

the

When

stoppedand

has

process

free steam

OF

OILS

or

60 per cent,

(5"B.),is

removed

21

to fillthe vat to obviate

fattymatter

the

tion
any discolorathe contents
of

air,whilst

should

in bulk

amount

taken, and

have

with

to

quantity (0'05per cent., or

the

boilingmay

end

of that

of

be

period the

the

of the

contents

be neutral

that

fattyacids

It is claimed
may

vat

boiled

are

Twitchell

with

to
so

be stored in wooden

HydrochloricAcid.
has carried out

"

of

treated

are

are

affected

not

(Journ.Soc.

experiments on

Ckem.

the

on

lard

most

by

the

oils,cocoa-nut, cotton-seed,whale

Ind.,1903,

fluence
inaccelerating

hydrochloricacid upon the hydrolysisof

show that acid of a specific
gravityof 1*16 has

effect

; the

packages.

Lewkowitsch

number

allowed to rest
methyl-orangeindicator.
vat

of

which

small

reagent requisite)

carbonate,previouslymixed with a littlewater ;

prolonged twenty or thirtyminutes, and at the

should
separated

air,and

the

in

barium

of commercial

water

fatty acids remaining

The

and

to 50

densityof

7^"
receptaclefor subsequentneutralisation
milk of lime, and, after the separationof sludge,
is ready for concentration.

Tw.

67)

FATS.

proceeded sufficiently
far,the boiling
is

allowed

with
of the fattyacids by contact
the vat settle.
The settled glycerine
water, which
of the

AND

oils and

fats,

very marked
and rape oils,
tallow
a

being broken

to the extent of
up into fattyacid and glycerol
8 2-96'per cent, after boiling
100 grams of the oil or fat with 100 c.c.
some
of acid for twenty-four hours.
of hydrolysis
The maximum
amount
was

attained
of the

in

with

cocoa-nut

oil,probably owing

of volatile
glyeerides

fattyacids.

to

Castor

its largeproportion
oil is abnormal

only undergoing about

to the

formation

but this is attri20 per cent, hydrolysis,

buted
different constitution
of its fattyacids,and the ready

of

also made
polymerisation
products. Experiments were
the addition of other catalytic
to whether
as
agents aided the action
the
of
hydrochloricacid ; mercury, copper sulphate,mercury oxide,
and aniline being
zinc, zinc dust, aluminium
chloride,nitrobenzene
made
The
tried,in the proportionof 1 per cent.
experiments were
lard
free
and
of
lard
neutral
cent,
5
on
fattyacids,
containing per
but in no case
e
ffect
was
produced.
any appreciable
So far this process has not been adopted on the practical
scale,
for
its chief drawback
the
of
time
required saponification.
being
length
Undoubtedly the hydrolysiswould be greatlyfacilitated if the oil
and acid could be made
to form a satisfactory
emulsion, but although
this
of attaining
saponin has been tried for the purpose, no means
objecthas yet been devised.
SulphurousAcid or Bisulphite. The use of these substances has
been patentedby Stein,Berge and De Eoubaix
(Germ. Pat. 61,329),
the fat beingheated in contact with the reagent for about nine hours
at 175"-180" C. under a pressure of some
18 atmospheres,but the process
does not appear to be of any considerable importance.
of oils and fats was
Lime.
The use of lime for the saponification
"

"

22

MANUFACTUBE.

SOAP

of candleadopted on the technical scale for the production

insoluble lime soap
The
making material, by De Milly in 1831.
acids steam
is decomposed by sulphuricacid,and the fatty
formed

first

distilled.
a
theoretically
necessary to hydrolyse given
catalytic
any
ignoringfor the moment
quantityof a triglyceride,
reaction
the
stearin
with
thus
calculated
be readily
;
influence,can
be represented
by the equation:
may

of lime

amount

The

"

GELOH

CH2OOC1SH35
CHOOC1SH35

3Ca(OH)2

3Ca(OOC18H3B)2+

CH2OOC18H35
milk

stearin

calcium

of lime

this instance, since the molecular

that of milk of lime is 74, it is at once

In
and

1,780 partsof stearin,222 parts of milk of

CaO,

would

be

required.

stearate

2 CHOH

OH2OH
glycerol

weight of stearin is 890

apparent that for every
lime or 168 partsof quicklime,

It is found

in

however,
practice^

of lime
of 3-5 per cent, above the theoretical quantity
carried on in
of a fat when
is necessary to complete the hydrolysis
be conthe
if
that
saponification
an
open vessel at 100"-105" 0., but
to
of lime necessary
ducted under pressure in autoclaves the amount
is reduced to 2-3 per cent. 011 the
almost perfecthydrolysis
secure
a pressure
of fats with 3 per cent, of lime under
fat,the treatment
of 10 atmospheresproducing a yield of 95 per cent, of fattyacids

that

an

excess

the pressure in the

will be the colour of the resultant fattyacids.

in seven

lower

autoclave,the lighter

"

It has

been

"

for the purpose.

It has also been
lime in the autoclave
the

proposed to
to obviate

fattyacids.
catalytic
agents

Other

have

zinc oxide in

use

to

some

been

extent

j
i

j
]"
?

proposed to substitute magnesia for lime

under
in the process of saponification
pressure, but comparative experimentswith lime and magnesia,using 3 per cent, of lime and 2*7
Ind.,xii.,163), show that
per cent, of magnesia (Journ. Soc. Chem.
with
less complete than
of
is
magnesia
saponification
by means
the reaction requires
a
higher temperature and
lime, and, moreover,
therefore tends to darken the product.
of zinc oxide as accelerating
Zinc
The use
Oxide.
agent has
Poullain and Midland,
been suggestedby two or three observers.
for
this
in 1882, were
a
granted patent
process, the quantityof zinc
oxide recommended
to be added to the oil or fat being 0:2 to 0*5 per
cent.
Eost, in 1903, obtained a Erench patent for the saponification
of finely
under
of oils and fats by steam
pressure in the presence
zinc oxide
divided metals or metallic oxides,and specially
mentions
Magnesia.

The

hours.

"

the

recommended

conjunctionwith
discoloration

from

time

of

to

\
kt

CONSTITUTION

time,

but

""oda

by

potash

conaraerce.

uncier
acicls
most

present

of

by

of
the

complete

pressure,

glycerol

preceding

and

could

their

in

always

are

the

fatty
of

use

be

used

the

agents
use

from
is

the

fully

the

in

contained

matter

They

are,

described

of

soap

to

quantity
oil

an

or

fat,

quantities,

smaller

fatty

point

formed

soaps

sufficient

considerably
of

the

constitute
in

accomplished.

practical

importance.
bases,

acids

aluminium

baryta,

and

water,

resolution

saponifying

important
work,

soluble

caustic

practical

any

the

reagents

doubtless,

and

are

whole

the

with

th.cru.gh

is

Unlike

23

FATS.

AND

oxide,

"

These

combine

these

Potash.

and

soda

of

none

and

OILS

lead

strontianite,

including

hyciirate,

OF

fatty

into

by
view

of
in

far,

the

of

the

Chapter

Y.

III.

CHAPTEE

Fats"

Oils"Waste

and

Fats

Oils.

and

Fats

of

matter,

The

be

oils and

All

cent.

in

fats
it

acidity, though

of

does

and

material.

making

latter

it is

efficientlyperformed,
be

may

tinder

following

each

suitable

for

Tallows.
Australia

of

not

to

of very

market

the

garine-making.
secondary
The

and

fats

and

them

in

produces
as

demand

country

rendered

importance

following are

to

the

the

typical samples
24

chemist

give,

we

tallow

is
of

possessed

tallows

South

most

America,

makes

of

of

bright

as

are,

America,

the

tallow

but

Australasian

and

the

of

melter.

'

"

comes

melt.
the

product

tallow

of tallow

which

home

or

fat, much

melted

tallow

be

in demand.

tallow,

separately,

Consequently

is

but

of

much

edible

from
mutton

Most

large quantities
for

how

qualities

tallow

those

and

and

amount

should

used,

American

consistence.

tion,
oxida-

the

the

comes

beef

than

quality

and

town

of

American

North

colour

soap-

to

parcel.

strong odour,

texture.
in

in

the

to

materials

the

American

glyceride,

due

oils

submitted

tallow

South

rather

uniform-

Britain

imported

South

paler

with

increasing
carefully selected,
of

the

per

excess

observe

to

necessary

of the
of

2*0

being formed,

ketones

of

sample

average

Zealand.

good body

are

the

the

short

of

New

compare

Great
Into

Most

rule, much

tallows

scarcely

sampling

that

good quality ;
and
yellow colour

general
do

the

of

deep

soap

"

of the

entirely

description
heading, figures for typical samples
soap-making.

and

usually

is

fairlyrepresentative

the

In

It

so

acidity ;

rancidity by determining

estimate

that

oils is

and

aldehydes

produced.

important

very

to

to

but

undesirable

is

dition.
con-

cholesterol,

0*2

decomposition

and

fats

fresh

as

from

free

rancidity,
of

unsaponifiable
sweet,

fats

less

or

the

to

denote

free acid,

proposed

been

these

of

to

more

due

in

oils and

various

Rancidity

in addition

It has

may

and

Alkali

intended

fats

naturally present

matter

contain
be

Rosin"

from

possible

as

appearance,

the

always

not

free

as

of Limited

Fats

oils and

vegetable

and

and

unsaponifiable

phytosterol,ranges

or

animal

colour

good

All

"

should

soap-making

for

Water"

Carbonated)"

and

(Caustic

and

Oils

Suggested for Soap-making"

Soap-stock.
Salt"

Oils

and

Less-known

Acids"

Fatty

Fats

New

Use"Various

SOAP-MAKING.

IN

USED

MATERIALS

RAW

for

Owing

rough
sold

for

fat

is

mar-

soap-making

is

26

Cocoa-nut

Palm-nut
them.

oil should

The

Oil.
"

from the west

palm-treefruit are "exported

Europe,and this oil obtained from
Englishand Hamburg oils tested :

kernels

Typicalsamplesof

Olive Oil.
"

and in

absorb 8-9 to 9*3 per cent, iodine.

of the

coast of Africa to

Palm-nut

The

MANUFACTUBE.

SOAP

oil should absorb 10 to 13 per cent, iodine.

The

of
portions

"

olive is

extensively
grown

Asia and Africa

fruit of this tree

the
bordering

in Southern
Mediterranean

Europe
Sea.

yieldsthe oil.

The free fatty

acid content of olive oil varies very considerably.
oils
Very fine oils contain less than 1 per cent, acidity
; commercial
free
be
their
under
to
5 per cent.,
gradedaccording
acidity,
may
e.g.,
under 10 per cent.,etc.,and it entirely
depends upon the desired
The
priceof the resultant soap as to what gradewould be used.
is
of high-class,
sample for use in the production
following a typical
toilet soap

:
"

MATERIALS

RAW

USED

IN

27

SOAP-MAKING.

termed
correctly
Sulphur olive oil.
acids
is
fatty
The
always high and ranges from
40-70 per cent., and, of course, its glycerolcontent
is proportionately
The
free
increases very rapidly,
variable.
acidity
and is,doubtless,
due to the decomposition of the neutral
oil by the action of

oil,more
Olive-kernel
of free

amount

ferment.
hydrolytic

sample of
representative

oil is

Palm
the

along

producedfrom

west

coast

parceltested

the

fruit of

of Africa.

Lagos

H,

Palm

absorb

to 5G

have

we
qualities

the lower

In

oil should

"

palm trees,which

abound

is the

best quality,whilst
Calabar oils are in good

Bonny, Old Calabar and New

requestfor bleachingpurposes.
samples of crude palm
Analysisof typical
Cameroon

oil has

per cent,

given :

"

iodine.

lytic
examplesof the result of hydrofree acidity
often amounting to

the

by enzymes,
deconipoKition
70 per cent.

Gfitton-swl Oil.
from

the

wool

"

and

in America

"

Tliis oil is

of the various

expressed from

kinds

of cotton

the seeds

separated

tree

largelycultivated

fluid

aginous
containingmucil-

Egypt.

ID, its crude stale

eotkm-seed

oil is

dark

for soap-making.
colouringmatter, and is not applicable
of
following figures are, representative well-refined cotton-seed

and

The

oils:-"

Kp,rifH(Jravity
at 17't'.

S:i|ioiiitica- A.-idity
fion

(asOli'iu Acid) i
iNir " 'flit.

0".W2f.l
0-921

Cotton-"i!cd oil Khoulcl absorb

Titrc.

Kel'ractive
It)dux
at 20" C.

1-4721
1-4719

104 to 110 per cent, iodine.

28

MANUFACTURE.

SOAP

posit
product obtained by pressingthe derefined cotton-seed oil.
chilling

Stearine.
Cotton-seed

which separateson
A

The

"

sample tested:
typical

Arachis

earth-nut

The

Oil.
"

"

or

from
ground-nut,

which

arachis

cultivated in North America, India and

extensively
are
exportedto Marseilles where
Africa. Large quantities
Western
into the composition
the oil is expressed. Arachis oil enters largely
White
"of Marseilles
Soaps.
samples of commercial and refined oils tested :
[Representative
oil is obtained, is

"

oil should

Arachis

maize

"

very

iodine.

large quantitiesof

oil.

Typical samples of crude

Maize

Sesame
from

90 to 98 per cent,

(U.S.) produces

America

Oil.

Maize

absorb

the

Oil.
"

seeds

oil should

Sesame

of the

refined oil gave

and

absorb

:
figures
"

120 to 128 per cent, iodiue.

oil is very

sesame

largely
pressedin Southern France
plantwhich is cultivated .in the Levant,

India, Japan
Africa.
A
fairly
representativesample of French
and

these

Western

expressedoil tested

"

HAW

MATKBIALH

Sesame

oil should

VISKD

absorb

IN

29

SOAP-MAKING.

108 to 110

per cent,

iodine.

L-inse.cd0/7." Russia, India, and

Argentine Eepublic are
which
countries
the flax plant,from
extensively
grow
principal
linseed oil is

seeds of which
in

making.
soft-soap
A good sample gave

on

pressed.

It is used

to

the

limited extent

analysis:
"

Aridity

Specitie.

(as Ohn,-

Gruvitv

the

Refractive

Acid)

Index

Per (Vnt.

Equivalent.

at 15" C.

1-4840

i/ms"*ed oil should

HcMp-wad
which

grows

all is

170 to 1HO per cent, iodine.

the seeds of the hemp plant

This oil is tised in soft soap-making,more

producuuifrom

in Russia.

the
on
particularly

absorb

Continent.

typical
sample,gave

the

:
followingfigures
"

Titre,

Univity

Iodine

"0.

ut. i:""'"'.

143

nil is producedlargelyin Russia.

Sitnflouwr
A

specimen tested

:"

Uravitv

W-\\
."it

G'92,59

K"{uiv;ileiit.

21)0-7

No.

30

SOAP

MANUFACTURE.

a native of India,but
Castor Oil. The castor oil plantis really
and Egypt.
it is also cultivated in the United States (Illinois)
commercial
A typical
sample tested :
"

"

Fish
until
a

Animal

and Marine

entered
recently,

demand
We

has

now

few

quote a

Oils.
"

Various

into the
largely

oils of this class have,

of soft soaps, but
composition

arisen for soft soaps made from

analysesof these oils :
typical

vegetableoils.

"

Fats.
Under this classification
be included marrow
may
greases, bone fats,animal
grease, melted stuff from hotel
restaurant
refuse,and similar fattyproducts. The following

Waste

"

fat,skin
and

"

is

fair typical
selection

"

MATERIALS

RAW

USED

IK

31

SOAP-MAKING.

The materials in the above

of

lor the presence

class requireto be carefully

examined
purities.
unsaponiiiable
matter, lime salts and other im-

We
have alreadydescribed the various methods
of
Fatty Acids.
fattyacids by hydrolysisor saponiiication.
liberating
also ho included
this heading should
stearines produced
Under
by submitting distilled fat to hydraulicpressure, the distillates from
"

and

recovered fat of woollen

neutral oils

acid free from

from

acids, and

oloine

pure;: oleines or
commercial
oleic

or

oleino,a bye-product

cocoa-nut

of edible cocoa-nut

palm-nut

only

used, opines

are

matter,
unsaponiiiable

from the manufacture

of free

silk mills,where

olive oil soaps

or

butter and
obtained

in

consistinglargely
a

similar

manner

palm-nut oil.

These

are

all available

LKSS-KNOWN

OILS

//!/*.- Shea
8liC(/,./"'///

Basxiti Parkil

and

fat is somewhat

for

e.x

FATS

AND

butter

LIMITKD

OK

is extracted

ported from

the following data

from

Africa, and

tough and sticky,anil the

present is sometimes

matter

soap-making.

considerable.

USE.

the, kernels

Hastens

of the

India.

This

of

unsu.poniiiabie
Samples examined
by us

amount

/*"?

:\(Y,\

Mawrtih-wd

making

O/7.

is derived

-The, mowrah-seed
the

from

sends

oil

offered

now

for

of Ihtxxht- Inntiifolitt.
and

soap/"V-,v,s'/r/,

It is large*!}'
latifoliti.
exported from India, to .Belgium,France
England. The following are the. results of some
analyses made

Acidif.y
,

a.nd

by

""I"'i"'
Arid)
Pt-r (Vnt.

1-451H

"f 1
Chinase
ad
found

MtjetiMc-tallow
coatingthe seeds of

in the
the

"

name

given

tallow tree"

to

the fat which

is

(^HUunjht selrifcra)

32

MANUFACTURE.

SOAP

which

is

to
indigenous

it nourishes.

The

and has been introduced to India where

China

is a typical
following
sample:

The

tree"

seeds of the "tallow

yieldan

"

oil (stillingia
oil)having

dryingproperties.
of several speciesof Hopea (or
which flourish in the Malayan Archipelago,
Dipterocarpus),
yielda
This fat is moulded (by means
fat known
as Tangawang fat.
locally
Borneo

Tallow.

"

The

kernels

canes)into the form of rolls about 3 inches thick,and

to Europe as Borneo Tallow.
data :
sample tested by one of us gave the following

of bamboo
A

ported
ex-

"

Kapok

oil is

the East and

from
produced

West

Indies.

The

tree which

Dutch

have

is

extensively
grown in
placedit on the market

figuresgiven by Henriques (Chem. *Zeit.,17, 1283) and

Philippe(Monit. Scient.,1902, 730),althoughvarying somewhat,
and

the

show

the oil to be similarto cotton-seed oil.

VABIOUS

NEW

Garapaor

FATS

Andiroba

AND

OILS

SUGGESTED

FOB

SOAP-MAKING.

oil,derived from the seeds of a tree (Garapa

Indies and tropical
America,has been

in West

Guianensis)
grown
Institute
suggestedas suitable for soap-making. Deering(Imperial
the
Journ.,1898, 313) gives
following
figures:
"

34
Africa.

Its

has

use

been

followingfigureshave

Mar
in

MANUFACTURE.

SOAP

ip a fat is

been

obtained

suggested for soft-soapmaking.

published:

from

the kernels of

palm

the

from

The

"

West
Indies, but, doubtless,the commercial
other trees of the same
family. It resembles

tree

flourishing

fat is obtained
cocoa-nut

oil and

gives the followingfigures

:
"

Mam

fat,

obtained

from

the seeds of

Lophira alata,which are

prepared by nativo"
Has
been
examined
by Lewkowitsch, and more
recentlyEdie has
published the results of aa analysis.The
figuresare as follows
lound

extensively

in

the

Soudan.

The fat,as

"

"

Bulletin,1903,

p.
1

tU*e'are

25^!

Calculated by

us

from

reCOrded

saponifloationvalue.

in the

MATERIALS

HAW

USKD

IN

SOAP-MAKING.

Siiponilicji-

Molting Point

tion

Iodine

No.

of

Fatty Acids,

Equivalent.

'iireiniQiMafimt tallow from

which
are

wild in

grows

the nuts of the mafouroira

Portuguese East

Africa,.

The

tree,

followingfigures

:"
published

tion

Equivalent.

Tit,tv, 0.
"

i
;

44-4H

253-8

; Di- Notfriand

40-1.4

IWI'

as

"

Kabris, Annul,
"l'"

'

''

'""'

del l.ah.
P"

"*'

Aridity
Oifitt Acid)

1'

232-8-23:* 7

Pout/am oil,obtained from the beans of tins pongam

trt*e,which
flourish(3Sin .Mast India,has been suggested as available for the soap
but the unsaponifiable
matter
industry,
present would militate against
Lewkowitseh
its use.
(An"tlt/xt,
1903, pp. "'M"2-:14)
sults
quotes these re:"

Sajjouilica|

...

"
.

UnsuiHHjiii-

Oil oxtracttid in lab

Indian specimen
.

Man/am
which

oil is ol)tairied from

is found

the Heeds of Mafia

ascdamr-h

tree

in most

Lewkowitseh

parts of India and

(Analyst 1903,
,

Burma.

pj". ^4^-344)

gives these* figures:

2H4-9

Calculated

by

UH

from

naponifixation

value.

"

"i

36

MANUFACTURE.

SOAP

Dikafat

of

kinds

various

1905,

p.
of

seeds
data

395)

examined

Irvingia

Nigeria) and

(South

bateri

Lemarie
is used

the

place
(Analyst,

obtained

gives

of

(Bulletin
in

fat

large sample of dika

kernels

Lewkowitsch

of soap.

manufacture

oil in the

of cocoa-nut

fat

this

that

states

Inst., 1903, p. 206)

Imp.

seed

the

Mango oil is obtained from

Irvingia by boiling with water.

Wild

or

the

from

following

:"

Unsaponifiable,
Per

Cent.

0"73

34-8

Ghem., 1904, p. 529,

(Journ. Pharm.
that
the
Soc. Ghem.
in Journ.
Ind., 1905, p. 34) states
abstracted
of boilingwater, from
the
of Madagascar extract, by means
natives
Oil.

Baobab-seed

baobab

of the

seeds

possessed of
with

it may,

an

tree,

whitish

similar

odour

Oil.

yellow colour, and

The
followingare

Wheat
been

having

he
taste

taken

from

oil,extracted

from

suggested as

J. S. C. Ind., 1905, p.

describes
and

Lane's

the

applicablefor
1074).

The

as

"

of solvents,
by means
soap-making (H. Snyder, abstr.followingfigureshave been published
germ

"

Calculated

by

us

from

manufacture.

semi-drying,of brownish
oil.
like pea-nut (arachis)

suggests that

Ind., 1905, p. 390) gives

G.

figures:

wheat

He

oil in soap

odour

rancidity,and

from

olive oil.

Tunisian

(J. S.

Lane

"

for this oil which

constants

to

solid oil,free

advantage, replace cocoa-nut

Persimmon-seed

has

Balland

"

saponificationvalue.

MATERIALS

HAW

USED

fat, from the socds

islands,is suitable
iKiighbourinjj;
ldh

the

IN

of

a,

for

tree

in ,Tava and

growing

soap-making.

abstnictod
n;io-("l(),
(Arch. l*karm., i(J()5,

128) gives thc-He vahms

37

SOAP-MAKING.

in ,/. ,S'.('.

Schroeder

Jnd., 1.906,p.

Iodine N"".
I*"r dent.

It is

odour

and

at about
solidifying

acteristic
char-

nor

27" (.).

West
Africa
""l""usafrom
l*n"ja
yieldon extraction
the
is suggested as
and
figuresquoted below,
gives

of

which

The

1906, p. 201).
Imp. ///,.s-/.,
""j ln.tri/-kt'r"if'.L~(/!ullt"tin

Oil
seeds

fat,nearly white, possessing neither taste

hard

maker's

material

an
a

oil

soap-

Saputiitiru

Inilint

tion

No.

Hi) "?5

BOSIN.

Kosin

is the

residuum

remaining

from the crude oleo-resin exuded

turpentine
1

Calculated

by

as

from

spiritsof
speciesof the

after distillation of

by

several

value.
saponification

MANUFACTURE.

SOAP

38

pine,which

America,

in

abound

Carolina,and

in North
particularly

forests of the United

gigantic

Spain. The
pine, Pmuspalmtru
of the long-leaved
States consist principally
and
Spanish oleo-resm is chiefly
whilst the French
(AustraUs),
cultivated.
which is largely
obtained from Pinus pinaster,
substance
having a
is a brittle,tasteless,transparent
Eosin
C. (275 F.)- 1J^e
135
smooth shiningfracture and meltingat about
and

also flourish in Prance

aromatic odour, which is

varietypossesses a characteristic
It is graded by samples
lackingin those from France and Spain.
American
taken

out of the

which

must

be

and cut into f of an inch cubes,

every barrel,
in size" the shade of colour of the cube
uniform

top of

determines its gradeand value.

The

II

gradesare

W.

W.

W.

G.

follows

as

"

(Water white.)
(Window glass.)

(Extrapale.)
(Pale.)
(Low pale.)
(Good No. 1.)
(No. 1.)
(Low No. 1.)
(Good No. 2.)
(No. 2.)

N.

M.
K
I.
H.
G.
F.
E.

(Good strain.)
(Strain.)
(Common strain.)
(Common.)

D.
C.
B.
A.

matter is present in rosin in varyingamounts.

Unsaponifiable
Below
few typicalfigurestaken from
are
a large number
a

collated determinations

ALKALI

The manufacture
with
for the

(CAUSTIC

of alkali was

soap-making, but

soap

alkali from

manufacturer

AND

CARBONATED).

at one

time carried

of late years it has become

to buy his caustic soda

in

on

more
or

conjunction
general

carbonated

the

alkali-maker.
there
are
Although
alkali-makers who
some

and

of

"

soda ash in terms

of actual

invoice caustic soda

oxide (Na2O),

percentageof sodium

MATERIALS

HAW

trade custom

it is the

English

weight of sodium
1 per

IN

and

39

SOAP-MAKING.

sell

what

is known

the
as
than
this.
higher
per
degree is a survival of the time when the atomic
believed to bo twenty-four
was
instead of .twenty-

three,and, since the

to about

buy

to

English degree,which
The

USED

is about

on

cent,

76 per cent.
be obtained
by

on

error

cent., may

Na20 due

to this amounts

adding this figureto the

oxide

sodium
reallypresent.
into commerce
Caustic soda (sodium hydrate)cornea
in a liquid
106"
90"
Tw.
and
ae
(and even
form as
other degrees
high as
Tw.),
of dilution,and also in a solid form in various gradesas 60",70",76-77,"

77-78". These degrees represent the percentage of sodium oxide

(Na20)present plus the 1 per cent. The highestgrade,containing
as
more

it does

available caustic soda and

more

advantageousin

less

is
impurities,

much

use.

Carbonate of soda or soda ash, 58",also termed

lightash,1*and
This is a commerciallypure sodium
"refined alkali".
carbonate
"

0*5 per cent, salt (NaOl). The 58" represents the

Englishdegrees and correspondsto 99 per cent, sodium carbonate

containingabout
"

(Na.,C03).
Soda

ash) 48",sometimes

called "caustic

soda

ash," often concaustic soda (sodium

tains besides carbonate of soda, 4 per cent,

and 10 per cent, salt (sodium chloride),
togetherwith water
hydrate),
and impurities.
of alkali present in terms of
The 48 degreesrefers to the amount
sodium

as Englishdegrees.
(Na^O),but expressed
potash (potassium hydrate)is offered as

oxide

Caustic

50-52" B.

strength,and

(98-103" Tw.)
88-92".

75-80" and

percentageof

also

in

solid

liquidof
form

The

degrees in the latter case refer

potassium hydrate(KHO) actually
present.
of Potash."

to

as

the

standard

of
for refined carbonate
potashis 90-92 per cent, of actual potassiumcarbonate (K2COS)present,
althoughit can be obtained testing95-98 per cent.

Carbofiate

The

MATBBIALS.

OTHEE
r."
as

intended for

Water

possible.If the
; the

soap-making should be as soft

chemisupply is hard,it should be treated cally

water

use

softeningagents may

ash alone,or caustic soda.

for water softening,
which
vary in mechanical
of
softening

hard

soda
together,

many excellent plantsin vogue

based on similar principles
and merely
are

advantagesaccruingfrom the
intended for steam-raising
are
sufficiently

arrangement.
water

be lime and soda ash

There
are

in

The

established and need not be detailed here.

Salt (sodium chloride or common
salt,NaOl) is

very

tant
impor-

soap-maker,and is obtainable in a very pure state.

in soapsaturated
solution of salt,is very convenient
Brine,or a
making, and, if the salt used is pure, will contain 26*4 per cent,
material to the

sodium

chloride and

have

densityof 41*6" Tw. (24*8"B.).

The

of

presence
chloride

sodium

salt

this

it

where

obtained

is

higher

salt

is

free

the

nigre

settled

Soapstock

course

the

the

spent

of

density

the
Tw.

(25"

is

largely

from

glycerine
the

brine

made

imported

from

by

treatment

boiling

the
is

treatment

of

excess

out

is

from
sold

with

the

the
of

America,

when

the

crude

with

is

mucilage,

Mucilage
and

times

converted

consists

resinous

oil.

water

several
it

termed

oil.

colouring

mucilage

repeated

colour,

residue,

cotton-seed

crude

together

soap,

during

this

of

from

B.).

dark-coloured

the

refining

oil

removed

from

from

produced

separated

with

substance

This

from

is

of

"

cotton-seed

matter

and

42"

than

of

recovery

sulphates,

ranges

Soapstook.

the

during

contains

often

lyes

and

density,

the

alters

sulphates

content.

produced

Salt

of

MANUFACTURE.

SOAP

40

The

and

ciples
princolouring

into

the

product

soap

it.
on

fatty

acid

basis

the

colour

well

graining

until

is

variable.

and

42

SOAP

further

heating)with

hot water

(which may

If
matter

contain

salt),to

remove

of chrome

liquor.
the above, operationis carried
will be completelyoxidised.

the last traces

if

MANUFACTURE.

out

the colouring
carefully,

important, however, that the temperature should not be

130" F. (54"C.) duringthe bleachingof palm
oil on saponification
is apt to yielda soap
the
resultant
otherwise
oil,
It is

allowed

of

to rise above

"foxy"

violet odour
It has
of this and
process.
Crude

colour.

bleached

The

oil.
original
suggestedto use

oil retains

the

characteristic

of the
been

dilute

sulphuricacid,or

salt,in the place of muriatic

common

Oil.

acid

mixture

in the

"

above

The

of crude
deep colouringmatter
mucilaginousand resinous principles,
with caustic soda lye.
removed
are
by refining
without
these impurities
The chief aim of the refiner is to remove
neutral
oil.
The
of
the
free
of
fattyacids
saponifying
percentage
any
the quantityof caustic lyerequired,
which
in the oil will determine
this acidity.
must
only be sufficient to remove
of free acidity,
the quantity
Having determined the amount
of caustic soda lye necessary
to neutralise it is diluted with
wa'ter
carried
to 12" or 15" Tw.
(8" or 10" B.), and the refining
process
out in three stages. The oil is placedin a suitable tank and heated
coil to 100" F. (38? C.),a third of the
of a close'd steam
by means
soda
weak
caustic
lye added in a fine stream or b,ymeans
necessary
of a
whole
well agitatedwith
and
the
mechanical
a
sprinkler,
of
the
air
laid
current
or
a
on
a
agitator by blowing
through pipe
Cotton-seed

cotton-seed

bottom

"

with the
oil,together

of the

tank.

with air has a tendency to oxidise the oil,

Prolonged agitation
which increases its specific
gravityand refractive index, and will be
found in the soap-pan
As the treatment
to produce a reddish soap.
of the
raised, by means
proceeds,the temperature may be carefully
steam
coil,to 120" F. (49"C.).'
The first treatment
havingproceededfifteen minutes, the contents
of the tank are allowed to rest ; the settling
should be prolonged as
much
to
allow
the impurities
to preas
possible,say overnight,
cipitate
and
least
down
the
of
amount
well,
entangled oil.
carry
these coloured
foots,"the second portionof
Having withdrawn
the weak caustic soda solution is agitated
with the partially
refined
the latter is sufficiently
oil,and, when
treated,it is allowed to rest
and the settled coloured liquordrawn
off as before.
The oil is now
is performed in the same
ready for the final treatment, which
the two
On
clear yellow
manner
as
a
previous ones.
settling,
"

oil

separates.
If desired,the oil may

produce a marketable
the soap-house,
this
The

residue

or

be

after refining
to
brightenedand filtered,
if it is beingrefined for own
in
use

article,but

be omitted.
may
"foots"
produced

during the refiningof crude

"

J.

BLEACHING

AND

into

"

soapstock

OF

in the trade

cotton-seedoil,known
"

TREATMENT

mentioned

as

"

as

in the

by a mineral acid and made

by superheatedsteam.

into

"

RAW

MATERIALS.

mucilage,"may be converted
posed
precedingchapter,or decomblack grease
tillation
ready for dis"

Oils."
Vegetable
hand in

The other vegetableoils come

to the soap-maker's
refined condition ; occasionally,
however, it is desirable to

also causes
portionof the free fattyacids, which treatment
be
matter
Thin
is
to
effected
the colouring
precipitated.
by bringing
solution of caustic lye into intimate contact.
the oil and a weak
Sometimes
it is only
Cocoa-nut oil is often treated in thin manner.
the oil with If per cent, of its "weight
of a
necessary to well agitate
12" Tw. (8"B.) solution of caustic soda and allow to settle. The
a

remove

foots

utilised in the soap-pan.

often
Pats." Tallows
are

are

Animal

greatlyimprovedby the above

(78"C.). It is one of the best methods

at 165" F.

alkaline treatment

acid processes" the caustic soda removes

possesses advantages over
the free acid and bodies of aldehyde
nature, which are most probably

and

the result of oxidation or polymerisation,

whereas
the neutral
the alkaline foots can be used in the
attacked,and further,

fat is not

of
production

by
'

soap.

contains calcium
substances in a soap-pan.

fat

Bone

often

with

treatment

(lime)salts,which are very

These impuritiesmust
be

hydrochloric

or

sulphuricacid.

jectionable
obmoved
re-

The

former acid is preferable,

is readily
as the lime salt formed
soluble and
fat
r
emoved.
The
is
with
solution of acid in
a weak
agitated
easily
a lead-lined tank
by blowing in steam, and when the treatment Is

completeand the
well washed
Rosin."

liquorwithdrawn, the last traces of acid are

fat with hot water.
liquid
methods have been suggested
for bleaching
rosin ;

waste

of the

out

Several

r-

instances the constitution of the rosin is altered,

and in others
some
the
the cost is too great or
process impracticable.
The aim of these processes must necessarily
be the elimination of
in

the

without

matter
colouring

of the
alteringthe original
properties
the
rosin
into
a reby converting

This is best carried out

substance.

sinate of soda

with

solution of either caustic soda

or carbonated alkali. The
by heating37 cwt. of
process is commenced
17" Tw, (11"B.) caustic soda lye,
and adding 20 cwt. of rosin,broken
into pieces,
and continuingthe boiling
until all the resinate is homogeneous,
when an addition of 1J cwt. of salt is made and the boiling

by boilingit

prolongeda little. On
of the
a

skimmer
a

the coloured liquor

rises to the
resting,

resinate,and may

pipe)and

be

face
sur-

siphonedoff (orpumped

the resinate further washed

away through
with water ing
contain-

littlesalt

The

with

alkali is performedin a similar

of
solution,consisting 2i cwt. of soda ash (58"),in
about four times its weight of water, is heated and 20 cwt. of rosin,
broken into small pieces,added.
The whole is heated by means
manner.

of the

treatment

carbonated

open

steam

coil,and

care

must

be taken

to avoid

boiling

if

of

number

large

of

and

and,

vessels,

the

into

pumped
where

will

it

cwt.,

in

sprinkled

added

by

and

refining

allowed

practical
fats
to

and

through
The

matter.

suspended

be

have

molten

passed
matter.

product

un-

be

to

it,

intermix

to

would

the

the

liquor

and,

1J

be

of

When

resinate,

rosin

or

whole

has
the

containing

after

removal,

processes
after

settle,
a

trap

settled

through

intended

melted

and

the

by

may

sieves

materials

sufficiently

the

saponifi

bleaching,
but

cation,

employed.

the

aid

condensed

arrangement

fatty

for

successfully

are

being

for

suggested

been

materials

of

thoroughly

withdrawn

should

oils

open

sufficient

be

washing.

methods

treatment

above

to

rest,

to

the

over

pan

in

addition

the

boiling.

the

allowed

float

another

other

Many

and

will

matter

replaced

All

boiled

prior

of

the

to

given,

example

the

in

finish

the

in

thoroughly.

solution

the

to

towards

sufficiently

colouring

which,

will

intended

is

it

saponified

finally

required,

be

may

which

with

portion

worked

easily

resultant

the

boiling

collected.

be

there

allow

to

soap

be

salt

The

the

remaining

rosin

combined

been

using

can

of

saponify

resinate

to

be

proportions,

above

the

or

only

(or

others

the

escape

method

the

obviate

ash

water

returns

to

gas
the

precaution

due

With

which

trap

carbonic-acid

the

allows

dissolving

to

with

connected

boiler

in

preparation

the

to

soda

and

rosin

the

mixing

prior

ash)

soda

the

devised

methods

many

suggest

Some

over.

and

soda,

of

resinate

for

place.

takes

frothing

gas,

granted

been

have

patents

C02

of

liberation

the

to

Owing

over.

be

MANUFACTURE.

SOAP

44

of

steam

and

water

for

en

route

fine

to

to

free

impurities
the

collecting
the

be

must

fatty

soap-pan

them

from

CHAPTER

Y.

SOAP-MAKING.
Combination

Classificationof Soaps" Direct

of Fatty

Alkali"Cold

with

Acids

Diminished
/Y"w"rd~"S'o/"
Marbled-"
and
Mcirine
Palling or
Soap
Soap"HydratBd Soaps, Smooth
Saponificatiwi"Graining Out" Boilingon Strenfltlt"
Fitting"Curd Soap*-"
Yellow Mow**Mottled"
and
Blm
Curd
Grey Mottled Soaps" Milling nose"
hold Soaps" Resting of Pans
Utilisation of Nigrtx"
and
Settlingof Soap
Transparent Soaps"Saponifying Mineral Oil Electrical JtyoductitMofSoap.
under
tioaps"Saponiflcation

Process

Itwreas"d

or

"

"

"

generallydivided into two classes and designated hard1*

"and "soft," the former being the soda salts,and the latter potash
salts,of the fattyacids contained in the material used.
According to their methods of manufacture, soaps may, howeverr
thus :
be more
convenientlyclassified,
(A) Direct combination of fattyacids with alkali.
of alkali and
of fat with definite amount
no
(B) Treatment
separationof waste lye.
"

SOAPS

are

"

(C)

Treatment

of fat with

of alkali and

indefinite amount

no

separationof waste

lye.
of fat with
of alkali and
indefinite amount
(D) Treatment
separationof waste lye.
(A) Direct Combination ofFatty Acids with AlkalL---rEhmmeihod
consists in the complete saturation
of fatty acids with
alkali,and
in chapter
permitsof the use of the deglycerisedproductsmentioned
section 2, and
ii.,

Fatty acids

are

of carbonated

alkalies

soda

caustic

or

readilysaponifiedwith caustic soda

potash*

or

caustic

or

potash

of all strengths.
The
formed
with

by
saponification
in

means

of carbonated

an
containing
open
removable
agitator.

vat

steam

alkali may

coil,or

in

pan

be

per-

provided

ash

soda

(58"),
amounting to 19 per cent, of
and dissolve it in water
saponified,
by
the aid of steam
until the densityof the solution is 53" Tw. (80" B.) ;
then bring to the boil,and, whilst boiling,
add the molten fattyacids
It is usual

the

weight of

slowly,but

to

take

fattyacids to be

not

Combination

continuously.
takes place immediatelywith

acid gas, which

causes
to
boil
over.
frequently
the flow
over.

of

the
The

contents
use

of the vat

of the

fattyacids,will sometimes

It is imperativethat the steam

45

evolution
or

pan

or
agitator,

tend

to

should not

of carbonic

to

swell,and

the cessation of

prevent the boiling

be checked

but boil-

MANUFACTUEE.

SOAP

46

ing continued

all the alkali has

until
as
possible
vigorously

as

been

absorbed and the gas driven off.

the carbonic acid gas
replacesteam in expelling
(Fr.Pat. 333, 974, 1903).
has been patented
with a
of procedure,
however, is to commence
A better method
half the requisite
from
solution of 64" Tw. (35"B.) density,made
has all been
of
alkali
this
amount
when
a
nd
soda ash (9Jper cent.),
added
been
have
acids
graduallyand
(which
taken
up by the fatty
ash is added
soda
of
the remaining quantity
with continuous boiling),
of fatty
each further addition
in a dry state, being sprinkledover
The

of air to

use

acid.
This allows the process to be
is avoided.

over

easilycontrolled

more

should

boilingby steam

It is essential that the

and

boiling

be well maintained

throughoutthe process until all carbonic acid gas has been thoroughly
that pointis reached,the steam
may be lessened and
expelled
; when
"
of the vat or pan gentlyboiled "on
strength with a
the contents
lye until

little caustic

being finished

in the

it

to

ceases

caustic

absorb

described under

manner

alkali, the

soap

(D).

extremelydifficult to prevent discoloration of fatty acids,

do not
in this way
compare
productsof saponification
neutral
the
those
from
with
in appearance
original
produced
favourably
It is

the

hence

oil

fat.

or

^Separation
of Waste

and

of Alkali

DefiniteAmount

no

Lye. Cold -process soap is a type of this class,

of productionis based upon the characteristic proits method
perty
which
the glycerides
of the- lower fattyacids (members of the

and

cocoa-nut

completethe
Sometimes
are

"

-oilclass)
possess

solution

soda

oil

with

of Fat

Treatment

combiningwith a strong
readily
a
temperature,and evolvingsufficient
saponification.
tallow,lard,cotton-seed oil,palm oil and even

used in admixture

soap is the

of

low

at

when

with

cocoa-nut

oil.

The

process

caustic
heat

to

castor

for such.

oil is

employed alone, with the

slightalteration in temperature necessary to render the fats liquid,
of caustic lye requiredwill be less.
and the amount
Soaps made of
these blends closely
in
In.
resemble, appearance, milled toilet soaps.
the glycerides
such mixtures
of the lower fattyacids commence
the
and by means
of the heat generated induce the otner
saponification,
w
hich
alone
would
materials,
the
or only with
saponifywith difficulty
follow
of heat,to
suit.
application
It is necessary
to use
high grade materials ; the oils and fats
should be free from excess
of acidity,
to which
of the defects of
many
be
traced.
with which,
cold-process
soaps may
Owing to the rapidity
free acidity
is neutralised by caustic soda, granulesof
soap are formed,
which

same

as

cocoa-nut

in the

presence of strong caustic lye are "grained out" and

without increasing
the heat ; the soap will thus
tend to become
thick and gritty
and sometimes
discoloured.
difficult to
The

remove

caustic

lye

should

be

made

from

the

purest caustic

soda,

47

SOAP-BAKING.

ing
containingas littlecarbonate as possible; the water used for dissolvcalcium
the caustic soda should be soft (i.e.,
free from
or
diluting
and magnesium salts),
and all the materials carefully
freed from particles
of dirt and fibre by straining.
The
should

be

low

as

as

must

(24"C.),but in mixtures containingtallow 100"

120" P. (38" to 49" C.).
carried out as follows :
The process is generally

alone
to

the season,
vary with
oil
and for cocoa-nut
fluidity,

of course,
with
is consistent

temperature,which,
be 75" F.

may

"

The

fluid cocoa-nut

oil is stirred in

suitable vessel with

half its

temperature,
weight of 71*4" Tw. (38"B.) caustic soda lye at the same
allowed
the
and
to rest.
when
is
covered
and,
thoroughlymixed,
pan
caustic lye should be
It is imperativethat the oils and fats and
intimatelyincorporatedor emulsified. The agitatingmay be done
constructed for
mechanically,there being several machines
specially
the purpose.
In one
of the latest designsthe caustic lye is delivered
the whole
with the stirring
which
rotates
through a pipe
gear, and
of a motor.
is driven by means
The agitation
beingcomplete,chemical action takes placewith the
of the fats.
results in the saponification
generationof heat, and finally
of the pan are
At first the contents
thin,but in a few hours they
the edges of the soap
solid
the
advances
become
As
a
mass.
process
become

to the whole

and

when

transparent,and

more

the

mass,

soap

is

the

transparency

extended

has

ready,after perfuming,to

be framed

crutched.
The

admixture

of

greatlyimproves
and

smoother
The

the

little caustic

potash

with

of the resultant

appearance

the

caustic

soda

product, which

is

milder.

glycerineliberated during

the

is retained
saponification

in

the soap.

produce neutral soaps of

method, cold-process
by
soaps
and
and
alkali
both
free
liable
contain
to
fat,
unsaponified
are
very
into disrepute.
fallen considerably
have now
Diminished
Pressure.
under
Increased
or
Soaps
Saponification
made
by boilingfats and oils,under pressure and in vacuo, with the
for complete combination,
exact quantityof caustic soda necessary
attempts which have
belongalso to this class. Amongst the many
of soap-making
been made
to shorten the process
at various times
be mentioned
Haywood's Patent No. 759, 1901, and Jourdaii's
may
Although it
good appearance

is

with
possible,

and

firm

care,

touch

to

this

"

French

In the
vacuum

in

the

No.

Patent

339,154, 1903.

is carried
former, saponification

chamber
other

providedwith

process

an

fat is allowed

elaborate

out

in

steam-

jacketed

of stirrers ;
into the
stream

arrangement

to fall in

thin

previouslyplaced in
lye requiredfor saponification,
vessel,which is providedwith stirring
gear.
saponification
is
admitted
been
steam
the quantities
added,
have
When
proceeds.
saponification
amount

of

the

and

SOAP

48

MANTJEACTUBE.

Amount
of Alkali and no
Indefinite
of this class.
is representative
Separation of Waste Lye." Soft soap
maize) are
olive, cotton-seed
vegetable fluid oils (linseed,
The
this
soap, though occasionally
used in making
the most

(C) Treatment

with

of Fat

part

for

fats and tallow

bone

are

employed.

ranging,according
proportion

to

the

Eosin

added, the

is sometimes

from
required,

grade of soap

15 per cent, of the fattymatter.

of Holland
stipulate
Soft Soap Manufacturers' Convention
The
contain
must
not
more
that the materials used in soft-soapmaking
that a patent
to note
5 per cent, rosin ; it is also interesting
than
of soft
manufacture
1900) for the
has been granted(Eng. Pat. 17,278,
50 per cent, rosin.
soap from material containing
largelyused as
Fish or marine animal oils" whale, seal,etc.,once
by vegetableoils.
material for soft soap, have been superseded
raw
be varied accordingto the season;
materials must
The
by
body with a less tendency to separate is
hot weather, more
materials
these
richer
stearine
in
;
the introduction of oils and fats
to

^during
given^

induce

also

The

"figging".
however,
importantmaterial,

should average

which
used

most

to

40" Tw.

is

the caustic

(24"B.),i.e.,if

weak

a
strongerlye must
saponification,

commence

potash lye
solution

is

be afterwards

employed to avoid excess of water in the soap, and these average 40"
Tw.
(24"B.). The potash lye must contain carbonates, which help
If the lye is somewhat
to the resultant soap.
to

givetransparency

be added in the form

deficient in carbonates, they may
of refined pearlash (potassiumcarbonate).

of

solution

admixed, to the extent of onelye is sometimes

the
soap firmer during hot weather,
fourth,with potash lye to keep
of soda givessoft soap
but it requires
great care, as a slightexcess
and a tendency to separate.
a bad
appearance
commenced
is
The
by running fatty matter and weak
process
potash lyesinto the pan or copper, and boilingtogether,whilst the
introduction
of oil and potash lye is continued.
when
emulsion forms, and the
The saponification
an
commences
thickening.
quicklyto prevent the mass
lye is then run in more
for
sufficient
added
"strength"
complete saponification,
Having
clear.
the boiling
is continued until the soap becomes
the
is
The
condition of
judged by observingthe behaviour
soap
the pan and dropped on glassor iron.
of a small sample taken from
it will set firm, have
If the soap is satisfactory
a short
texture and
and
be
clear
held
the light.
when
towards
slightly
quite
opaque edge,
If the cooled sample draws
out in threads,there is an
of water
excess
present. If an opaque edge appears and vanishes,the soap requires
more
lye. If the sample is turbid and somewhat
white, the soap is
Caustic

too

alkaline and

TKe
soap

soda

and

needs

more

liberated
glycerine
no

doubt

Hydrated

plays a

soaps,

both

oil.
is contained in the
during saponification
part in the productionof transparency.
smooth

and

marbled,

are

included

in this

50

MANUFACTURE.

SOAP

the
tion ; the presence of soap will often assist this by emulsifying
fat and thus bringingit into intimate contact with the caustic soda
solution.
the action has started,caustic soda lye of a greaterdensity,
When
ing,
added,with continued boil29" to 33" Tw. (18"to 20" B.),is frequently
which
it
is
as
absorbed,
is
in small quantities
being
as
long

ascertained

by takingout samples from

time

to

time

and

examining

them.

should be

There

no

sample,but when pressed

dry.
faint caustic taste on
applyingthe
when
it
is ready for
permanent,

in
greasiness

the

be firm and

fingerand thumb it must

Boilingis continued until the
cooled sample to the tongue is
consists of the soda salts of
now
grainingout ". The pasty mass
emulsified diglycerides
the fat (as imperfect
soap, probablycontaining
with
in
which is dissolved the
.and monoglycerides)
water,
together
the
union
of
liberated
radicle from
formed by the
glyceryl
glycerine
the fat with the hydroxyl radicle of the caustic soda, and any slight
The
of caustic soda and carbonates.
excess
object of the next
is to separatethis water
(spentlye)from the soap.
operation
(b) Graining Out or Separation."This is brought about by the
of common
salt,in a dry form or in solution an brine, or by
use
the salt is spread
caustic soda lye. Whilst the soap is boiling,
uniformlyover its surface,or brine 40" Tw. (24"B.) is run in,and
be thoroughlyboiled
the whole well boiled together. The soap must
and care taken that too largea quantityis
after each addition of salt,
between

"Y

41

not

added at

once.

As the soap is

thrown
gradually

transparentappearance,
When

out of

and becomes

opaque

sample,taken out on a wooden

of
which
grains soap and a liquidportion,
a

salt

brine

or

spent lye allowed

as

more

or

has
to

been

added

it losen itssmooth
solution,

and

will

cient
easilyseparate,suffiis stopped and the
the boiling

settle out, whilst the soap

less thick

granular.

trowel,consists of distinct

remains

on

the

face
sur-

mass.

The

separatedspent lye consists of a solution of common

salt,
and alkaline salts ; the preparation
of crude glycerine
from
thereglycerine,
is considered in chapterix.
The
of water (spent
degreeof separation
lye)dependsupon the
of precipitant
used.
The
amount
aim
is to obtain a maximum
of spent lyeseparatedby the use of a minimum
amount
quantityof
salt.
The

amount

material

of salt

used.

requiredfor "grainingout"

varies with the

"

tallow soap is the most

more
easilygrained,
salt is requiredfor cotton-seed oil soap, whereas
made
from
soaps

raw

and

of salt
palm-kerneloils requirevery largeamounts
to
in
the
weak
brine
thoroughly.Owing
solubility
latter
of these
to grainthem with caustic soda
soaps, it is preferable
sufficientcaustic lye
lye. This is effected by adding,duringboiling,
20"
to
o
f
the
the
Tw.,
B.) produce
separation
granulesof soap.

cocoa-nut
to

grain out

"

51

SOAP-MAKING.

whole

The

is allowed

and

drawn

to rest ; the

be used

may
After the removal

with sufficient water

of the
to

separated half-spentlye is with-

for the

pastingof fresh materials.

settled lye,the grained mass

dissolve the

grainand

make

it smooth

is boiled
"

("close
strength".

and is now
it),
ready for the next operationof boilingon
portant
(c)Boilingon Strength or Clear Boiling. This is the most imoperationand is often termed
making the soap ". The obis
harden
to
and
the
to ensure
ject
complete saponification.
soap
Caustic soda lye(32|"Tw., 20" B.)is graduallyadded until the soap
is againopened or grained,and boilingcontinued
by the use of the,
the caustic soda lye is absorbed, another
as
dry steam coil. As soon
is
and
this is continued
until the caustic soda
portion
slowlyadded,
or
strength remains
permanent and the soapy mass, refusingto absorb more, is thrown out of solution and grained. The granularmass
will boil steadily,
and the boilingshould be prolonged, as the last
of
neutral
with alkali.
traces
difficult to completelysaturate
oil are
the
takes place gradually,and
Thorough saponification
operation
be
hurried
cannot
this operahas to be bestowed
care
; special
upon
tion to effect the complete combination
of fat and alkali.
After restingfor several hours, half-spent
lye settles to the bottom
of the pan.
In the case
of yellow soaps or millingbases the settled
in the
to a suitable receptacle
and reserved
for use
lye is removed
of
for
the
is
other
and
the
then
saponification
material,
ready
soap
final operationof
".
fitting
If
the
(d) Fitting.
operationsjust described have been properly
The
is
performed,the fittingshould present no difficulty.
soap
boiled with open steam, and water
added until the desired degree of
As the water is thoroughlyintermixed
closingis attained.
throughthe thick paste graduallybecomes
reduced
out the mass
to a smooth,
thin consistence.
Samples are tested from time to time as to their
behaviour
in dropping off a hot trowel held sideways; the thin layer
should
drop off in two or three flakes and leave the surface of the
trowel clean and dry. ,The soap is then in a condition to allow the
to gravitate.According to the required soap, the fit may
impurities
b'e "coarse/'("open") when
the flakes drop off the trowel readily,
fine
ojr
(" close ") when the flakes only leave the trowel with difficulty.
If the dilution with water has been allowed to proceed too far,and
would
be denoted
too fine a fit is produced,which
by the layerof
littlecaustic
brine
not
the
be very
trowel,
a
or
leaving
lye
may
soap
added
and the whole well boiled until the desired condition
carefully
"

"

"

"

"

"

"

"

"

"

is obtained.
A

good

contents

to

pressure of steam
swell as high as

of impurities
settling
; steam
the boil allowed
The
such

appliedto the pan, causing the

this greatlyfacilitating
the
possible,

is

now

is then

for several

turned

off,the pan

covered, and

days.
of the pan
in
consists in leaving the contents
fitting
and
condition that,on standing,
all the impuritiesprecipitate,
art of

to rest

52

SOAP

MANUFACTURE.

containingthe

the settled soap,

correct

of water, is clear and

amount

bright.
is

above

generalpracticaloutline of the ordinarysoap-boiling

be modified or slightly
It
a
ltered
to the
may
according
process.
the
it is
individual
of
material
the
soap-maker or
fancy
particular
Pats and oils not only vary in the amount
of alkali
desired to use.
but
they absorb during saponification, also differ in the strength of
and palm oil requirelye of a density
the alkali they require. Tallow
of 15" to 18" Tw. (10"to 12" B.),but cocoa-nut
oil alone would
not
unless
the
42"
was
33"
to
more
Tw. (20"to
lye
concentrated,
saponify
25" B.). Cotton-seed oil requires
weak
and,
lyes for saponification,
difficult
to
is genersaponifyalone even with prolongedboiling,
being
ally
The

fat.

with animal

mixed

fats

When

mixed

are

become

modified,and

lye,other

with weak

which

strengthwith

materials

the

with
saponification

weak

order

as

it is being added

to

take

to

the

commence

space, it is the

the soap -pan

by

alkali of

up

combine.

strong caustic lye (60"to 70" Tw., 33"

store
it

they would not

procedure to
lye.
tank

quirements
varying alkali reis begun
saponification

induced

best

economise

to

once

are

their

the

alone

It is considered

In

however,
together,

the

generalpracticeto
37" B.) and

to

pastingor

simultaneous

to dilute

addition

of water.

Many manufacturers

brine wash
to remove
giveall their soap a
the last traces
of glycerineand
free the soap
from
bonates.
carThis operation takes place prior to
sufficient
fitting;
brine is
it and then
water is aqlded to the boiling
soap to "close"
in
it.
to
run
grain
the liquoris withdrawn.
After resting,
described
the necessary operationsin general,
will now
we
Having
to the preparationof various kinds of hard
consider their application
"

"

"

"

"

soap.
Curd
curd

Soaps.
"

Tallow

is

largelyused

in the manufacture

of white

oil sometimes
enters into their composition.
soaps, but cocoa-nut
The first three operations
above described,viz.,pasting,graining

out, and

by

"

boilingon
of

means

and

boiled

out

cooled

should

strength,are

closed

steam

the spap
be hard.

the

to
pan is allowed
for
i
nto
ready
filling

proceeded

with

coil is continued

is free from

froth.

; the

until
A

clear

the

boiling

"head"
taken

is
and

sample
Boilingis then stopped,and, after covering,
rest for eightto ten hours, when
the soap
is
where
it
is
crutched
until
frames,
perfectly

smooth.
Cwrd
grease.
Its

mottled

is

usuallymade

from

melted

kitchen

stuff and

bone

the same
for curd soap, but
as
preparationis substantially
is
carried
of
The
not
curd
mottled soapfar.
art
so
boiling
making lies in the boiling. If boiled too long the mottlingwill not
form properly,
and, on the other hand, insufficient boilingwill cause

the clear

53

SOAP-MAKING.

the soap to contain an

its correct concentration

excess

after which

the soap
a
nd
the frames
peditiously
Some
in

entangledlye. Having boiled

it to

considered

covered

and
as

and

oil,and, in

curd, unable

to sink, and

as

the soap

the

Mottled

"

instances,rosin.

choice of

"

solution.
skill and

acquires the

experienceis necessary to
correct
mottlingstate. It should

spatulain largethick flakes,take

surface should not be glossy.
When

this

matter, which
ganese

!
*

4
i''"

"/
'*'

'('

;;
!
!j

^
^
/1
'*,;i
"'

;
i

f|
*"f
;fi)

/"'

/,

l\
Y;

Considerable
the soap

|.

cools

charge will naturallydepend upon the cost ; the

is characterof liquor,
which
property of absorbinga largeamount
istic of soaps made
from cocoa-nut
oil and palm-kerneloil,is taken
advantageof,as are also the physicalpropertiesof the various fats
and oils,with a view to the crystallisation
of the resultant soap and
the development of the mottle.
The
fat is saponified,
grained and
boiled on strength,
After
described.
as
withdrawing the
previously
the
with
closed
is
half-spentlye,
water, and is
just
by boiling
soap
then ready for the silicate or other saline additions.
Soap intended to be liquoredwith silicate of soda should be
of the soap
nature
distinctly
strong in free alkali;the crystalline
is increased
Some
and
mottled
intensified.
the
effect
thereby,
fit
to
the
allow
makers, however,
a nigre
deposit;
soap coarselyand
the settled soap to
then, after removing the nigre,or transferring
another
copper, containingscraps of mottled
soap, get the soap into
To
for mottling,and add the silicate of soda solution.
a condition
1
cwt. of soap, 28 Ib. of silicate of soda solution,32^" Tw.
(20"
every
of the silicate solution,
B.) is added, whilst boiling;the strengthoil and palmhowever, will depend upon the proportionof cocoa-nut
kernel oil present in the charge. Many soap-makersuse 20" Tw. (13"
B.) (cold)silicate solution,whilst others prefer140" Tw. (59'5"
B.),
with the gradualaddition of water
until the
to the soap, kept boiling,
product is in the correct mottling condition,and others, again,use
bleach liquor,
soda crystals,
pearlash, and salt,togetherwith silicate
The

;.j

Grey

some

fats used, remains

the

Soaps. These are silicated or liquored

the natural
soaps in which
mottling,due to the impure materials
used in the earlydays of soap-making,is imitated by artificial mottdifferent to curd mottled soaps.
ling,and are, consequently,entirely
The materials employed in making mottled soap comprise bleached
palm oil,tallow,bone fat,cocoa-nut
oil,palm-kerneloil,cotton-seed
Blue

mottling. The mottling may, therefore,

the impurity
of the soap, in which
crystallisation

forms

up.

the colour.

forms

"t

'

lye,containingthe impuritiesfrom

the interstices of the

it is enclosed
be

of

two
the pan is allowed
to rest about
hours,
be done exis ready for framing,which should

considerable

be ultramarine

dioxide for the grey mottled

when

drop off the

to set, and

the

"*

j-'
^

mottlingcondition has
would

time

discern

been

for the
soap

obtained, the
blue mottled

(3-4 Ib. ultramarine

colouring
and
or

man-

1-3 Ib.

5,

MANUFACTURE.

SOAP

54

littlewater and added to the boilingsoap"

"untilall is thoroughlyamalgamated,and when
a

the contents of the pan

off

is shut

the steam

ready for cleansing.

are

Mottled soap is run

covered over and allowed

soap),is mixed with

is continued
the boiling

of

for 1 ton

being sufficient

dioxide

manganese

frames, which, when

wooden

into

to cool very

result in

producedwhich

full,are

coolingslowly,

gradually.On

if

distinct bold mottle

;
are
large crystals
and the mottle is
obtained
i
s
small
is
too
a
crystal
rapid,
the cooling
resultingin either a small mottle, or no mottle at
not distributed,
In fact, the entire art of
all,and merely a general coloration.
mottling soap consists in properlybalancingthe saline solutions and
out
colouringmatter, so that the latter is properlydistributed throughat the
the soap, and does not either separatein coloured masses
whole
the
mass.
colour
of the frame, or uniformly
bottom
test 45 per cent, fattyacids,and
A sample of the soap should

the

range from J to 1 per cent.

those
English mottled soaps, especially

of salt would

amount

of the

Some

give a yellow-colouredground, are

2 per
in brine containing
brine, or pickling

soakingin

The

resultant

soap
be made

has

white

made

by

cent, of bleach

is firm.

ground and

from

bleached

which

materials

liquor.

The

by mining 1 cwt. bleachingpowder with

10 cwts. of soda
(15" Tw., 10" B.), allowingto settle,
and using the clear liquid,
or
by mixing 2 parts soda ash solution
with 1 part of bleachingpowder solution,both solutions being 30"
Tw.
(18'8"B.).
Milling-base.The materials generallyused are tallows and
is thoroughly
oils of the finest quality. The
tallow
cocoa-nut
and the graining is performed by the aid of caustic
first,
saponified
to salt. The
soda lye in preference
half-spentlyes are withdrawn,
and when
oil added to the pan.
and the cocoa-nut
This is saponified,
is complete,
the saponifi
cation
boiling-on-strengthis proceeded
should
with.
be devoted
to the
boiling-on-strength
Specialcare
in
its
value
be over-rated
cannot
operation
good soap-making
and perfect
be ensured.
The half-spent
must
saponification
lyes are
allowed to depositduringthe night,and the soap must
be carefully
liquormay

bleach

ash

solution

"

"

"

"

"

"

examined

"

next

morning to ascertain if any alkali has been absorbed.

plete,
permanent the strengthening
operationis com-

If the caustic taste is

but should

any caustic have been absorbed, further addition of

be made and the boiling
These remarks
continued.
apply

alkali must

equallyto
The

all soaps.
soap, when

Bleached
in the

palm oil,olive oil,castor

productionof

suitable
specially
Yellow
from
best

an

qualityis known
is

oil and

lard

are

also

special
millingsoap bases,a palm
productionof a violet-scented
Soaps, (a) Bar
Soaps. These
"

admixture

of from

in the South

in
designated

employed

oil soap being

toilet soap.

for the

Household

tallow with

Soap, but

ready,is fitted.

15-25

and West

the North

of

of

per

are

cent, rosin.

England as
England by such

made
The

Primrose
names

as

55

SOAP-MAKINO.

Golden

Pale, Imperial Pale, Gold

produces a

hard

very
soap
with alkali to form

combines

Medal

Pale,

alone

; but rosin
latheringqualities
body, which, although not a soap
mixture
readilysoluble in water, and in ad-

soft

in the strict

of the term, is
sense
with the durable tallow
soap renders it more
thereby increases its latheringproperties.

and

Tallow

etc.

of inferior

soluble

in water

The

rosin may
be added
to the soap-pan
after a previous partial
with
soda ash, and removal
of colouringmatter, and
saponification
finallysaponified with caustic soda lye, or, as is more
generally
adopted,as a rosin change. The pan is opened with caustic soda lye
and
saturation of the rosin takes place rapidly; when
completely
saponifiedit is grained with salt,and the coloured lye allowed to
withdrawn.
depositand finally
The four operationsalreadydetailed apply to this
soap.
be made
from
lower
Cheaper pale soaps may
grades of tallow
and rosin and are generally
silicated.
has arisen for soap of
(b) Tablet or Washer
Type. A demand
free latheringqualities,
which
has become
very popular for general
household
of cottonseed
This soap is usuallymade from a mixture
use.
"

oil,tallow,and
tallow

The

oil,with

cocoa-nut

yieldsfirmness

all assist in the

As to what

and

durabilitywhilst

ready productionof

more

of rosin.

amount

varying

the
a

other

stituents
con-

copiouslather.

yielda finished soap of

sufficient body and satisfactory
colour, this naturallydepends upon
the grade of raw
material
at the
soap-makers'disposal. Those
fats and oils which yieldfirm soaps, will,of course,
allow a greater
proportionof rosin to be incorporatedwith them than materials producing
soaps of less body. Bosin
imparts softness to a soap, and
of rosin

amount

can

be used

to

also colour.
This
been

is

fitted soap

given.
Cheaper soaps

with

produced from

lower

have

.gradematerials

already
hardened

Settling
of Soap. The fitted soap is allowed
fluenced,
days. The period allowed for restingis inhowever, not only by the size of the boil,and the season,
also by the composition of the soap, for if the base has been
from firm stock it is liable to cool quickerthan a soap produced

Bestingof Pans

but

full details of manufacture

alkaline solutions.

to settle from

made

are

and

from

soft-bodied

On

and

"

four to six

materials.

subsidence,the

contents

of the pan

will have

divided

into the

following:
"

First. On
coloured

good

top, a thin crust

fob, which is returned

of soap, with perhaps a little light

of the
after the removal
the pan

to

soap.

Second.
acids.

The

good settled soap, testing 62-63 per cent, fatty

of this layeris fully
subjectof removing and treatment
in the next chapter.
weak
which on
A layer of darker
nigre,"
soap, termed

The

dealt with
Third.

"

"I-

I1

to the particular
per cent, fattyacids,and, according
of the
cent,
from
15-20
to
fit employed, will amount
per
of soap in the pan.
total quantity
of
quantityof nigre may vary not only with the amount
The
the
amount
influenced
also
is
but
by
added
finishing,

"em

/I

33

tests

average

an

t!

MANUFACTUBE.

SOAP

56

during

water

If the
of caustic alkali remaining in the soap paste priorto fitting.
will
the
a
is
alkali-content
large
require
caustic
high,
soap
free
the
renders
This
water
fit.
the
desired
attain
water
of
to
amount
caustic into

weak
lye sufficiently

consequently,
as

with

is increased.
the quantity
settling,
solution containingalkaline salts,
mostly

Fourth. A
chlorides, with

layer is

Utilisation of Nigres.
"

by grainingwith
be

nigresare
Nigre may

salt.

used

several

which

from

it

the

nigre.
liquorseparated

materials.

new
"

Washer
of times

it

type.
be

can

soap of
In this case

obtained.

was

the

be utilised in various
with

times
"

one

boiled and

The

(1) It may
refers to soaps of the
particularly
the number
the nigre will determine
be
It
incorporatedwith
(2)
may
the

doubtless, under

variable,and

very

physicalconditions,this liquorhas separatedfrom

certain

carbonates

littlecaustic.

of the

amount

The

quantityof soap,
of soap together
salt which gravitates

solution

the

during
and

dissolve

to

weak

or
carbonate)and
(caustic

of alkali

excess

any

"nigre" is

the

The

ways.
This

colour

of

employed.
grade than

lower
a

system

is generally

adopted ; for example,soap of the best qualityis made in a clean

pan, the nigreremaining is worked
up with fresh material for soap
of the next
the nigre from
that boil,in its turn, is admixed
quality,
with a charge to produce a batch of third quality,
and the deposited
the' nigreobtained
nigre from this is again used for a fourth qualitysoap
this latter boil would
from
probably be transferred into the
dark in colour into the
or
cheapened "washer"
perhaps if it was
"

brown

soap-pan.

(3) The

nigre
from

original
soap
a

little fat with

be

may
which

it

fitted and

it.

several
(4) Nigres
and
fitted.
collected,
boiled,
from

with

unless

produce a soap similar to the

deposited. It is advisable to saponify

was

boils of the
The

chargingto keep the

new

same

settled

kind

portionmay

resultant

soap

of soap can
be
be incorporated

uniform

this is

materials

in colour

boils from
done, the difference in colour between
alone, and those containingnigre,is very noticeable.

nigre settled

from

this fitted

nigre boil

would

"

"

new

The

be utilised in brown

soap.

(5) According to its colour, and consistence,a nigre may

be
for the productionof disinfectant,
or
cold-water soaps.
be bleached
(6) Nigre may
with
20 per cent,
by treatment
a

suitable

solution

of

stannous

chloride

heated)is sufficient to bleach

"

cwt.

20 tons

of

of this

solution

(previously

nigre.
Transparent Soaps. The productionof transparentsoaps has
recently been fullystudied,from a theoretical point of view, by
"

MANTJFACTUBE.

SOAP

58

being thoroughlycrutched,the pan is covered and

and a half
hour
or
one
allowed
to proceed for one
saponifioation
be
for some
reason
retarded, a.
the saponification
Should
hours.
the
admitted
to
be very cautiously
jacketof the pan,
may
littlesteam
whole

Ib.

50
by dissolving
(76"C.)" *" whick ma7
soft

as

as
possible,

as

solution'' is pared
prein 50 Ib. water, at 168" F.

cane

sugar
5 Ib. soda

be added

The

colouring matter.

hard

the whole

and

until the reaction commences,

time.
allowed to rest the specified
the " sugar
is
Whilst saponificationproceeding,
well crutched

the mass

water

used

and
crystals,

for this solution

is liable to

water

sary
any necesshould be

streaks-

produce opaque

of lime

soap.
before proceedingfurther to ensure
It is absolutelynecessary
is complete. A greasy, soft feel and the presence-that saponification
of

"

strength
only
can

"

this

would
(caustic)
be remedied

of caustic
is

by

denote
further

alkali should

greatcare
required,

must

be

also

incompletesaponification
ficiency
heatingand crutching. Debe avoided,and, if more
lye^
"

exercised in its addition.

beingcompleted,the
Saponification
crutched into the soap ; when
gradually
become

and syrupy
the pan is covered for one
should not exceed 170" F.

homogeneous

and
in the pan

rested

Having
froth

on

the

the

necessary
will be

and
sugar solution is carefully
the contents of the pan have
tinued,
mass, the crutchingis disconhour.

The

(77"C.).
period,the soap

surface,but

clear underneath

heat

of the

will have
and

appear

soap-

slightdark.

be withdrawn, cooled,and
now
examined
priortomay
If
the
has
been
the
framing.
successfully
performed
process
soap
of uniform colour,and possess only awill be firm and transparent,

Samples

alkaline taste.
faintly
If the sample be

firm

but

quired
sugar solution is rewhilst crutching,
; this should be added very carefully
an
excessbeing speciallyguarded against. If the sample be soft, although
dently
transparent,and the alkaline taste not too pronounced, the soap evicontains
of water, which
an
excess
be remedied
by the^
may
addition of a small quantityof soda ash ;,too much
soda ash (carbonates)

must

be

avoided,lest

opaque,

it should

more

produceefflorescence.

the soap and found it to be correct,or having

Having
remedied
its defects,
the soap in the pan is allowed to cool to 145" F.
and
(63"C.)
The
perfume added.
soap is now
quicklyfilled intoframes and allowed to cool rapidly.
narrow
examined

The

blocks

of soap should not be stripped

until quitecold throughout,
should
be
allowed
to stand open
they
for a while before
slabbing. When
freshlycut into tablets,the soap may
appear
somewhat
turbid,but the brightness
with the exposure
comes
it will
receive prior to stamping and
wrapping.
and

SaponifyingMineral Oil. This sounds somewhat

incongruous,
mineral
oil is entirely
Most
of the suggestions,
unsaponifiable.
for this
consist of the incorporation
of mineral oil,
purpose
or
mineral
"

as

SOAP-MAKING.

emulsified

oil
in

by

all

oil

mineral

of

means

this

In

the

connection

'dilute

of
the
Dr.

properties

(for

it

oil)

mineral

the

In

by
in

and

latter

deposited

thereby

of

1903,

sorbing
ab-

soap

He

when

composed
de-

organic

formed

tained
ob-

magnesia

which

various

yielded

Zelinsky

37).
upon

petroleum,

the

of

by

be

acids.

tri-octin,

Soap.

which

Messrs.
also

and

by

origin

of

petroleum

as

in

under

the

natural

pressure.

have

Attempts

"

animal

present
oils

and

fats

the

described

hydrocarbons

animal

of

of

theory

might

the

all

1897),

former

electricity
the

into

been

Nodon,

Brettonneau

Messrs.

Merry

made
and

and

to

Shee

Noble

(Eng.

is

agitated

1900)

2,372,

Pat.

states

these,

work

dioxide

glycerine

what

distilling

22,129,

Pat.

(Bug.

electrically

soap

heat

fat.

Production

Electrical

produce

heating

almost

by

Chem.,

of

acid,

obtained

contained

interesting

carbon

with

confirmation

in

Engler,

the

fractions

on

of

petroleums,

some

and

and

converted

are

Angew.

sulphuric

acids

these

One

to

proposes

alcohols,

which

with

acting

by
chlorinated

of

by

suspension.

alkali,

strong

into

quoted

Zeits.

Ges.

substances,

had

be

may

Chem.

compounds

and

acids,

fatty

in

and

soap,

alkali.

Phys.

(Russ.

1902),

hydrocarbons

become

exists

however,

spermaceti

the

oxygen,

by

321,510,

oil

cocoa-nut

merely

hydrocarbon

with

together

with

bark,

Quillaia

Pat.

transforms

he

that

of
the

(Fr.

Eeale

G.

aid

instances

these

59

patent,
at

caustic
on

saponified.

of

temperature
alkali

wire-netting

of

mixture

is

soda-lye

194"-212"

electrolytically
in

the

presence

and

fat

(90"-100"
produced
of

C.),
from

fat,

which

while

brine,
is

VI.

CHAPTEB
OF

TREATMENT

SOAP.

SETTLED

Cleansing Crutchmg Liquoring of Soaps Filling Neutralising, Colouring

Slabbing Barring Open
and
Perfuming Disinfectant Soaps Framing
and
Close Piling" Drying" Stamping" Cooling.
"

"

"

"

"

"

"

"

"

and allowingthe
Cleansing. After completion of saponification,
the
various layers,
described in
as
of the pan to settle into
contents
the actual soap, forming the second
the precedingchapter,
layer,is
termed
ing"
cleanstransferred to the frames, this being generally
now
The
thin crust or layer at the top of the pan
is
the soap.
gentlyremoved, and the soap may be either ladled out and conveyed
from
the
above
to the frames, or withdrawn
by the aid of a pump
of a
(Fig.1), and pipe,attached by means
.nigrethrough a skimmer
"swivel joint(Fig.2) (which allows the skimmer
pipe to be raised or
"

"

1."

Skimmer,

with

flangefor

attachment

Jto

skimmer-pipe.
lowered
side

if

I !";

at will

of the

pan

by
as

means

FIG.

of

2."

Swivel- joint.

winch, Fig.3),to a pipe fitted in the

in Fig. 4, or the removal
be
may

fullyshown

performed by gravitationthrough some

mechanical

device

from

the

nigrein

the

side of the
copper.

Every precaution

is taken

soap being cleansed.

The temperature at which

to avoid

soap

60

may

the presence

of

be cleansed depends

on

the

TREATMENT

grade"
particular
a

SETTLED

61

SOAP.

to be liquored
requiring
should not be cleansed
will
take
separation
place,150" P. (66"C.) may be taken
suitable temperaturefor this class of
soap ; in the case of firm

too hot
as

OP

or

soaps

Fi"". 8."

i*.

4,-

"Hiwip-kiillng
j"fi"showing skimmer

soaps, such as milling

the pan (and thus

170" P.

(74"~77*s
0.)-

to the

Winch.

pipe,swivel and winch.

coolingis liable to take placein

be 165"the temperaturemay
yield),

where
the
This

latter elass of soap

and crutohed

by

hand, or, to

save

is

generallyran
labour,

manual

62

SOAP

Fw,

MANUFACTURE.

5." Hand

orutoh

Fie. 6." Mechaiidoal oratoher.

TBEATMENT

it may

OF

SETTLED

SOAP.

63

material
power-drivencrutchingpan (neutralising
if necessary) and stirred a few times before framing.
the hot soap in the frames
Crutching. This consists of stirring
lowered
by hand crutches (Fig.5) until the temperature is sufficiently
and
the soap begins to assume
a "ropiness".
Crutching may also
be performed mechanically. There
various types of mechanical
are
crutchers,stationaryand travelling.They may be cylindrical
pans,
rotated
which
in
of
the
is
centre
an
or
jacketed
otherwise,
agitator,
several blades
consistingof a vertical or horizontal shaft carrying
(Fig.6) or the agitatormay take the form of an Archimedean screw
working in a cylinder(Fig.7).
be

run

into

being added

"

FIG.

The

kind

7.
"

Mechanical

crutcher.

mine
will detercrutched,whether thin or stiff,
cludes
former class inThe
suitable type for the purpose.
and coloured
is generally
neutralised,
soap which

of soap. to be

the most
"washer"

perfumed, if necessary, in these crutchingpans, and in that

case
they are merely used for mixing the liquidswith the hot soap
lets
priorto its passage along wooden spouts (Fig.8) providedwith outthe crutchingis continued by hand.
the frames, in which
over
the
of liquor,
of stiffsoaps requiring
In the case
completeincorporation
the
the soap being forced upwards by
screw,
screw
type is preferable,
the
of
and
sides
the
the
between
and descending
pan, while
cylinder
"

and

MANUFACTURE.

SOAP

the

reverse

action

can

broughtinto play. ^Thecompletionof

also be

and

the smoothness

stiffness of the

soap
crutchine is indicatedby
this
out
at
and
taken
and
a
point
portion
trowel,
moved with a
when
well
When
mixed
the
rounded
a
appearance.
cooled should present

resultant productis

into
emptieddirectly

wheel-frames

placedunder.
It is importantthat

neath the outlet of the pan.

of the agitatinggear bo
the blades or worm
with
covered
soap to avoid the occlusion of air

preventthe soap becoming softand spongy.

Liquoringof Soaps," This consists of the

and to

addition of various alkaline solutions to soap toand is tost performed

producedifferent qualities,
machines, althoughit is in Homo
in the crutching
carried out

instances

in

the

frames.

historyof soap-makinga largenumber

In

and

the

variety

have been suggestedfor the purof substances

pose
real or Bupiwsed
of accomplishingsome
desirable effect when added to soap.
Many of

only a very short existence,and

fallen out of use.
gradually
additionn most
Amongst the more
practical
|
be
mentioned
oarfxnmto
adopted
frequently
may
ash
and
silicateof
of
soda,
soda,
(impure
pearl
"
of soda.
The
of
carbonate
carbonate
potash).
a
"| may be used in the form of ""oda crystals,"
had

these have

others have

|
|
*

which, containing62'9 per

solves in its

heating,and

own

water

is in that

In the

cent,

of

of water, dis-

on
crystallisation

to the hot

added

manner

ttoap, this
firmness
increasesthe
and
addition gives
tends to

|j soap.

case

of weak-bodied

detergentqualities.
soda

The
soap

as

also be added to
carbonate may
either
solution of soda ash (58"alkali)

concentrated,62" Tw. (34" B.)t or of various

from 25" Tw. (16"B.) upwards. Thin
strengths
solution stiffens and

addition,which

must

hardens
not

be

soap,

and

escence
excessive,or efflor-

will occur, is generally

made at
of 140" F. (60"
should
Car"
C.).
be taken in the choice of solutions for

Strong soda ash solution with

result in
of

the

firm

brittle product,
whereas

perature
tem-

always
liquoring.
will

the texturo

improved by
soap would be greatly
such addition.
A slightaddition of a weak
solution of pearl ash, 4"-8" Tw"
7-5-4"
the
(2of many
B.), improves
appearance
soaps intended for
household purposes."
For

weak

low percentageof fattyacids,

yellow soaps, containing
a

MANUFACTURE.

SOAP

prefer to
soap manufacturers
cleansing,althoughsome
this duringthe millingoperation. Various materials have

^-B

during

accompli^

for the purpose, those

bicarbonate,boric acid,cocoa-nut

NaHC03

soda

soda)

of

in aqueous

is necessary

care

sodium

equation:
Water

borax

in

"

H20

of soda

and
glycerinesolutions,

used, but

sometimes

are

or

the

Na2CO3
Carbonate

oleic

the caustic alkali

converts

being

acid,and

quantityof

exact

an

expressed by

of soda

Bicarbonate

acid

be

reaction may

The

earbonate.

33oric

of

oil,stearic

which
(acidsodium carbonate),

foicar bonate
Into

is the addition

method

best

generaluse

in most

been, recommended

(biborate

employing these

is liable to

decompose the soap.

the greatobjection
Tb-e addition of cocoa-nut oil is unsatisfactory,
is
difficult
to
that
and, further,
ensure,
completesaponification
being
of ranciditydeveloping. Stearic and
is always the liability
there
substances,

as

acids

oleic

that oleates

patented,for
be mentioned

these may

Among
alkali,
bib"sie

the
neutralising
Alder

"

salt,the acid radicle

ammoniacal

caustic

free

Wright'smethod

of which

beingliberated ; the

ammonia

but oleic acid has the

very liable to go rancid.

substances
have been proposed,and

are

of other

number

instances

many

suitable for the purpose,

more

are

disadvantage
A
large

excess

any

the

neutralises

of sodium

use

of

and

in

alkali.

using an
caustic

potassium

phosphate (Eng. Pat. 25,357, 1899) ; a substance formed by

treating albumen with formalin (Eng. Pat, 8,582, 1900) ; wheat glutenin
albnrainoses
(albumenafter acid or alkaline treatment)
tract
ex; malt
and egg, milk,or vegetable
albumen.
;
used
matter
be of either vegetable
Tne
coal-tar
or
colouring
may
origin, and is dissolved in the most suitable medium
(lye,water, or
The
older
of
such as cadmium
fat).
colouringmatter
types
yellow,
have been superseded.
ochres, vermilion, umbers
the production of washer
In
household
soaps, a small quantity
of perfume
is sometimes
added.
DisinfectantSoaps. To the soap base, which must be strong to
"

"

"

"

"

is added

taste,

from

3 to 4 per

cent, of coal-tar derivatives,

such
as
acid, cresylic
acid,creosote,naphthalene,or compounds containing

carbolic

carbolic acid and its homologues.

in

th.e

the

crutchingpan, and further

crutchingmay

is made
incorporation
be givenby hand
in

frames.

Framing.
into

The

"

blocks.

slow

The

allow

in

general
is

As

in
as

soon

is

of

allow the soap to

to

for mottled

wood,

lyeto accumulate

The

use.

shown

frame

constructed

of

excess

objectof framing is
frames intended

cooling,are

to

the

The

"

often

with

for other

frame manufactured

by

soaps, which

solidify
require

well in the

soaps, iron frames

H.

D.

Morgan

base
are

of Liverpool

Eig.9.

the

frame

the
finished,

is
soap

or
filled,

as

is smoothed

soon

by

as

the

means

crutchingin
of

trowel,

TUKATMENT

OF

SETTLED

SOAP.

67

IM

m,

Fia,

y."

10.-"

Hotipframe.

Blabbingmachine.

MANUFACTURE.

SOAP

in the centre

v-oor,
hea

which
which

slopes towards the sides.

slopes

Next

""

(Fig.11).

of the slab

ness

Fio.

All tallow soaps

bars

11."

Banjo Blabber.

should be slabbed whilst still warm,

^andao"P:n-piled
immediately;
type,

of soap

if this

Slab"rp"^^^
the

"-

"

out

into

cold when

fay~

of

boTd^re^
machine (Fig.18),the lower
usuallyby
ol
through the soap
rk
which, containingwires, is drawn
or

on

"the

the

more

and the
base-board; the framework is raised,

bars fall

shelf ready for transference into piles.It has long teen

and wdghto cut bars of soap 15 inchesloug,

ZcuSom
t EngSd

!n!
Tib^ch 111
bars of soap to the owt., but in recent years
h":
^
arisen for bars of
demand
many various weightsthat it must
or

so

be sometimes
In another

Indthe
is

cut to

matter
difficult

to know

what

sizes

to stock

type of barring machine, porfconsof the slab,previously

framework
a
size,are pushed against
carrying wire*,

ready for handling Fig. 13

household soap
machines, through which "washer"
In cutting
the bar is pushed at rightanglesthrough another
being passed,
bars slide along a table

ramrcoltaintog
wires, which

be received upon

racks and

are

divides it into

tablets ; these, may

dryingand stooping. It
tablets are cut with a view
to

readyfor

is needless to say that the slabs and

69
OF

TREATMENT

Fw.

Fw.

12."

18."

SETTLED

SOAP.

Barring machine.

machine.
Bar-cutting

{,

70

SOAP

MANUFACTUBE.

THKATMENT

reducing

the amount

machine, made

by

Open- and

for
may

of waste

to

Forshaw

"

SETTLED

71

SOAP.

the lowest

limit. Su"3a a
possible
in Pig.14.
tallow soaps
previously,
or
stacked
open-piled,"

Son, Ltd., is shown

Clone-pUimi."ka remarked

whilst warns, and the bars

each other in such a way that air has free access
to each
and next
day. The bar of soap will skin or case-harden,

should
across

K.

OF

be

ho cut

"

or
"olose-pikul,"
placed in

should remain
condition for

for two

or

the

storage bins, where

three weeks, when they will be in

ready for distribution.

bar

day
they
perfect

packinginto boxes

Fiti. 1/1."

Hemp Htamp.

an
/"f//Wf'/,~"()il
soaps,1'
soaps of the washer type are termed,
the
skin sufficiently
treatment, and are generopen-piling
by
ally
in
chamber
in
air
hot
a
racks
of
to
current
on
a
drying
exposed
of
and
order to produce the skin,which preventsevaporation water,
allows of an impressionbeing given by the stamp without the soap
adhering to the dies. It is of course understood that heavilyliquored

do not

soaps are, as ft rule,unsuitable for the dryingtreatment,

and lose water rapidly,
become unshapely,

as

the bars

of a handstamped by means
Stamping." liar soaps are usually
stamp containingremovable or fixed brass letters (Fig.15),with a

72

SOAP

brand

MANUFACTURE.

of the manuof qualityand the name

facturer
designation
are
now
ready for packing into boxes.
A very large bulk of the soap trade consists of the household
These
are
qualityin tablet form, readilydivided into two cakes.
the
moulds
dies
and
box
with
bottom
in
two
ordinary
stamped
top
being removable, allow the impressions
impressions the die-plates,
to be changed. This type of mould
(Pig.16) can be adjustedfor
of
of
tablets
the compression
varying thickness, the box preventing
certain

or

vendor, and

or

"

"

We
the escape of soap.
for this illustration.

indebted

are

16.

FIG.

The

power
be

stamping
driven.
be

the
the

dies

by

may

of the

many

employed,the
of endless

means

Box

mould.

be

worked

of
largequantities

Where

stamped, one
may

machine

"

automatic
tablets
belts.

Forshaw

E.

to

by

"

hand

(Fig.17)

or

tablet have
particular

mechanical

stampers

being conveyed
Such

Son, Ltd.,

to

and

in

from

is shown

machine

to
istence
ex-

in

accompanying illustration (Fig.18).

If necessary,
air,after which

the soap is transferred to racks and

is
it is ready for wrapping, which

by manual
wrapping machines
Cardboard

labour, although in
are

in

some

exposed to the
generallyperformed

instances

automatic

use.

cartons are also used for encasingthe wrapped tablets,

men
convenientlyhandled by tradesobjectbeing that these are more
and may
used to form an attractive window
be advantageously
display.
Cooling.Many attempts have been made to shorten the time

the

"

74

MANUFACTURE.

SOAP

for
required
as

soap

the

framingand finishingof

it leaves

With

revolvingdrum

by coolingthe liquid!

the pan.

millingbase, this

is

accomplishedin
successfully

sonnieres'plant,by allowingthe hot

of

soap,

which

can

soap

to fall upon

cooled

be

the

internally
by

the Ores-

periphery
means

of

water.

In the
be

of

case

of household

good appearance
bar

producea
soap which

soaps, where
firm
a

have

and

fit for sale after the

has

been

the resultant

coolinghas

suddenlychilled lacks

FIG.

18.

Automatic

"

productmust

is to
texture,the difficulty
been

performed,as

the appearance

of that.

stamper.

treated in the

is

Several patents have been

ordinaryway.
granted for
of moulding into bars in
tubes,where the hot soap
by being either surrounded
by runningwater in a machine

methods

various

cooled

of similar

construction

coolingmedium
mechanical
the

and

to

passing

the
chilling,

machine,

or

rotated

through

claims have been made

both for
for methods
of removing or discharging

appliancesand
cooling. In many instances these have
satisfactory,
proved unpwmg to fracture of .the crystalline
structure.
over,
More-

bars after

candle

numerous

soap

through some
1S

churned

by

of the devices for solidification

after
means
of a worm
or
and
this
screw,

THKATMKNT

OF

SETTLED

75-

SOAP.

interferes with tho firmness of the finished bar,for,as is well known,

has boon handled too much, does not
soap which
regainits former
its appearance
is rendered unsatisfactory.
firmness, and
of apparatus which is now
results is thegivingsatisfactory
cooler (Fig. 19). This consists of a fixed
Leirndoerfor continuous
A form

charging hopper,A,

portabletank,B, containing tubes,and a detachable

bo
raised
can
or
lowered by means
of a
I). Tho bottom of the hopperis fitted with holes correspondscrew,
ing
with tho cooling tubes,e, and closed by plugs c, attached to a
terminates
above
in a screw
frame hr which
of
spindlea, by means
a

box, (.),which

cooler.

Fin.

which tho frame* ami

plugscan

be raised and

lowered

so

as

to

permit

are
outflow of noap into the coolingtubes. The
in
which
and
the
box
glides
bottom
B,
dt
they are
by
mounted, is carried on a truck running on rails. The charging
hoppercan b" connected with the Hoap-pan by a pipe,and when the
hopjmrIB filledwith liquid
soap the plugsc are raised and the air in

or

stop

tubes

the

cloned at the

the

box

exhausted, thus causing

the

soap

to

descend

into the-

cooling tubes,
I) released,and the box B
At the end of the rail track
for another.
moved away
to make
room
is an ejecting
device which pushes the cooled soap out of the tubes,
for use over
and the truck in run back on a side track to the machine
The

Blidtm A

are

cloaod, the

screw

76

again.

In

being

soap
for

this

to

{Eng.

Pat.

the

idea

similar

24,440,

moulds

having

screws

and

the

way

received

transport
A

water

MANUFACTURE.

SOAP

open
pressure

apparatus

or

press
has

cooling

the

from

store

Fig.

1904,
sides,

pipes

the

suitable

of

subject
The

20).

which

is

soap
closed

are

by

cooling

between

plates

on

continuously,

"

oHonflMoHo

'20."

Holouhek'fl

prli'

coolor.

patent
run

being

tubes

circulates.

Fie*.

the

arrangement

room.

made

been

worked

be

can

by
into

Holoubek
frames

clamped
through

or

with

which

CHAPTER

VIL

AND

MISCELLANEOUS

TEXTILE

TOILET,

Soapa"tiettkd

/'rams

Toilet Soapa"CM

Boiled

SOAPS.

Noeips"Remelted Soaps"Milled

ami
Soai*8~~Drying~~Millintj
Colour,Perfume, or Medicament
Incorporating
Matter" Neutralising
and
"I'trfumt'"GotouriHg
Sup"rfattingMaterial"
( utti ng "Stomping" Medicated
CompWH* i ng
Soaps" Stner Soap Floating
Httaps"Storing SQtiw"Tej'iil*Soap*" -Soaps for Woollen,Cotton and Silk
1 Client Textile Soaptt"Mfaci'llaneouit
Jndwtrw^"Soaps.
'

"

"

"

the terra "toilet soap" is inferred a

Soaps."By
soap
not
its
of
gent
deteradapted for toilet use by reason
specially
only
good
but also on account
and latheringqualities,
of its freedom from
cauBtic alkali and any other ingredientlikelyto cause
irritation or
Toilet

Injuryto

the skin.

ToilfltBoapB

may

be

into the
of preparation

simply classified according to

followingfour classes

(1)Gold

their method

:"

process soaps.

(2) Bottled boiled soaps.

(3) Bamelteti soaps.

(4) Milled uoaps.

Hoapi of the

flrsticlass

are

of

trifling
importance,
comparatively

qualities.Details of the "cold

given on page 46 ; it is only necessary to
proceRB
to the soap.
add the deBired perfume and colouringmatter
having

been
'*

Hupemult'dby

have

the other

alreadybeen

Becoiul class consists of good quality

settled soaps, direct from
have
which
been lidded,priorto framing,suitable perthe copper, to
fume
The

materials.
colouringmatter, also,if necessary, dealkalising
The third class IH represented
by soaps made by the old English
which are often termed "perfumers',"or "little
method of twtielting,
and

soap-baseor mixture of various kinds of soap is

a steamjacketedpan, or pan providedwith steam coils,
agitated. The agitationmust not be too vigorousor lengthy,or

"

soaps.
pan
remeltciclin
and

The

aerated.
the soap will become
of pearlash solution are made

allthe soap is molten, additions

to give it a finer and smoother texture,
When

transparent, and increase its latheringproperties.

well incorporated,
and
The
necessary colour,in a soluble form, is
of the perfume is
much
the perfume. Owing to volatilisation,
lastly
render

it

lost when

more

added

to hot soap, and

it is necessary

to add

largequantity

get the desired odour ; hence the cheaperessential oils have to

be used, BO that the perfume of this class of soap is not so delicate
to

77

MANUFACTURE,

HOAP

78

to produce reit is quitepossible

that of milled soaps, although
alkali as a milled toiletsoap.
melted soaps as free from unoombined
and brown
toilet
Palm-oil soap often forms the basis for yellow
Windsor
Brown
old-fashioned
class. The
scmp was
soaps of this
had acand
with
remdfcing
that
quired
frequcmt
age
a curd soap
.originally
"~tl
"f
acids
the
u"
"
tenor refatty
tint by oxidation of
a brown
"as
wo

melted the better the resultant soap.

sometimes acldod to those soaps, e,tj,,camphor,
are
Medicaments
and bran have.*boon rwmimcmded
or carbolic. Oatmeal
borax coal-tar,
with soap for toilet purposes, and

in combination

granted for the

a putcmt ( F"n".Pat.
of those* substances

use?
1896) has been
boric
with
with wood-fibre impregnated
together

.26 396,

acid.

After coolingin small frames, the noap is slabbed, and cut into
suitable for stamping in a press
into portions
blocks,and finally
each side,
on
(hand or steam driven)with a designor lettering
the
all high-class
on
Milled Toilet Soaps." Practically
soaps now

throughthe French or millingprocess. This treatment,

first practised
was
by the* French who introduce*!
its name
implies,
AS
of
(ii")
millingand
it to this country,and consists briefly (I)drying,
and
colour,perfume or medicament, (ill)cewiprossing,
incorporating
cuttingand stamping.
(iv.)
toiletsoap produce*!
by other
The advantagesof milled soap over
market

pass

.methods

are

soap, is

more

that the former, containing less water

economical

more

does not shrink, or

finish,
elegant
and essential oils and delicate perfumes may
composition,
without

fear of loss

Only soap made from

base being that obtained
tallow with

actual

better Rpiwaraneo, and

in more
uniform
lose its Hhaj"o,

in use, possesses

more

In

and

or

corporated
In* in-

deterioration.

fats is usually
a suitable
milleel,
quality
blend of the fluent white
a
by saponifying
best

not exceeding25 per ccmt., of oocoa-nut

oil,
proportion,
"and prepared
as described in Chapter V.
first essential of a millingbase in that the Haponification
The
.should be thorough and complete
; if this i" not ensurm!, rancidity
liable
to occur
is
and a satisfactory
b" produced.
toilet soap cannot
'The soap must not be short in texture or brittleand liableto split,
but of a firm and somewhat
plastic
coriBmtency.
The
after solidificationin the frames,
(i.)
Drying."
milling-base,
a

contains almost

from
invariably

28 to 30 par cent,

of water, und this

to rather lews than half before the*
quantitymust
Hoap
be satisfactorily
can
milled. Guttingthe soap into Imrs or Htrips
and
be reduced

facilitatesthe drying,which
openpiling
greatly

chippingthe soap and

At

exposingit
95-105" F. (3540"C.).
There

of
warm

are

several forms

chips are

of

on

apparatus with fan made

The older method

of

trays to

dryingchambers

placedupon
air circulated through,and
a

is
a

usually
current

in which

the trays
above anothor,and
one
21 shows
a
soap drying

series of racks

Fig.

by W. J. Fraser

heatingthe air

by

of hot air

"" Go,,Ltd., London.

by allowingit to

TEXTILE

a
or
a

pipe
coal

small

drawn*-

flue

or

fire are

shaft
or

through which

AND

MISCELLANEOUS

79

SOAPS.

productsof combustion from a coke

the floor of the dryingchamber
to
been
superseded by steam heat. The air IB either
of quickly revolving fans through a
means
by
the

undor
proceeding
has

forced

fr
T?
CM

"M

cylinderplaced in a horizontal positionand containing steam coils,

the iron gratingforming the
steam- pipes laid under
or passed over
floor of the chamber,
It will be readilyunderstood that in the case of a bad conductor
it is difficultto evaporate moisture withof heat, like soap-chippings,

"m
SOAP

80

them

constantlymoving

out

MANUFACTURE.

and

exposing fresh surfaces

to

the

action of Heat.
the shavings of chilled
Cressonnieres'
system, where
carried
a
through heated chamber
dried by being
upon a

the

In
are

soap

lower

series of endless
belt which

the contents
bands (the first discharging
in the
and
the
is
at
moving
end,
projects

direction, and

on),this is

so

to

on

opposite

rollersmilling
performedby intercepting

system of belts (Bng. Pat. 4,916, 1898) whereby the surfaces

in the

tion
the dryingare altered,and it is claimed that the formaof hardened crust is prevented.
of drying, the chipsare
frequently
In the ordinary methods
hand to assist uniform evaporation.
moved

exposed to

by

degreeof saturationof

The

consideration

into

through

ill #,

It
IfI

f;*
r/

II

l!

is

in

the

air with

the
regulating

moisture

temperature

the dryingchamber,and for this purpose

the

be taken

must

and
use

flow
of

of

air

meter
hygro-

advantageous.

of moisture should
that the correct amount
It is very important
little
too
the
exact pointcan
too
not
nor
much,
in
the
;
be left
soap,
and
and
determined
depends to a
judgment
experience,
by
only be
of the soap, and also on the
considerable extent upon the nature
to be added, but speakinggenerally,
If the soap
14 per cent, givesgood results.
11
to
of
range
it is liable to crumble
less than this amount
during the
contains
and the finished tablet may
milling,will not compress satisfactorily,

of

amount

perfume or medicament

have
in

tendency to

use.

crack and contain

so objectionable
gritty
particles

If, on the other hand, the soap is left

stick to the rollers and

mill with

too

moist, it is apt to

and
difficulty,

duringcompression
sticky
appearance.
of Colour,Perfumeor Medicament.
Millingand Incorporatioji
(ii.)
is to render the soap perfectly
The objectof milling
homogeneous,and
to reduce it to a state in which colour,perfume,or any necessary neutralising
be thoroughly
material or other substance may
incorporated.
consists of smooth
fitted with
The milling machine
graniterollers,
suitable gearing and working in an iron framework
(Fig.22). The
connected in such a manner
that they rotate at different
rollers are
of the milling,
and ensures
speeds,and this increases the efficiency
of rubbingrather than crushing.
that the action of the rollers is one
of suitably
the pressure of the rollers
arrangedscrews
By means
t
o
another
be
the
can
on
one
adjusted give
issuingsoap any desired
the surface

assumes

blistered and

"

thickness

care

thick
The

should be taken
or

that the sheets of soap are not

odour will not be uniform.

necessarily
un-

the colour and

soap, in the form of

a
hopper,and after

chips,is introduced on to the rollers

one
through the mill,from
passage
to top, one of the serrated knife edges is appliedand the
bottom
ribbons of the soap are delivered into the top of the hopper where
the colour,perfume,and any other desired admixture is added, and
the millingoperation
three or four times.
the incorWhen
poration
repeated
is completethe other scraper is fixed againstthe top roller
through

MANUFACTURE.

SOAP

82

soaps the quantitywill range from

but rarelyexceeds 18-20 ozs,, whereas

gradesof milled
per

cwt., and

soaps
cwt.

much

as

as

40-50

fluid

ozs.

are

10-30 fluid ozs.

in

more

added

sometimes

costly
to

the

years an outcry has been made

and
the highestclass soaps have been
againsthighlycoloured soaps,
cate
manufactured either colourless or at the most with only a very deli-

'ColouringMatter.

tint.

only the
any

"

During recent

It is obvious

that

highestgrade oils and

white

rosin,and, so far,the desire for

Many perfumes,however, tend

FIG.

of
guarantees the use
excludes the introduction o"
white soap is doubtless justified.
soap

fats,and
to

23.

"

quicklydiscolour

soap, hence

th.e

Compressor.

advantageof givingit a slighttint. For this purpose a vegetable

and chlorophyll
is very suitable.
colouringmatter is preferable,
A demand
stillexists for brightly
coloured soaps, and this is -usually
the
met
of
coal-tar
use
by
dyes. The quantityrequired is of
course
result could
extremelysmall, so that no harm or disagreeable
possiblyarise from their use.
Neutralisingand SuperfattingMaterial. If desired, the final
neutralisation of free alkali can
be carried out during the milling
material
superfatting
process, any
time.
being added at the same
The
chief neutralising
have
reagents
-in
already been mentioned
Chapter VI.
"

TOILET,

With

AND

MISCELLANEOUS

83

SOAPS.

regard to superfatting
material,the quantityof this should

very small, not

be

TEXTILE

exceeding6-8

ozs.

The

per cwt.

most

suitable

vaseline,lanoline,
or
spermaceti.
(Hi.)Compressing. The next stage is the compression and

materials are

"

of the soap

ribbons into

plantused (Fig.23) for

factories. The

"

soap

\r

"

Fxo.

tube
conical-shaped
and

in which

this purpose

is fed

24.

like

solid bar suitable for

the same
substantially
through a hopper into a strong

Hand

"

ing
bind-

stamping,and

is

the

in all
metal

soap-stampingpress.

cannon,

which

tapers towards

the nozzle,
the soap is

is moving, and
singleor twin screw
m
etallic
disc,subjected to great
through a perforated
The
and
must
be kept uniformly
screws
compressed.
pressure,
covered
with shavingsduringcompression to obviate air bubbles in
a

therebyforced

the soap.
The soap
a

cutter

finally
emerges

of suitable

throughthe

shape and size

nozzle

(towhich

accordingto the

form

is attached

it is intended

SOAP

MANUFACTUBE.

FIG.

25.

"

Screw

press.

TOILET,

TEXTILE

AND

MISCELLANEOUS

85

SOAPS.

the final tablet to take)m

a long,polished,
solid bar,which
with a knife or wire into lengthsof 2 or 3 feet,and if of

is cut

satisfactory

is

ready

appearance,
plodderis heated

by

for

cuttingand stamping.
of

means

Bunsen

The

nozzle of the

burner to about

120"

or

130"

(49"-55"G.) to allow the soap to be easilyforced out, and this

also impartsa good glossand finish to the ejectedbar
ifthe nozzle
P.

"

hot, however, the soap

is too

will be

whereas
blistered,

insufficient

heat will result in

streakysoap of a poor and dull appearance.

and
(iv.)Cutting
Stamping. In cuttingthe soap into sections
similar to the
stamping, the cutter ghould shape it somewhat
"

for
quired
re-

finished tablet.

Many

manufacturers

the soap into sections having concave

ends,and in stamping,the corners
forced into the concavity,
with
are
that
result
the
unsightlymarkings are producedat each end of the
tablet. It i" preferable
to have a cutter with convex
ends, and if the

stamping is to
largerthan the

cut

be clone in
exact

the shape should

a pin mould
"im of the desired tablet.

be

trifle

is*i",'JM.-~-Pin mould.

Tim
a

Hcnnv

HtiunpinKmay be performedby a hand stamper (Fig.24),

stamper. The screw
press
prtwn (Fig,SJ5),or by a steam

for toilet soaps.

work* very Katmfaotoriiy
There are two ktrtcb of moulds in use for milled soaps :"
in which tablets of one size and shape
(a) Pin JtfVw/ffjf

onlycan

edgesof the mould meet very exactly,

carries
the
die
the upper part of
two
pins attached to the shoulder,
and theme are received into two holes in the shoulder of the bottom
plate. The mtperfluouK
soap is forced out as the dies meet.
Moultl*."In
this Form (Fig.27) the mould
Collar
Rand
or
(b)
be

produced (Fig.2("). The

may
OSH,

The

to stomp various sized tablets,

adjunteci
say from 2 ozs. to 5|
of
removable die plates.
and different impressions
givenby means
out sideways. We are
the soap squeezing
band or collar

be

to E. Forshaw

" Son, Ltd.,for the loan of this illustration.

It is usual
of

MANUFACTUBE.

SOAP

86

to moisten

the

if it should have a
glycerine
The soap is then readyfor

soap

or

final

MEDICATED
inherent

dilute solution

tendencyto stick to the die

cleansingpower

plates.

trimming,wrapping,and

PIG. 27." Band

The

with

mould

boxing.

mould.

SOAPS.
of soap renders it invaluable

in

while it also has distinct germicidalproperties,

a
combatingdisease,
2 per cent, solution provingfatal to B. coli communis
in less than six
1
and
marked
cent,
solution
action on
a
a
even
hours,
having
per
in fifteen minutes.

germs

Many makers, however,

seek

more

or

less

to
successfully

still

the value of soap in this direction by the incorporation

of various drugs and chemicals,
and the number
of medicated
soaps on the market is now
very large. Such
soaps may consist of
further

increase

soft soaps to which

certain medicaments have been
or
and
be
divided
into
two classes,
can
added,
(a)those which
roughly
for various definitediseases,
contain a specific
the intention being that
hard

either

the

remedy should

penetrate the
to act
ants

be absorbed

system, and
as

by

(6)those

the

pores

of the skin and

thus

with
impregnated

or
antiseptics
germicides,or,

tended
chemicals inas
disinfectgenerally,

The
taken

up

preparationof medicinal soaps appears

m

the

scientificmanner

by Unna

of

of soap in preferenceto
the application
of certain remedies.
advocated

use

Hamburg
as
plasters

he
soap-stock made
"nsi?ered
toll"ef(TtiCallr'
tallow the most suitable for the
but in
a

purpose,

to have

been

in 1886
a

first
who

vehicle for

from
entirely

beef

practicefound that

TOILET,

TEXTILE

AND

MISCELLANEOUS

87

SOAPS.

obtained by usinga superfatted

the bent results were
soap made from
of
of
olive
oil
with
blend
one
of
beef
a
part
eightparts
tallow,
saponified
with a mixture of two parts of soda to one
of
cient
potash, suffipart
fat

being employed

to leave

researches

ponified..Recent

an

of 3

excess

4 per cent,

or

unsa-

have

shown, however, that even

ig
beneficial for the preparationof
superfattedsoap-base

if

toilet
which
is
to
it
is
doubt),
open
soaps (a point
quiteinadmissible for
of gennicitlal
and disinfectant
the manufacture
soaps, the bactericidal
o
f
is
much
which
restricted
efficiency
by the presence of free fat.
of
the
medicaments
added
to
Many
methods
soaps requirespecial

therein,as they otherwise react with the soap and

incorporation
decompOHO it,forming comparativelyinert compounds. This applies
of

to salts
particularly

and
chloride,,

of mercury, such as
biniudide of mercury,

considerable germicidalpower,
If
BoapH.
taken
quickly

to

niniplymixed
placebetween

and

with

are

corrosive

sublimate

both of which

or

curic
mer-

have

very

added
consequentlyfrequently

the soap

in the mill,reaction

very

the mercury salt and the soap, with formation

of the* inBoluhle mercury
of
the
compounds
fatty acids,a
bo readilyseen
in such a soap by the
to occur
change which can
rapid development on keeping,of a dull slaty-green
appearance.
have
been
and
NumeroiiH
in
cases
suggested,
some
proccBgeB
to
patented,

this

overcome

In
difficulty.

the

case

of corrosive

limate*,
sub-

that the soap to which this reagent is to be

GeiHsIer BUtftftwted
of fattyacids,and would therebybe
should contain an excess

added
rendered

stable.

This

salt has

also been

with milled
incorporated
with ammonio-mercuric
Htate in conjunction,
chloride,
/3Hoap in a clry
It
and eucalyptol.
is claimed that these
methylnalicylate,
naphthol,
in
and become
bodiett are
an
active
condition,
unchanged
present
whan the soap in added to water as in washing. Ehrhardt (Eng. Pat.
of making antiseptic
a method
2,407, 1H98) patented
mercury
soap by

alhuminate~~a

using mercury
casein,which

IB

combination

chloride and
soluble in alkali,
and added to the soap in an alkaline
of mercuric

solution.
obviated
With hiniodide of mercury the interaction can be readily
of
the
biniodide
of
potassium
by adding to
mercury an equalweight
in 1886,
iodide. This process, devised and patentedby J. Thomson
has been worked

Birice that time with

results.
extremelysatisfactory

|, 1, and 8 percent, biniodide are sold,but owing to

the readiness with which it is absorbed by the skin a soap containing
than | par cent, should onlybe used under medical advice.
more
of bromide of mercury with potassium
A similar combination
Strengthsof

sodium, or ammonium

bromide

has

recentlybeen patentedby Cooke

for admixtures with liquid,

hard, or soft soaps.
%itu? and oth"r Metallic Halts." At various times salts of metals
solubilit
other than mercury have been added to soap, but, owing to their inin water, their

medicaments
as
efficiency

is very

trifling

nil. Compounds have been formed of metallic oxides and other

or
salts with oleio acid,and mixtures made with vaseline and lanoline,

88

MANUFACTURE.

SOAP

and

incorporatedwith

but

soap,

they

have

not

met

with

much

cess.
suc-

of
In view
commonly added to soap is Borax.
is
no
this
litmus
salt
blue,
red
litmus,turning
on.
doubt generallyregardedas alkaline,and, as such, without action
salt
cess
exacid
the
On
an
containing
contrary,however, it is an
soap.
to
when
it is added
hence
of boric acid over
the soda present,
the
to
acids
quickly
liberated,causing
are
soap
soap, fatty
necessarily
become
rancid.
As a remedy for this it has been proposed to add sufAnother

chemical

its alkaline

reaction

to

ficient alkali to convert

which

into neutral mono-borate

the borax

of

soda

the
added to the soap.
This process is patented and
"
salt.
The
neutral
Kastilis
has been
tion
incorporagiven to the
forms the subject of
of borax with the addition of gum
tragaspl
tergent
patents (Eng. Pats. 4,415, 1904 ; and 25,425,1905) ; increased dethe
for
Another
and
soap.
lastingpropertiesare claimed
is then

"

name

two

patented process (Eng. Pat. 17,218, 1904) consists of coatingthe borax

with
before adding to the soap with,
a
protective
layerof fat or wax
acid
the idea that reaction will not take placeuntil required. Boric
and
of
the defects of borax in a greaterdegree,
would,
course,
possesses
simply form sodium borate with liberation of fattyacids,so should
be added

never

to

neutral

soap.

Acid is often recommended

for certain skin diseases, and
Salicylic
here
again the addition of the acid to soap under ordinaryconditions
and free fattyacids.
results in the formation of sodium
salicylate
this a process has recently
been patentedfor rubbing
To overcome
the acid up with vaseline before addition to soap, but the simplest "way
to be to add

appears

the

Amongst
Tar

Birch
a

for

salt of the acid to soap.

milled medicated toilet soaps
to the above :

common

in addition

mentioned,
has

the soda

more

Soap, containing5

characteristic

be

may

"

birch tar, which,

per cent,
is recommended
as
a remedy

10

or

odour

pungent

and

and

psoriasis.
than
3
Soap. A toilet soap should not contain more
of pure phenol,for with largerquantities
irritation is likelyto
cent,
skins.
experienced by susceptible
eczema

Carbolic

Coal

"

Tar.

"

These

soaps

contain,in

homologues, naphthalene and

Various
naphthol, bases, etc.
tar

used, but

are

point
this

of view

case

are

with

as

exceed

should

not

should

also

be

the most

other

blends

valuable

of different fractions

constituents

of it

are

of its

account

unpopular.

The

by and blends well with

cassia, lavender, spike,and red thyme.

Formaldehyde.
"

known,

from

of

its

coal,
coal

disinfectant

undoubtedly the phenols,or tar acids,though in

and
of phenols
cresylic
soaps, the amount
3 per cent, in a toilet soap. An excess
of naphthalene

modified

of

from

carbolic

avoided, since, on

containing much

addition to carbolic acid and

hydrocarbonsderived

per
be

This

and

substance

it may

be

is

one

strong odour, soaps

odour
a

of coal

tar is

siderably
con-

perfumv containingoils

of the mosfc

introduced
readily

powerful

into soap

infectants
dis-

with.ou.ti

f
I

90

MANUFACTURE.

SOAP

The

Terebene.

"

of this substance

addition

to soap,

ing
though impart-

and pleasant odour, does not materially

increase
a very refreshing
A suitable strengthis 5 per cent.
the disinfectant value of the soap.

septic
unpleasant,and very useful antif
or
the
of
ulcerated
especially
cleansing
soap,
normal
and restoringthe skin to a healthy state.
The
wounds
It
is
t
o
the
preferable replacepart of
thymol
strengthis 3 per cent.
to
odour
with red thyme oil,the thymene of which
sweeter
a
imparts
A suitable blend is 2-Jthe soap than if producedwith thymol alone.
a
nd
of
cent,
of
cent,
a good red thyme oil.
1J per
thymol crystals
per
of less known
vast number
Of tlpie
proposed additions to toilet
in
made
be
passingof ,:
may
soaps, mention
These have been somewhat
Fluorides.
popularduringrecent years
This furnishes

Thymol.
"

not

recommended

"

"

of breweries, etc., and

for the disinfection

as

preservatives.Of

food

only

course

also used

neutral

to

fluorides

extent

some

available

are

in soap, acid fluorides and soap beingobviouslyincompatible.

In the authors' experience,
however, sodium fluoride appears to have
for

use

little value
found

as

The

"

The

it

"

such

soaps

being

albumen
a

are, that it neutralises

copious

more

lather,and

free

helps to

and
closely,

more

soap,

"

to

yield

to

to

change colour.
egg, milk,and vegetable in soap
this country during the past few

in

attributed

the soap

causes
alkali,

bind

of albumen

use

claims

added

and

advocated
persistently

been

years.

rancid

rapidlybecome

to

Albumen.
has

germicidewhen

further

inducement

held

out

is that

it

left in the soap without

water
to
its firmness.
allows more
affecting
made
the
authors
did
not
to
Experiments
justify
by
appear
be

enthusiasm

any

in this

making
be

may

for

and
subject,

Continent.

the

to be very

country appears

the

on

the

on

Numerous

use

of albumen

however
slight,

other

substances

for

soappopular it
have

been

addition

to
proposed
including yeast, tar from
soaps,
peat
wood
S
wedish
of
(sphagnol),
tar, permanganate
potash, perborates
and percarbonatesof soda and ammonia, chlorine compounds, but

of these has at

none

present come

only ephemeral existence.

to admix

the skin, the

and
Ether

we

in soap

for

not

into

many

drugs that it has

favour, and

some

been

had
gested
sug-

in

allayingan irritable condition of

ments,
obviouslybetter appliedin the form of oint-

majorityare
need

Of the

much

use

consider

Another

Soap.
liquidether

form

them

further.

of medicated

by a few
soap made
mercuric
and
intended
iodide,
soap containing
for surgeons'use.
from olive
This,as a rule,consists of a soap made
oil and potash,dissolved in alcohol and mixed with ether,the mercuric
firms is

"

iodide

being dissolved in a few drops of water containingan equal

and this solution added to the alcoholweight of potassium iodide,
ether

soap.

FloatingSoaps. Attempts have

been

"

soap

that will float upon

floats,or
between

metallic

the

metal

the

platein
.and

made

to

produce tablets

of

surface
such

the soap.

of water, by insertingcork, or
that there is an air
manner
space

The

more

usual

method

is to in-

TEXTILE

TOILET,

corporateinto

hot soap

AND

MISCELLANEOUS

91

SOAPS.

sufficient

of a specially
air,by means
designed
jacketedcruteher,in which two shafts carryingsmall
blades or paddiesrotate in oppositedirections,
to reduce the density
of the soap below that of water
and so enable the compressed tablet
to float. The difference in weightof a tablet of the same
size before
self-contained

and

after

to 10 per cent.

aeratingamounts

is used

Ordinarymillingsoap

as

basis for this soap ; the settled

(77"G.) is carefully
ised
neutralstearic
or
acids,or boro-gly-

soap direct from the copper at 170" F.

with bicarbonate of sodium, oleic

ceride,perfumedand aerated.
which

Floatingsoap,

be recommended

cannot

as

owing
properties,

usuallywhite (some are of a cream

tint),
in lathereconomical,whilst its deficiency
ing
occluded air,is a serious drawback
to its

is

to

toiletdetergent.

popularityan a
Shavht-j*SVwyM?."Thofirst essential

of

from

any

from

its freedom

caustic

alkali

the skin,is the

lather which in lasting.Gum

effect upon
irritating

creamy
eases

give lastingpower

to

this property is
of

The

shaving soap, apart

substance

exertingan
a
profuse

quick
tragacanthis used
productionof

but
durability,
of
the
use
by

in

some

is not
a

necessary, as
suitable proportion

best

shavingsoaps are mixtures of various proportions

tion
potashsoaps, producedby the combinaof ordinarymillingbase with a white potashsoap, either melted
milled together. Glycerineis sometimes added,and is more
factorily
satis-

potash soap.

of neutral

or

or

attained
readily

or

soda and

milled in.

Every precautionshould be taken

to ensure

thorough saponifiea-

tion of the soaps intended for blendingin shaving soap, otherwise

there will ba a tendencyto become discoloured and developrancidity

with age.
Shaving soaps are delicately
perfumed,and are placedon
the market either in the form of sticks which are cut from the bar
of soap as it leaves the compressor, or stampedin flat cakes.
nature
and pastes are of the name
as shaving
Shaving creams
of
contain a largerproportion
soaps, but usually
and considerably
water,
more

TEXTILE

material
superfatting

SOAPS.

the use of soap

In the woollen,cloth,and silk textileindustries,
for detergentand emulsifying
purposes is necessary in several of the
in
of the kinds of soap
processes, and the following a brief description

successfully
employed in the various stages.
1. Woollen
Indmtry."The scouringof wool
operation"it is the firsttreatment

raw

is the most

wool is

ant
import-

to, and
subjected

sequent
efficientmanner,
givesrise to serious subfinisher.
troubles to manufacturer,dyer,and
the wool-fat and wool
The objectof scouringwool is to remove
terol
(exuded from the skin of sheep),consistingof cholesperspiration

if it is not

and

performedin

an

and potassiumsalts of fattyacids,

together
isocholesterol,

92

MANUFACTURE.

SOAP

other salts,such

with

as

phosphates. This
solution,containingin

chlorides,and
sulphates,

dilute soap
washing in a warm
of soda ; the fatty
of low quality
wool, a little carbonate
the case
removed.
and
is therebyemulsified
matter
easily
for
the
be free from uncommust
suitable
be
to
purpose,
Soap,
and rosin.
bined caustic alkali,
fat,silicates,
unsaponified
solution of caustic
in
dilute
be
dissolved
a moderately
Wool
can
in small quantities,
soda, and the presence of this latter in soap, even

is effected by

liable to

is therefore

possess

"

harsh

injurethe

feel,"and

fibres and

be devoid

fabric

the resultant

make

of lustre.

besides reducingthe
Unsaponifiedfat denotes badly made soap
this fat may
be absorbed
emulsifyingpower of the liberated alkali,
trouble in
but also cause
by the fibres and not only induce rancidity
dyeing.
"

Soaps containing silicates

have

may
to become

deleterious

action

upon

damaged and broken.

By generalconsent soaps containingrosin are unsuitable for use
by woollen manufacturers,as they produce stickyinsoluble lime and
magnesia compounds which are depositedupon the fibres,and give
in the dyeing.
rise to unevenness
A neutral olive-oil soft soap is undoubtedlythe best for the purpose
in water, it
of wool
scouring,as, owing to its ready solubility
out, and produces a
quickly penetratesthe fibres,is easilywashed
good feel so essential in the best goods,and tends to preserve the
of the fibre.
lustre and pliability
The high priceof olive-oil soap, however, renders its use
tive
prohibibe
for lower class goods,and in such cases
better soap can
no
suggested than the old-fashioned curd mottled or curd soaps (boiled
The
caustic alkali.
very dry),as free as possiblefrom uncombined
after
with
oil
this
olive
i
s
raw
or
wool,
cleansingoperation, oiled
oleine,priorto spinning; after spinningand weaving,the fabric,in

the fibres,causingthem

"

"

the form

of yarn

in

soap

oleine-soda
such

or

cloth,has

general use

most

Some

soap.

to be

for

scoured

manufacturers

fabrics

prefera cheap

The

oil.

to free it from

scouringwoollen

is neutral
curd

soap,

"

is

second
where
curd," and in cases
generallytermed
lower gradesof wools are
the
is
often
to
user
handled,
willing have
containingrosin (owing to its cheapness)and considers a little
soap
desirable to assist in removing the oil.
alkalinity
Another
operation in which soap is.used, is that of millingor
fulling,
whereby the fabric is made to shrink and thus becomes more
The
fabric is thoroughlycleansed,
compact and closer in texture.
as

for which
and

the
purpose
otherwise
silicates,

Curd

soaps
oil,with or

or

finely-fitted
soaps

without

All traces
to be

be neutral and free from rosin

soap should
harsh
a
feelingor stickiness will be produced.
made

the addition

of soap

must

from

of cocoa-nut

tallow

or

bleached

oil,give the

palm

best

sults.
re-

be

removed
carefully

if the

on

the

assist the mill-

fabric is

dyed.

The

woollen

dyer uses

soap

dyed piecesto

TEXTILE

TOILET,

AND

MISCELLANEOUS

SOAPS.

93

ing, and finds that a good soap, made from either olive oil,bleached
and, althoughit is generally
palm oil,or tallow,is preferable,
specified
a little
is not of consequence, for the
to be free from alkali,
alkalinity
woollen goods are, as a rale,acid after dyeing,and this alkalinity

instantlyneutralised.
fibres are unacted upon by caustic
2. Cotton Indwtry."Cotton
the
used
in
that
so
cleaningand preparingcotton goods
alkali,
soap
for dyeing need not be neutral,in fact alkalinity
is a distinct advantage
in order to assist the cleansing.
Any curd soap made from tallow,with or without the addition of
would

be

quantityof cocoa-nut

oil,may be advantageously
used for removing
the natural oil.
additions of soap are often made to the bath,
In cotton dyeing,
the
be of good odour and neutral,lest
and in such cases
soap must
the colours should be acted upon and tints altered. Soaps made
kind of
from olive oil and palm oil are recommended.
The same

small

used for soapingthe

soap is sometimes
The calico-printer considerable
the printod-cloths. The soap not

dyed cotton goods.

of soap for cleansing
quantities
only cleanses by helpingto
of the adheringprinting
and
constituents
the
starchy
remove
gummy
the
paste,but also playsan importantpart in fixingand brightening
colours. Hoaps intended for this class of work must be quiteneutral
alteration in colour by the action of free
(to obviate any possible
from

free
alkali),

These

in water.

odour and rosin,and readily

soluble
objectionable
olive-oil
are
qualities possessedby
soaps, either

in
A neutral olive-oilsoft soap, owing to its solubility
for
used
with
most
delicate
be
fibrescoloured
cold water, may
dyes,
and this soap is emin hot soap solutions,
ployed
be fugitive
which would

hard.

soft or

for the moHt

work.
expensive

generaluse ; those made from

recommended, although theyare not so soluble as

Olive-oil curd (soda)soaps

palm oil

are

also

are

in

Tallow curd soaps are sometimes

used, but th"
theydissolve is a drawback, and renders them
unsuitable.
somewhat
the sericin or silkis scoured to remove
NUk
3.
Imlmtrij."Bilk
producingtherebylustre
glueand adheringmatter from the raw silk,
the dyer.
it
for
th" softened fibre and thus preparing
on

the olive-oil soaps.

with which
difficulty

olive-oilsoft soap ; oliveThe very

soap for the purpose is an
The soap is often used
oil and oleino hard soaps may also be used.
in conjunctionwith carbonate of soda to assist the removal of the
itis necessary to avoid
sericin,
but, whilst carbonates are permissible,
an

excess

Tallow

of caustic soda.

soaps are
the scouringof silk.

so

slowlysoluble that they are

not

to
applicable

of a pleasant
soap, which is neutral and
dyer of silk requires
is given to neutral olive-oil soft soap, but
odour.
The preference
hard
(made from olive oil,oleine,or palm oil)are used chiefly
however, that the soap
of cheapness. It is essential,
account
on

The

94

should

rosin

from

free

be

cling

would

acids

Patent

of

finishing

and

the

of

obviating
solution

of

It

special

soap

additions

use

with

together
to

carbonate,

ash,

or

scarcely

soda
contain
be

or

termed

of

have

the

by

soaps

ordinary

been

and

petroleum,

and

dry

made.

turpentine,

action

of

85
soap.

to

soaps),

stains),

tar

soap),

(tooth
are

other
90

per

mentioned

soap),
(for

these

ox-gall

alkali

sulphides

home-dyeing
oil, in

pine-needle

massage

soaps

and

be

may

colours

soaps),

(for

crystals,
from

the

from

classed

be

essentially

carpet-cleaning

carbonate

powders

object

sulphonating

by

may

increased

is

aniline

(silversmiths'

magnesium

of

additions

(for

oil

chalk

its

liberated

substances

various

soap

other

lanoline

remove

for

this

heading

fractions

tripoli (motorists'

and

often

deposited

it

grease.

many

lead-workers),

of

of

the

therefrom

derivatives

Soap

precipitated

is

nor

the

sulphuric

not

alkali

of

consisting

and

naphtha,

removing
the

Amongst

chalk,

goods

soap.
this

"

of

power
in

substances

pumice

with

is

has

accomplish

to

Under

additions
of

1897).
wool,

upon

the

purposes

which

detergent

(for

used

cotton

by heating

oil

soap,

1897)
be

to

of

prepared

product

the

16,382,

Pat.

making

Soaps.

to

With

or

Soap,

castor

ordinary

is

as

proposed

is

in

used

fat

for

intended

the

of

that

effects

injurious

Miscellaneous

boiled

stated

(Eng.

soap.

the

of

soap

24,868,

Pat.

printing

is

treatment

dye-bath

patent

Another

part

dyeing
The

rosin
results.

fibres.

the

upon

the

on

is

it

and

the

in

used

when

textile

alkali,

with

Monopole

in

quent
conse-

liberated

any

termed

and

and

use

disagreeable

produce

and

(Eng.

fabrics.

(obtained

oil

sulphonated
acid)

oils

when

Stockhausen
soap,

Turkey-red

of

place

for

frequent

its

bath,

dye

fibres

silk

Soaps."

claim

special

makes

to

Textile

acid

the

the

of

account

on

in

decomposition

in

MANUFACTURE.

SOAP

soaps),
instances

some

pearl-ash

magnesia,

rouge,

powdered

orris,

(for

soap

tended
in-

ammonium

precipitated

soaps).
powdered
chemicals,
cent,

mixtures
whilst

siliceous

of

soap,

polishing
matter,

and

soda

soaps
can

VIII.

CHAPTER
SOAP

Oils

Essential

"

and

Source

PERFUMES.

and
Preparation"-Properties-Artificial

Synthetic

Perfumes.
THE

of

number

raw

materials, both

natural

and

at the
artificial,

perfumer, has increased so enormously during recent

become
of soaps has now
art. requiring
an
years that the scenting
of
the
and
a
considerable
thorough knowledge
skill,
productsto
very
Not only does the all-important
be handled.
questionof odour come
of
the soap, and
the perfumes on
into consideration, but the action

disposalof

on

the

other,

has

also

bo

taken

to

essential oils and

on

some

added,

soap, and soon

while in a few cases,

not

bergamot oil,the

oils like

chieflyon

decompose any
the blendingof
odour

content, it is very
containing much
soaps

their ester

be added

to

soap
two

reaction,in the effect of each

results,by mutual
of

account.

cause

with

case

into

Thus, many
the
darken
to
perfumes
synthetic
rapidly
soap
vanillin. Further,
keeping, e.g., clove oil,cassia oil,heliotropin,
patible
odoriferous substances, from their chemical nature, are incomeach

value

to

which

unsuitable

they are
perfumes

being lost.
of

In

the

which

depends
important that these should
free alkali,
as

those

esters

Some

are
perfumes possess the property
readilydecomposed thereby.
other and more
to retain
delicate odours conof helping the soap
siderably

are

known

longer than would otherwise be possible. Such

and among
as
"fixing agents" or "fixateurs,"

perfumes
the most

be mentioned
ficial,
musk, both natural and artimay
and
civet,the oils of Peru balsam, sandalwood, and patchouli,

important of these
benzyl benzoate.
The

natural

for addition to soaps are almost

consist of essential oils,balsams,

perfumes employed

entirelyof vegetable origin,and

and resins,animal
perfumes such as musk, civet,and ambergris bein^
reserved principally
for the preparationof
extraits",
As would
be expected with products
of such diverse character,
the
the methods
siderably.
employed for
preparationof essential oils vary conthe
be
divided
however,
Broadly speaking,
processes may
into three classes
(1) expression,used for orange, lemon, and lime,
oils ; (2)distillation,
employed for otto of rose, geranium,sandalwood,
and
oils
other
(3) extraction, includingenfleuraye,
; and
by
many
which the volatile oil from the flowers is either firstabsorbed by a neu"

"

95

II
96

MANUFACTURE.

SOAP

tral fat such

as

and
lard,.

then

extracted
directly

or
alcohol,

solvent such

as

extracted therefrom

from

the flowers

by

by
means

maceration
of

benzene, petroleum ether, or chloroform.

in

volatile
The last

furnishes productsmost
nearlyresemblingthe
process undoubtedly
which does not destroythe
natural floral odours, and is the only one
delicate fraganceof the violet and jasmine. The yield,
however, is-

extremelysmall, and concrete

therefore somewhat
costly.
The essential oils used
botanical

Africa

Thus, from

bay,bois de

are

and
families,
have

we

are

perfumes preparedin
derived from
obtained

geraniumand

rose, Canadian

this way

are

ent
upwards of twenty differ-

from

all partsof the world.

clove oils ; from

America,

snake root, cedarwood, linaloe,

mint,
pepper-

and sassafras ; from Asia,camphor,cassia,cinnamon,

petitgrain,
and the grass oils,
sandalwood,star anise,ylang-ylang,
viz.,
patchouli,
citronella,
lemongrass,palmarosa,and vetivert ; from Australia,
bergamot,lemon
eucalyptus
; while in Europe there are the citrus oils,
and orange, producedby Sicily,
neroli,
aspic,lavender,
petitgrain,
and rosemary
by Prance, caraway and clove by Holland, anise by
Eussia,and otto of rose by Bulgaria.
essential oils either on
a
Attempts have been made to classify
botanical basis or accordingto their chemical
composition,but
the chief conneither method is'verysatisfactory,
stituents
and, in describing
have
and properties
of the more
we
preferred
importantoils,
ence.
therefore to arrange them alphabetically,
as
being simplerfor referf

TV

III

to judge the purityof essential

difficulty
complex nature, but owing to the very
effect
their
producedby growing the plantsin
properties
great
upon
and
and stillmore
different soils
under varyingclimatic conditions,
to
the highlyscientificmethods of adulteration adoptedby unscrupulous
will be found,however, to include all
vendors.
The following
figures

It is

matter

of

some

onlybecause of their

not
oils,

oils.

normal

Anise Stell,or Star Anise, from the fruit of Illicium verum,

tained
obfrom China.
Specific
gravityat 15" C., 0'980-0'990;optical
2" ; refractive
+ 0" 30' to
or laevo-rotatory,
20" C., 1'553-1'555;solidifying
bility
point,14"-17" C. ; solu-

dextrorotation,faintly
index

at

in 90 per cent, alcohol,

1 in 3 or 4.
chief constituents of the oil are

The

anethol,methyl chavicol,
and in older oils,the oxidation productsof
1-phellandrene,
d-pinene,
anethol,viz.anisic aldehydeand anisic acid. Since anethol is the most
valuable constituent,
and the solidifying
point of the oil is roughly
anethol
oils
its
with a higher solidifying
to
proportional
content,
the
best.
pointare
Aspic oil,from the flowers of Lavandula
spica,obtained from
France and Spain,and extensively
employed in perfuminghousehold
and
cheap toilet soaps ; also frequentlyfound as an adulterant
in lavender oil. Specific
gravityat 15" C., 0 '904-0 '913 ; optical
rotation,French, dextro-rotatory
up to + 4", rarelyup to + 7",

'[I

SOAP

98

MANUFACTUBE.

inverted beaker, the inside of which

ffi

When

4!

and

t^

is burnt, the

the

is moistened
is rinsed

paper
the filtrate tested for chloride with
snake

Canada

oil,from
C., 0*940-0*962

root

;[,)

gravityat 15"
Specific

|:il

rotatoryup to

|1

tion* number,

'

with

distilled water.

with

water, filtered,
silver nitrate solution.
Canadense.
the root of Asarum

beaker

laevorotation,slightly
optical

4" ; refractiveindex at 20" C.,1*485-1*490

100-115; soluble

in

or

volumes

saponifica-

of 70 per

cent.

alcohol.
constituents of the oil are
principal
and methyl eugenol. The
another alcohol,
toilet soaps.
used in* other than high-class
The

terpene,asarol alcohol,

oil is too

expensiveto

be

Cananga or Kananga oil,the earlier distillatefrom the flowers of

Cananga odorata, obtained chieflyfrom the PhilippineIslands.
-17" to
Specificgravityat 15" C., 0*910-0'940; opticalrotation,
30" ; refractive index at 20" C., 1*4994-1*5024 ; esters,Wculated as
-

8-15

benzoate,
linalyl
per

cent. ; soluble in
on

1*5

to 2 volumes

further addition.

of 95

'

similar in composition
to Ylang-Ylang oil,
qualitatively
benzoate and acetate,esters of geraniol,
cadmene,
linalyl
\
methyl ester of p-cresol.
oil is

The
and

per

alcohol,but becoming turbid

cent,

contains

and

carui.
Specific
oil,distilled from the seeds of Carum
fractive
C., 0*907-0*915 ; opticalrotation,+ 77" to + 79" ; \reof ^80
at 20" C., 1*485-1*486 ; soluble in 3 to 8 volumes

Caraway

gravityat 15"
index

per cent, alcohol.

which

The

oil should

contain

is estimated

with a
by absorption
of
sulphite. The remainder

sodium

50-60 per cent, of carvorie,

saturated solution of neutral
the

oil

consists

limonene.
Cassia

,.t

'i|

oil,distilled from the leaves of Cinnamomum

cassia,and\
\
this country from
China in lead receptacles.Specific

shipped
gravityat 15" C.,
to

1 '060-1*068 ;

dextro-rotarotation,slightly
optical

tory up to +3" 30' ; refractive index at 20" C.,1-6014-1*6048 ; soluble

in 3 volumes
of 70 per cent, alcohol as a generalrule,but occasionrequires1
jally
The

I;I

chieflyo)f
\

value

^constituent
with
:are

to 2 volumes

of the

of 80 per cent, alcohol.

oil depends upon its aldehydecontent, the chief

being cinnamic

aldehyde.

This is determined

tion
by absorpbisulphite.Three grades
80-85 per cent, aldehydes,
the
containing
cent.,and the lowest grade, 70-75 per

hot saturated solution of sodium

usuallyoffered,fhe
quality,75-80

second

best
per

scent.

Other constituents

of the oil are cinnamyl acetate and cinnamic

givesthe characteristic odour to Brown Windsor soap,
and is useful for sweetening
coal-tar medicated soaps.
Cedarwood oil,distilled from the wood
of Juniperusvirginiana.
Specificgravityat 15" C., 0*938-0*960; opticalrotation,-35" to
-45*; refractive index at 20" C., 1*5013-1*5030.
The
principal

acid.

ft

l\
1,|

This

constituents

oil

are

cedrene

and

cedrol.

Cinnamon

from the bark of Cinnamomum

oil,distilled
zeylanicum.
Specific
gravityat 15" C.,rOO-l*035 ; optical
rotation,

Isevo-rotatory

j||

HOAP

PERFUMES.

99

2" ; usuallysoluble in 2 to 3 volumes

of 70 per cent, alcohol,
up to
1 volume
of 80 per cent, alcohol for solution
but sometimes
requires
-

"

by
aldehydes,
cent. ; and

potash,not

sodium

bisulphite
solution,
55-75 pet
by absorptionwith 5 per cent.

phenols,as measured
exceeding12 per cent.

value of this oil is not determined

in the case
with cassia oil,and
as

The
content

75 per

than

absorptionwith

aldehydesmust

cent,

admixed
probably

be

entirely
by its aldehyde
any

oil

more
containing

regarded with

suspicion,
being

with

either cassia oil or artificial

cinnamie aldehyde.
leaf oil which has a specific
The addition of cinnamon
gravityat 15"
r()44-rO("5
of
detected
Is
C.
by causinga material risein the proportion
of phenols. Besides cinnamie aldehyde
the oil contains eugenol
and phollandreno.
Citronella OIL" This oil is distilledfrom two distinctAndropogon
the former beingthe
pangiri,
grasses, the Lana Batu and the Maha
the
of
bulk
of
a
nd
the latter beingcultivated in the
source
Ceylon oil,
The oils from these three localities
Straits Settlements and Java.
show woll-definod chemical differences.
at 15" C.,0'900-0'920 ;
Ceylon Citronella ailhaH the specific
gravity

rotation,huvo-rotatory
optical
up
1 "480-1*484 ;

to

soluble in .1 volume

lisahlc constituents,calculated
XinyaiHM Citnmdla Oi/."

as

12U

refractiveindex at 20"

of 80 per cent, alcohol ; total

54-70
geraniol,

C.,

acety-

per cent.

Specific
gravityat 15" C.,0'890-0*899;
laworotation,usuallyslightly
optical
rotatoryup to -3"; refractive

*20" C., I '4(17-1*471 ; soluble in 1 to 1*5 volumes

alcohol ; total acetylisahle
calculated as
constituents,

index

at

of 80 per cent.
geraniol,80-90

per cent.
('UrtmrJ-la O*7.~- Specificgravityat

I5'J C., 0*890-0*901;

calculated
rotation,
acetylisable
constituents,
optical
in
1-2
volumes
soluble
cent.
of
75-00
80
as
gt"raniol,
;
per cent.
par
alcohol.
The chief constituents of the oil are
geraniol,citronellal,
Jinalol,
Jura

"-

I'1to

("" ; total

bornttol,methyl ougt'.nol,
camphone, limouene, and dipentene. It is
very

inning cheap soaps,

jxirf
of geraniol.
for the production

largelyuwtl

source

mtt

tie Itone. Femdle

litan
wood

for

of trotw

Q'874-0'880 ;

or

Cay mine

and

Imaloe

also

serves

as

oil,distilled from

species. Specific
gravityat 15" C.,
rotation, -11" 80' to -1C"; refractive index at
optical
of the Jiursoracou^

20" C!., l'4(KJ8-r4030

soluble iu 1'5 to 2 volumes

of 70 per cent.

alcohol.
The

oil consists almost

fiabla bodies,but appears

by Barbiar and Bouvoault
finer in odour

than

with traces of saponientirelyof linalol,

from
he
free
to
methyl heptenone,found
in Mexican

source

tinctly
oil is dis-

product.
unripeblossoms of Eugenia

the Mexican
the

Cltmi oil, distilled from

the chief
phyllata,

linaloe oil. This

of which

is East

caryo-

Africa (Zanzibar and

gravityat 15" C., 1*045- 1*061 ; opticalrotation,

Pemba). Specific
1" 80' ; phenols,estimated by absorpIf"vo-rotatory
slightly
up to
-

MANUFACTUEE.

SOAP

potashsolution,86-92

per cent. ; refractive index

of 70 per cent.
soluble in 1 to 2 volumes
at 20" 0., 1*5300-1*5360 ;

with 5 per cent,

iaon

alcohol.
of the oil
constituent
principal
and
acet-eugenol.While
caryophyllene

is

The

its

value of this oil is determined

eugenol, togetherwith

within

certain

limits

the

eugenol content, oils containing

in odour,
usuallyless satisfactory

by
than 93
phenols are
more
at the expense of the
of phenols being obtained
the high proportion
with less than 88
Oils
of
the
sesquiterpene.
decompositionof some
in odour.
weak
will be found somewhat
This oil is
per cent, phenols
is
and
toilet
an
stituent
importantconsoaps
extensivelyused in the cheaper
As alreadymentioned, however,it causes
of carnation soaps.
in colour somewhat
and must
fore
not therethe soap to darken
rapidly,
in
coloured
in
used
be
except
any quantity,
soaps.
substance
obtained by steam
tion
distillaConcrete orris oil,a waxy
per cent,

of Florentine

orris root.

Melting point,35-45" C., usually40"-45" C.

free

lated
calcuacidity,

myristicacid, 50-80 per cent. ; ester,calculated as combined

acid, 4-10 per cent.
Htyristic
The greaterpart of the productconsists of the inodorous myristic
The
acid, the chief odour-bearingconstituent being irone.
high
its
renders
of
the
oil
in
use
the
best
only possible
price
quality
very
as

soaps.

EucalyptusOil." Though there are

oils belongingto this class,only
to the

hundred

some

two

or

of much

are

more

ferent
dif-

importance

soap-maker. These are :

(L) Eucalyptuscitriodora. Specific
at 15" C., 0'870-0*905 ;
gravity
opticalrotation,slightly
dextro-rotatory
up to + 2" ; soluble in 4-5
"

volumes

of 70 per cent, alcohol.

almost
entirelyof citronellicaldehyde,and on
absorptionwith saturated solution of sodium bisulphite
should leave
The

oil consists

littleoil unabsorbed.

very

the
(ii.)
Eucalyptusglobulus,

oil used

in

pharmacy,and

ing
contain-

50-65

percent, cineol. Specific

gravityat 15" C., 0'910-0'930
1"
+
to + 10" ; soluble in 2 to 3
optical
rotation,
parts of 70 per cent!
alcohol; cineol (estimated by combination with phosphoric acid
"

pressing,
decomposingwith

hot water, and

not less than 50

fflneol),
per cent.
and
d-pinene,
valeric,butyric,and

medicated

in

Fennel
grown

in

measuring the liberated

Besides cineol,the oil contains

caproic aldehydes.

(sweet)
oil,obtained from
Germany, Eoumania, and

the fruit of Fceniculum

other parts of Europe.

rln1^^^
'

hi
but

+6'to

USUaUy S"luble in
1'.61fi-1V6*8
;

occasionally
requires1 part of

vulgare
Specific

reSve

25";

2-6 Parts 80
Per ce"t

90 per cent,
'

Geranium

It is chiefly

soaps.

alcohol

fenchone"d-P

oils,distilled
from plants of the
Pelargoniumspecies.

SOAP

There

101

PERFUMES.

three

kinds of this oil on the market

the African,
principal
and
the
the
Algeria
Bourbon, distilled
neighbourhood,
in the Island of Reunion, and the Spanish. The oil is
principally
also distilled from plantsgrown in the South of France, but this oil
is not much
used by soap-makers. A specially
fine article is sold
of
by a few essential oil firms under the name
Geranium-sur-Rose,"
which
its name
as
is supposed to be geranium oil distilled
implies,
Tins is particularly
suitable for use
roses.
in high-class
over
soaps.
The
the
o
f
these
oils. It will be
are
following
general properties
that the limits for the figures
seen
overlap to a considerable extent.
are

"

obtained from

"

both free,and combined

geranioland citronellol,
with tiglie,
The
and acetic acids ; also 1-menthone.
valeric,butyric,
varieties are the two most
African and Bourbon
commonly used for
soap-perfumery,the Spanish oil being too costlyfor extensive use.
'Gwt/Gr-i/raxfi
oil,formerly
regarded as an inferior kind of palmastated
from
different source.
to
be
but
an
rosa
now
entirely
Specific
rotation,+ 15".
gravityat 15" C., 0'B89-0*897 ; optical
of geraniol,
The oil contains a largeamount
togetherwith di-hydroand i-carvone.
cuinin alcohol,d-phellandrene,
d-limonene,dipentene,
Tho

oil containH

oil,distilled from the wood of Bulnesia sarmienti.

Specificgravityat 30" C., 0"967~Q*975 ; opticalrotation,-4" 30' to
umes
7"; refractive index at 20" C., 1'506-1BB07 ; soluble in 3 to 5 vol(.hullo?*wood

of 70 per cent, alcohol.

The principalconstituent of the oil is

This

oil,which

has

used
occasionally

what

as

an

is

guaiac alcohol,or

termed
generally

adulterant

for otto of

"

tea-rose

guaioi.

odour// is

rose.

oil,distilledfrom the flowers of Lavandula

vera, grown
ably
England, France, Italyand Spain. The English oil is considerand is seldom, if ever, used in soap. The
the most expensive,
Lavender

in

French

and

Italian oils

are

the most

article,of
new
comparatively
resemblingaspicoil.
closely

English Oil"

common,

doubtful

Specificgravity

at

the

Spanish oil being

botanical origin,and

15" C., 0*883-0*900;

more

optical

10" ; esters,calculated as linalyl

acetate, 5-10 per
rotation, 4" to
of 70 per cent, alcohol.
cent. ; soluble in 3 volumes
-

MANUFACTURE.

SOAP

at 15" C, 0'885-0'900 ;
gravity
French and Italian Oils." Specific
20" C., 1'459-1'464 ;
at
index
refractive
9"
2" to
;
ootical rotation,
20-40
cent., occasionally
acetate,
per
calculated as linalyl
-

esters

hidaer

There

at

was

the higherthe

theorythat

theory has

this

the oil,but

is

there

discredited,and

become

extent

time

one

better

of ester the

of 70 per cent, alcohol.

soluble in 1*5-3 volumes

now

that

doubt

no

to

proportion

very

some

large
of the

30 per cent, of esters.

finest oils contain less than

gravityat 15" C., 0'900-0'915

SpanishOil" Specific
esters, calculated

tion,
rota; optical
acetate,2-6 per cent. ;
linalyl

2" to + 7" ;
of 70 per cent, alcohol.
soluble in 1-2 volumes
of lavender oil are
The chief constituents
-

and
geraniol,

linalylbutyrate,while

and
from Sicily
obtained almost entirely
rotation
0'856-0'860
15"
at
C.,
optical
;
gravity
Italy.Specific

frnit of Citrus limonum,

Southern

58"

acetate, linalol,
linalyl
English oil also contains a

oil,prepared by expressingthe peel of the nearly ripe

Lemon

the

of cineol.

distinct amount

\:

as

and

63"; refractive

to +

at 20"

index

C., 1'4730-1'4750

aldehydes

2*5
(citral),

'

and citral,
principalconstituents of the oil are limonene
of
octyland nonyl
togetherwith small quantities pinene,phellandrene,
and
the
acetate,
stearopten,
geranyl
aldehydes,citronelM, geraniol,

cent.

to 4 per

The

'

citraptene.
verbena] oil,distilled from the grass
Lemon-grass (so-called
in
recently,
dropogon citratus,which is grown in India and, more

West

their

/*
";

?
;
4

oils from

The

Indies.

these

two

differ somewhat

sources

Anthe
in

and also in value, the former beingpreferred

on
acproperties,
in alcohol.
of its greatersolubility
count
East Indian.
Specific
gravityat 15" C.,0'898-0'906 ; opticalroof
tation, 0" 30' to 6" ; aldehydes,by absorptionwith bisulphite
soda solution,
65 to 78 per cent. ; refractive index at 20" C., 1*485"

1*487

soluble in 2-3 volumes

West

Indian.

of 70 per cent, alcohol.

Specificgravity at 15" C., 0'886-0'893 ; optical

rotation,faintly
Isevo-gyrate
; refractive index at 20" C.,1 '4855-1 '4876 ;

soluble in 0*5 volume

Lime

the

fruit

"

of 90 per cent, alcohol.

oil,obtained
by expression or distillation of the peel of
of Citrus medica, and produced principally
in the West

Indies.

Specificgravity at
Expressed^!."
rotation,4-

Distilled Oil.

"

oil

Its

rotation,+ 38"
alcohol.

15" C.3 0'870-0'885 ; optical

importantconstituent is citral.
This is entirely
different in character to the expressed
specificgravityat 15" C. is 0'854-0'870 ; optical

38" to +

to +

50".

Its most

54" ; soluble

in 5-8

volumes

'

of 90 per

cent.

Linaloe oil,distilled from the wood

of trees of the Burseraceee
family,and obtained from Mexico.
Specific
gravityat 15" C., 0'876u WJ
; opticalrotation,
3" to
usuallyIsevo-rotatory,
13", but oomsionaHy dextro-rotatory
to + 5" 30';
up
esters, calculated as
-

SOAP

103

PEBFUMES.

linalylacetate, 1-8 per cent. ; total alcohols

54-66 per cent. ; soluble in
by acetylation,

as

1-2

linalol,
determined
volumes

of 7O

per

cent, alcohol.

mainly of linalol,togetherwith small quantities

of methyl heptenone,geraniol,and d-terpineol.
Marjoram oil,distilled from Origanum majoranoides,and obtained
entirelyfrom Cyprus. Specificgravity at 15" C., 0*966 ; phenols,
chieflycarvacrol, estimated by absorptionwith o per cent, eaxistic
oil consists

This

potash solution, 80-82

cent, alcohol.
This oil is used

per cent.

; soluble

in

2-3 volumes

in place of
occasionally

in soap

red

of 70

thyme

per

oil.

Biyarade oil, distilled from the fresh blossoms of the

Citrus bigaradia. Specificgravity at 15" C., 0"875bitter orange,
0'882 ; opticalrotation, -f Ou 40' to 4- 10", and
much
occasionally
refractive
1
index
20"
at
C,, '468-1*470; esters, calculated as
higher;
10-18
cent.
80
of
acetate,
; soluble in 0*75-1*70 volumes
linalyl
per
Nerali

per cent, alcohol,becoming turbid

chief constituents
of the
The

on

further addition of alcohol.

Hmonerie, linalol,
linalyi
acetate, geraniol,methyl anthranilate,inclol,and neroli camphor.
OranyG (sweet)oil,expressedfrom the peel of Citrus aurantiuzxu
at 15" C., 0*849-0*852; opticalrotation,+95"
'gravity
to
Specific
index
refractive
at 20" 0., 1*4726- 1/4732.
4- 99";
oil

are

togetherwith nonyl
citronellal,
alcohol,d-linaiol,
citral,
d-terpineol,
decylaldehyde, and
anthranilate.
methyl
Palmarosa, or East Indian (jeraniuni oil,distilled from Andropoin India.
Specific
gravity
gon SchamanthuH, a grass widely grown
at

The

oil contains

15"

C., 0*888-0-895; optical

rotation, 4- 1"

index

at

some

90 per cent, limonene,

20" CM 1 '472-1*476

per cent. ; total alcohols,as

70 per cent, alcohol,1 in 8.

esters,calculated
75-93
geraniol,

as

per

to

;..f
; refractive

linalyl
acetate, 7-14
in
cent; solubility

chieflyof geraniol,free,and combined with acetic

used in cheap toilet
and caproic acids,and dipentene. It is largely
in rose
It is also a favourite adulterant
soaps, particularly
soaps.
of goraniol.
for otto of rone, and is used as a source
Patchouli oil,distilledfrom the leaves of Pogostemon patchouli,
herb
in India and the Straits Settlements.
a
Specific
gravity
grown
at 15" C.,0*965-0*990
45"
refractive
f"8u
index
to
r
otation,
optical
;
;
at 20" C., I"504~r611
number, up to .12; sometimes
; saponification
soluble in 0*5 to 1 volume of 90 per cent, alcohol,becoming turbid on
of the oil in alcohol increases with
further addition.
The solubility
The

oil consists

age.

The

of 97 per cent, of patchouliol

and
its odour, and the bodies relittleinfluence on
sponsible

oil consists to the extent

cadinene,which

have

and
for its persistent

characteristic odour have not yet been

isolated.

Peppermint oil,distilled from herbs of the Mentha family, the

European and American from Mentha piperita,and the Japanese
The
beinggenerallysupposed to be obtained from Mentha arvensis.

104

MANUEACTUBE.

SOAP

on
localityin which the herb is "grown has a considerable influence
show :
the following
as
the resultingoil,
figures
tion,
gravityat 15" C., 0'900-0'910; opticalrotaEnglish."Specific
-22" to
33"; total menthol, 55-66 per cent.; free menthol,
"

of 70 per cent, alcohol.

soluble in 3-5 volumes
per cent. ;
tion,
American."
gravityat 15" C.,0'906-0'920; opticalrotaSpecific
menthol,
20" to -33"; total menthol, 50-60 per cent.; free
of 70
The Michigan oil is soluble in 3-5 volumes
40-50 per cent.
but the better Wayne
County oil usually requires
per cent, alcohol,
of
of 80 pei*cent, alcohol,and occasionally
0*5 volume
1-2 volumes
50-60

90

alcohol.

per cent,

French."
Specific
gravityat 15" 0.,0'917-0'925 ; opticalrotation,
10" ; total menthol, 45-55 .per cent. ; free menthol, 35-45
6" to
of 80 per cent.
per cent. ; soluble in 1 to 1"5 volumes
rotation,
gravityat 25" C.,0'895-0'900 ; optical
Japanese." Specific
-

Isevo-rotatory
up

to

43" ; solidifies at 17 to 27" C.

65-85
70-90
per cent., of which
of 70 per cent, alcohol.
volumes

oil is fluid at

dementholised

The

per

gravityof 0'900-0'906
specific

at

is

cent,

total menthol,

ordinarytemperatures,

15" C., and

contains

3-5

in

free; soluble

has

per cent.

50-60

total menthol.
Some

twenty

different constituents

have

been

found

in

American

peppermint oil,includingmenthol, menthone, menthyl acetate, cineol,

amyl alcohol, pinene,1-limonene, phellandrene,
dimethyl sulphide,
isovalerianic
aldehyde,acetaldehyde,acetic
menthyl isovalerianate,
acid, and isovalerianic acid.
balsam
Peru
oil, the oilyportion (so-called cinnamein
"

")

tained
ob-

Specificgravityat- 15" C., 1 "100-1 '107 ;

opticalrotation, slightly
dextro-rotatory
up to + 2" ; refractive index
at 20" C., 1'569 to 1*576 ; ester,calculated as benzyl benzoate, 80-87
from

Peru

balsam.

; soluble in 1 volume

per cent.

oil consists

The

with

styracin,
or

and

benzoic

of
chiefly

cinnamic

cinnamylcinnamate,and

the

South

bigaradia.There
American,

gravityat 15"
index

at 20"

by distillationof
two

are

the former

C., 0'886-0'900

C., 1'4604-1'4650

40-55 per

cent., for the

soluble

as

small

ther
toge-

quantity of free

acids.

oil,obtained
Petitgrain
of Citrus

of 90 per cent, alcohol.

benzyl benzoate and oinnamate,

best

rule in 2-3 volumes

the

twigsand unripe

varieties of the

oil,the French

fruit
and

valuable.
being the more
Specific
6"
3"
to
+
rotation,
optical
; refractive
;

esters, calculated

as

qualities
usually above
of

70

per

cent,

linalylacetate,
50

cent. ;
per
but
alcohol,
sionally
occa-

1-2 volumes
of 80 per cent, alcohol.
requires
its
constituents
are
Among
lirnonene,linalyl
acetate,geraniol and
geranyl acetate.
Pimento
oil (allspice),
distilled from the fruit of Pimenta
offioinalis,
which
is found in the West
Indies and Central America.
Specific
gravityat 15" C., 1'040-1'060; optical
rotation,slightly
laevo-rotatory
up to -4"; refractive index at 20" C.,1'529-1'536 ; phenols,estimated

i il
gOAp

santalol,92-97 per
cent.
cent, alcohol,thougH
an

cent, alcohol.

Australia^.-

West

rotation,+ 5
insoluble m
volumes

to + 7

70 per
of 80 per cent,

West

Indian.

MANUFACTURE.

usuallysoluble in 4-6 volumes

old oil occasionally
is insoluble

at 15" 0.,0'950-0'968 ; optical

Specific
gravity
73-75 per cent. ;
alcohols,calculated as santalol,

alcohol,but readilydissolves

cent,

in

1-2

alcohol.

'Specific gravityat

rotation,+ 13 30' to
In addition to

of 70 per
in 70 per

30"

15" 0., 0'948-0'967

optical

insoluble in 70 per cent, alcohol.

santalol,the oil contains esters of santalol and

-f-

free

santalal.

oil,distilled from
Sassafras
from.
chiefly
America.

obtained

rotation,~f~
optical

1"

50' to +

the bark

of Sassafras

and
officinalis,

at 15" 0., 1'06-1'08

Specific
gravity

4";

refractive index at 20"

0., T524-

1'532; soluble in 6-1O

of 85 per cent, alcohol,frequently
volumes
soluble in 1045 volxaro.es of 80
per cent, alcohol.
The chief constituents
are
safrol,pinene,eugenol,
camphor,and
The
phellandrene.
either intentionally
removal
of safrol,
or
by ac-

cident,owing to cooling
is readily
detected
safrol,

of the oil and

of
consequent deposition

the reduction

by

of the

the

below
specific
gravity

1'06.

Thyme oil,red
c"nd
white, distilled from the green or dried
herb,Thymus vul^aris,
both French and Spanishoils beingmet with.
These oils are
French."

entirely

different in character.

laevoSpecific
gravityat 15" 0., 0'91-0'933 ; slightly
rotatoryup to 4", font usuallytoo dark to observe ; phenols,
by abwith 10 per
cent,
caustic potash,
25-55 per cent. ;
sorption
aqueous
-

refractive index

2O"

at

C., 1'490-1'500;

soluble in 1-1*5 volumes

of 80 per cent, alcohol.

Spanish."Specific gravityat 15" C.,0'955-0"966 ; optical

rotation,
l88vo-gyra,te;phenols, 70-80 per cent. ; refractive index at
slightly
206C.,I'5088-r512l2
; soluble in 2-3 volumes of 70 per cent, alcohol.
In addition to tHe
these oils contain
phenols,thymol or carvacrol,
axiLd.
pinene.
cymene, thyrnene
The white thym"
the red oil,which
oil is produced by rectifying
effected.
of a considerable reduction in
a,t the expense
is generally

phenolcontent,ancL
Verbena

Oil."

"

laence
T3o.e

in real odour
oil

value of the oil.

usuallysold under

this

name

is

really

supra). 'The true verbena oil or French

met with. This is distilledin France
occasionally

oil (wlxicli
lemon-grass

see

verveine is,however,
from the verbena oJ9S.cinalis,and has the following
: Specific
properties
dextro- or
rotation,slightly
; optical
gravityat 15" G., O"891-0*898
of
; alcielaydes, 70-75 per cent. ; soluble in 2 volumes
lavo-rotatory
70 per cent. alcob.ol
citral.
The oil contains
.

Vetivert

Cus

oil,distilled

Cus,and growxi.
gravity
Specific

in
at

from

the

grass,
the East Indies.

Andropogon muricatus,or

15" C., rOl-1'03; opticalrotation,

+ 20"

to

SOAP

-f

26"; saponification
number,

1*521- 1*524

|
I

oil makes

at

20" C.,

of 80 per cent, alcohol.

prohibitive
except in thehighestclass soaps.
of this oil,the
WinteryreenOil. There are two natural sources
and
Betula
the
lenta.
Gaultheria
Both
oils consist.
procumbens
of methyl salicylate
almost entirely
and are practically
identical in
the chief difference being that the former has a slight
properties,
its

use

"

while
Isevo-rotation,

the latter is inactive.

Specificgravityat 15" C., 1*180-1*187

1", Betula oil,inactive
oil, up to

|
!

15-30; refractive index

soluble in 2 volumes

price of this

The

jf

107

PEBFUMES.

theria

at

soluble

Gaulopticalrotation,
as
methyl salicylate,

; ester
cent. ; refractive index at 20"

least 98 per
in 2-6 volumes

Besides

methyl

ketone, and

C., 1*5354-1*5364

of 70 per cent, alcohol.

the oil contains triaconitane,
an
salicylate,

ihydeYlamj-ylantjoil,
or

an

aide-

alcohol.

distilled from the flowers of Gananga odorata,

being the PhilippineIslands and Java.
Specific
-80"
to
15"
at
Q*924-0'95G
rotation,
-60", and
C.,
gravity
; optical
higher; refractive index at 20" C., 1*496-1*512;ester,
occasionally
calculated as linalyl
benssoate,27-45 per cent., occasionally
up to
50 per cent. ; usuallysoluble in i volume of 90 per cent, alcohol.
the same
The compositionof the oil is qualitatively
that of
as
more
expensiveand therefore can
Cananga oil,but it is considerably
only be used in the highestgrade soaps.
the

chief

sources

SyntheticPerfumes.

and
Artificial

During the past few yearn

studied by a considerable

of essential oils has

the constitution

of chemists,and the composition

that very good
oils has been BO fullydetermined
of many
at cheaper pricesthan those of the
imitations can
often be made
been

number

genuine oils,rendering it possibleto produce cheap soaps having

expensive
formerlyonlypossiblein the more
perfumes which were
article.
There
between

in
an

however, often lost sightofy

distinction,

considerable

and
artificial

oil.
synthetic

An

artificialoil may be
from certain natural

produced by separatingvarious constituents

oils,and HO blending these,with or without the addition of other
.substances,as to produce a desired odour, the perfumebeing,at any
rate in part,obtained from natural oil#. A synthetic
perfume, on
the other hand, is entirelythe productof the chemical laboratory,
position.
natural oil or substance derived therefrom enteringinto its comno
The

followingare

among

important bodies

the most

of

this

class :"
the
Amyl salicylate,

acid,sometimes
used for the

known

ester
as

of
production

preparedfrom amyl

"Orchidee"
a

or

alcohol and

"Trifle".

clover-scented soap.

salicylic

This is much

It has the

specific

108

SOAP

MANUFACTURE.

1" 16' to + 1" 40' ;

ro tation,+
15" G., I'052-r054 ; optical
refractive index at 20" G., 1*5056 ; and should contain not less than
97 per cent, ester, calculated as amyl saiicylate.
Anisic aldehyde,or aubfyine,preparedby oxidation of anethol,
at
gravity

and

possessing

hawthorn
pleasant,

odour.

This

has

the specific

20" G., 1*5693

; is optically
gravityat 15" 0.,1*126; refractive index at
inactive,and dissolves readilyin one volume of 70 per cent, alcohol.
Benzyl Acetate,the ester obtained from benzyl alcohol and acetic
coarse,
acid. This has a very strong and somewhat
penetrating
Its
at 15" G.
specific
g
ravity
resemblingjasmine.
odour, distinctly

index at 20"
is 1 '062-1*065;"refractive

G., 1*5020; and

it should

tain
con-

at least 97-98 per cent, ester, calculated an benxylacetate,

in lemon-grassand verbena
the aldehydeoccurringlargely
Citral,

oils,also

to

intense

an

less extent

lemon-like

ami
arid orange oils,
possessing
It has a specific
at
15
G.,
gravity

in lemon

odour.

inactive,and should
0'896-0'897, is optically
a

hot saturated solution of sodium

be

absorbed by
entirely

bisulphite,

an
Citronellal,
aldehyde possessingthe characteristic odour of
of about 20 per cent,,
to the extent
citronella oil,in which it occurs

90 per cent, of eucalyptuseitrioover

considerably
constituting
dora oil. Its specific
gravityat 15" G. is 0"8("2 ; refractive index at
it should be en20" G., 1*447; opticalrotation,
+ 8" to -h I4!';and
tirely
absorbed by a hot saturated solution of sodium
bisulphite.
Coumarin, a white crystalline
productfound in Tonka beans, and
from salicylic
acid.
It has an odour resembling
prepared synthetically
new-mown
hay, and melts at G7' G.
in geranium, paltnaGeraniol, a cyclic
alcohol,occurringlargely
citronella oils. Its specific
gravity at If/" 0, in 0'8H3rosa, and
0*885; refractive index at 20" C., 1 '4762-1 '4770; it in optically
inactive,
and

and

boils at 218"-225" G.

which possesses
the characteristic odour of heliotrope,
Heliotropin,
is prepared artificially
in small
from safrol. It crystallises
86"
at
G.
prisms melting
Hyacinth. Most of the articles sold under this name
secret
are
blends of the different makers.
odour
Styrolenehas an
vary much
of these
resemblinghyacinth,and probablyforms the basis of moat
and other artificialbodies. The
togetherwith terpineol,
preparations,
o
f
the
oil
for different makes.
properties
vary considerably
lonone,a ketone first prepared by Tiemann, and having when
diluted a pronounced violet odour.
It is preparedby treating
ture
a mixof citral and acetone with barium hydrate,
and distilling
in racuo.
Two
isomeric ketones, a-ionone and /S-iorione,
are
produced, the
article of commerce
being usually a mixture of both. The two
ketones have the followingproperties
:~
Alpha-ionone."Specificgravity at 15" 0., 0'9338 ; refractive
"

index

at

16*5" G., 1*50048

Beta-ionone."
at

it is inactive.
(Chuit); optically
Specific
gravityat 16" C., 0-9488; refractive index

16*8" G., 1*52070

(Ohuitj
it is inactive
; optically

also.

productis usuallysold

The

ready for

This

is

of the

one

few

20

or

per

alcoholic solution

cent,

in which

cases

that obtained

is probablysuperiorto

from

delicacyof the

the extreme

to

in 10

use.

Jasmine."

siblydue

109

PERFUMES.

HOAP

the artificial
oil

the natural

odour, and

flowers,
pos-

its

consequent

slight decomposition during preparation from the flowers. The

chemical compositionof the floral perfume has been very exhaustively
studied,and

the artificialarticle

now

on

the market

may

be

of

triumph
synthetical
chemistry. Among its constituents
benzyl acetate, linalylacetate, benzyl alcohol,indol,.
methyl anthranilate, and a ketone jasrnono.
Linalol, the alcohol forming the greater part of linaloe and bois
de rone
oils,and found also in lavender,neroli,petitgrain,
bergamot,
other oils. The article has the specific
and many
gravityat 15" G.,
rotation, 12" to
14n; refractive index at 20"
0"870-0'87("; optical
and
when
.1*464;
estimated
l"46;j;
by
C.,
acetylation,
yieldsabout 70
described

as

are

per

of alcohols.

cent,

Linalyl

acetate

b"rtjamntoil,is the
artificial

formed
when linalol is treated with acetic anhydride. It possesses a bergamot-like odour, but it in doubtful whether its value in commensurate
with its greatlyincreased priceover that of ordinarybergamot oil. It
has

specific
gravityat 15" (1, 0*912.
I
I
rt
Musk
(.
fiaial)." Bo vend forum of this are

enter

the

all of which
The

or

to lie obtained,practically

nitro-dorivativog of aromatic

aro

originalpatent of Baur,

obtained

in

1889, covered

hydrocarbons.
the tri-nitro-

The

derivativo of

melting pointof the pure

tortiarybutyl xyiene.
108" and 112' G., and the.solubility
in 95
article usuallylinn Iwtwoem
120
from 1 in
to 1 in 200, though more
uble
solper cent, alcohol nmgas
forms

ara

also made.
should

important adulterant,which

always lie tested for,is

by the characteristic
may
musk
odour
produced whcm
containingthin substance is
isocyariiclo
boiled with alcoholic; potash,and a few drops of chloroform added.
An

be detected

which
acetanilido (antifobrin),

Acetanilide also increases the

Neroli Oil (.-Irtifir,
w/)."
oil is

in 95
solubility

per cent, alcohol.

Like jasmineoil,the chemistry
of neroli

fullyknown, and

it is therefore

possibleto prepare an
approximationto the natural oil,
the market, which, on
of their
such are now
and many
account
on
themselves to the soap-perfumer.
comparativecheapness,commend
These
consist
of
linalol,geraniol,
chiefly
linalylacetate, methyl
now

very

artificial productwhich

is a very good

and citral,
anthranilate,
Mirbanc

Oil

bitter almonds,

or
or

Ni/.r"4"j;t^w6"."Thisis
and is
btjn/.aldehydo,

only suitable
by the action

of

use
a

cheap substitute

for oil of

very coarse, irritating

fume,
perin the very cheapestsoaps.
It is prepared
mixture
of nitric and sulphuric
acids on

gravity
.temperaturenot exceeding 40" (3. Its specific
1'205-1*206 ; refractive index at 20" Q, 1*550; arid boiling"
point,

benzene
is

for

a
a

206" C.

at

110

MANUFACTUBE.

SOAP

Niobe oil,or ethylbenzoate, the ester obtained from ethylalcohol

benzoic acid, and having the specific
gravityat 15" C., 1*0941'095 ; refractive index at 20" C.,1*5167 ; boiling
point,196*5"-198"C. ;

and

soluble in 1*5 volumes

of 70 per cent,

alcohol.

possessedof a sweet carnation-like odour

and
having as a basis,eugenol or isoeugenol.Its propertiesvary
of supply.
with the source
Several good and fairly
Bose Oil (Artificial).
cheap artificialrose
of citronellol,
linaoils are now
obtainable,
chiefly
geraniol,
consisting
cases
lol,phenyl ethyl alcohol, and citral. In some
stearoptenor
Oeillet is

combination

"

similar in appearance
to
added, to render the oil more
but as these are inodorous,no advantageis gained
the natural article,
in cold weather
in this way, and there is,further,the inconvenience
other

of

first melt the oil before

having to
Safrol,

-an

ether which

much

used

is very
in
Its specific
gravityat

household

soaps.
1*106; refractive index at 20" C., 1*5373; and
of 80 per cent, alcohol.
volumes
or

Santalol,the alcohol

mixture

or

oil,and

It is sold

as

an

or

potaj

15" C. is 1*103-

form

of

glyc"

it dissolves in fifteen

of alcohols obtained

from

sandal-

0'862-0'868

specific
gravityat 15" C. is
d
extroor
frequentlyslightly
Isevo-rotatory
;

medicated

the oil is

the refractive index

the result

as

In Chapt
(1)the glyeei
is contained
salt and
chief

C., 1*470-1-478.

last

Much

att

oentration
been

'

othe

source

earlyin

Its

soaps.

at 20"

pointed c

perfuming cheap

oil. Its specific

gravityat 15" C. is 0'9795 ; opticalrotation,
-18"; and refractive index at 20" C., 1*507.
Terebene,a mixture of dipenteneand other hydrocarbonsprepared
with concentrated
irom turpentine
oil by treatment
sulphuricacid,is

chieflyin

As
soda

wood

uised

ofj
Dynamite

of Q-Lyceri')

quantityin camphor oil.

oil, and

artificial sassafras

Treatment

use.

is the chief constituent of sassafras

in considerable

also found

toilet

GLYC

is

wax

of

devised

Treatment

alcohol also prepared from turpentine oil by the

an
Terpineol,
termediate
inof sulphuricacid, terpene hydrate being formed
as
an
It has a distinctly
characteristic lilac odour,
substance.
of its cheapness is much, used in soap perfumery,
and on
account
lilac
for
Its specific
or
a
lilysoap.
especially
gravityat 15" C. is
0-936-0*940; refractive index at 20" 0., l'4812-l-4835 ; and boiling
and readilysoluble
inactive,
pointabout 210"-212" G. It is optically

only upon

the

also upon

th"

in 1*5 volumes

caustic

action

Vanillin,a

by

of 70 per cent, alcohol.

white crystalline
solid,meltingat 80"-82" C. and

the oxidation

odour, and

vanilla bean.

light-coloured
soaps,

soap.

isoeugenol. It has

associated

occurs,

in the
hteliotropin,
in

of

as

it

It

with
can

traces

only be

quicklytends

strong

prepared
istic
character-

of benzoic
used in small

to darken

acid

pans

the colour of the

coo

sation in the

their content

soda, s

the presence
o
if it is desired

The

and

quantity

are

is car
cooling,

and

lyes a;

treated

'

sulphate,
suffic
and
alkali,

ren

pletely
precipit
and

the point

litmus paper
The

b"

whole

the tank and

fi,

Having obi

CHAPTEE
GLYCERINE

Treatment

IX.

MANUFACTURE

AND

PURIFICATION.

of Lyes Evaporation to Crude Glycerine

Dynamite Glycerine Chemically Pure Glycerine
colorisation
Glycerine obtained by other Methods
of Glycerinefrom Fats and Oils.
"

"

"

"

"

Distillation

Distilled and
Charcoal
for Deof Saponification Yield
"

Animal

"

As

with
pointed out in Chapter II. the fattyacids,which, combined
form
in
almost
nature
i
n
or
potash,
invariably the
soap, occur
form of glycerides,
and
i.e.,compounds of fattyacids with glycerol,
is set free.
of a fat or oil glycerine
as the result of saponification
In Chapter V. processes
in which
of soap-making are
described
(1) the glycerineis retained in the finished soap, and (2) the glycerine
in the lyes,in very dilute solution, contaminated
is contained
with
salt and other impurities. These
the
constituting
lyes,though now
of profitin the manufacture
chief source
till
of cheap soaps, were
last
the
drains
waste
as
liquor.
earlyin
century simply run down
Much
has been devoted to the purification
attention
and
centration
conof glycerine
lyes,and elaborate plantof various forms has
soda

been

devised for the purpose.

from the soapof Lyes. The spent lyes withdrawn
has
cooled, and the soap, which
separated during the

Treatment
pans

are

"

sation
soap-housefor utiliin the manufacture
of brown
Spent lyes may vary in
soap.
this depends not
from 3 to 8 per cent., and
of glycerol
their content
the
but
the
of
the
in
working
only upon
soap-pans,
system adopted
the materials
used.
also upon
Although, in these days of pure
free from impuritiesthan formerly,
caustic soda, spent lyes are more
be carefully
the presence of sulphidesand sulphitesshould
avoided,
if it is desired to produce good glycerine.
The
size,
lyes are transferred to a lead-lined tank of convenient
aluminium
acid
and
with
commercial
treated
and
hydrochloric
the free
of
the former
to neutralise
added
sufficient
being
sulphate,
and
latter
of the
to completely
alkali,and render the liquorfaintlyacid,
should
acid
in
be
acids.
The
the
run
slowly,
precipitate fatty
indicated
blue
is
has
been
and
the point when
added,
by
enough
reddened
litmus paper being slightly
by the lyes.
with
a
is then agitated
The
whole
air,when
sample taken from
-the tank and filtered should give a clear filtrate.
Having obtained this clear solution,agitationis stopped, and

removed
cooling,is carefully

and

returned

111

to the

112

SOAP

the contents
which

of the tank

accumulates

the treatment

on

suspended

drain

The

by

it.

the addition

ready for
The

tank, and

of caustic

soda

or

the

liquorallowed to"
slightlyalkaline
is
carbonate,and, after filtering,

filtered liquoris

and

alum

carefullyexamined

rendered

now

salt used, in the above

for the

Lime, bog

ore,

and

various

chloride,and
instances

copper
instead

be

must

deliveries

any

impurity,rejected.

metallic

ferric chloride,
suggested, and in

such
salts,

sulphate have

used

are

treatment

of arsenic, and

presence
contain that

of either article,which

some

the

over

evaporation.

acid

barium

filter press.
The
scum,
tank, may be transferred to

passed through a

perforatedhox
from

MANUFACTUBE.

as

been

of aluminium

sulphate,but

the latter

is

generallyemployed.
Evaporation to Crude Glycerine. The clear treated lyes,being
free from fatty,
now
ing
resinous,and albuminous
matter, and consisto
f
solution
of
salt (sodium
common
practically an aqueous
is converted into crude glycerineby concenchloride)and glycerine,
tration,
"

which

eliminates

the water

and

of the salt to be

most

causes

deposited.
This

concentration

fire

originally
performed in

was

combustible

open pans heated

of each pan was

or
by
gases.
lifted
and this dish was
placed a dish in which the salt deposited,
out periodically
and
the contentsby the aid of an overhead crane
washed.
and
continued
until
Concentration
the temperwas
emptied
ature
of the liquorwas
300" F. (149"C.),when it was
allowed to rest

before

waste

storing.

This

10"

In the bottom

per

salts

cent,

80 per cent, glycerol

and
hence
the present standard

analysisgave

liquoron

(ash);

from

9 to

for crude

glycerine.
Concentration

in open

has

been

supersededby evaporation
vacuo.
subject
gradual development of the
modern
efficient evaporatingplantfrom the vacuum
pan, originated
in
and successfully
in 1813
the sugar industry,
applied by Howard
is too lengthyto detail here, suffice it to say that the multipleeffects
distinct advantages the greatestof these
in vogue
now
possess
with economy.
increased
efficiencycombined
being
pans

The

in

of

now

the

"

The
each

fitted with

hollow

direct steam,
into

lower

or

chamber

steam

with

steam

through
lyes circulating
temperature, with

the

one

which

fixed vertical

the exhaust

of the

steam

the heated

reduced

are

vessels,

more

first vessel is heated

from
(supplied
waste

or

tubes

pressure,

steam

factory)
;

is made
than

with

is

the

to boil at

possibleby

pans.

given

largepipes into the

latent heat

of the

the

passes

consists of

through

chamber

exhaust

which

heatingin open
The
vapour

further

evaporator

steam

The

tubes.

receiver
treated

of

present type

is utilised

reduced, as

off

steam

in

by

the

chamber

boilingliquoris conveyed through

of t)ae second

vessel,where

the
producing evaporation,

this second

vessel is under

pressure

greatervacuum

its

being
than

114

SOAP

MANTJFACTUBE.

producersthemselves ; others sell it to firms engaged

in the refined glycerine
tr,ade.
more
particularly
is distilledunder vacuum
Crude glycerine
wifch the
Distillation.
The
heated
stillis
aid of superheatedsteam.
with a coal or
directly
and in this fire space is the superheater,
which
consists of a
coke fire,
coil of pipesthrough which
high pressure steam from the boiler is
superheated.
at a temperature of 356" F. (180"C.).
The distillation is conducted
and
To prevent the deposition
burning of salt on the still-bottom
false
bottom
is supported about 1 foot from
ths
a
distillation,
during
the same
the base of the still. With
object in view, it has been
the
with
contents
an
suggestedto rotate
agitatorfixed in the still.
by

cases

the

"

Every

that

is taken

care

the

still does

not

overheated

become

not only prevents loss of glycerine

tion,
precaution
through carbonisabut also obviates the productionof tarryand other bodies which
might affect the colour,taste, and odour of the distilled glycerine.
The vacuum
to be used will,of course, depend upon
the heat of the
fire and still,
but as a generalrule good results are obtained with an

this

18 inch

vacuum.

There

of designs for still heads, and

quite a largenumber
"catch-alls,"
having for their object the preventionof loss of glycerine.
The

are

distillate passes

is attached

into

row

of

condensers,to

each

of which

receiver.
It is needless to state that the
or
receptacle
should
be
in
of theoretical requirements.
excess
condensingcapacity
The fractions are of varyingstrengths
and quality;that portion,
with
than
less
14" Tw. (19'4"B.), is returned to the treated-lyes
a density
tank.
The other portionof the distillateis concentrated
of
by means
coil in a suitable vessel under a 28 inch vacuum.
a dry steam
When
concentrated
the glycerine
sufficiently
be decolorised,
may
if necessary, by treating
with 1 per cent, animal charcoal and passing
".
througha filterpress, from which it issues as
dynamite glycerine
The residue in the still,
o
f
consisting 50-60 per cent, glycerine
and varyingproportions
of various sodium salts
e.g. acetate,chloride,
and combinations
with non-volatile organic acids
sulphate,
is generally
a

"

"

"

boiled with
The

and

water

lar,which

is

treated with

acid.

separated,floats on
by ladles,or

and may be removed

cooling,
charcoal,and filtered.
The
are

filtrateis then

driven

Distilled
of limited

use

is

ready

for

"

outlet in the manufacture

the

liquoris

other

as

mixed

volatile

finallymixed

it
distillation,
or

Glycerine. This
in various

surface

the whole

evaporated, when

off ; the concentrated

which
glycerine

the

may

the

liquoris

with

waste

organicacids
with

crude

be distilled1
ately.
separ-

class of commercial

branches

of

glycerine,
although
industry,finds its chief

of

explosives.
Specifications
are
usually given in contracts drawn
to which
buyers and sellers,
the productmust
conform.

up

between
,

GLYCERINE

The

MANUFACTURE

AND

115

PURIFICATION.

chief

for dynamiteglycerine
is its behaviour in the
stipulation
When
nitration test.
i
s
glycerine graduallyadded to a cold mixture
of strong nitric and sulphuric
acids,it is converted into nitro-glycewhich
as
an
rine,
oilylayeron the surface of the acid. The
separates
definite and rapid the separation,
more
the more
suitable is the
for
glycerine dynamite-making.
Dynamite glycerineshould be free from arsenic,lime, chlorides,
and fattyacids,the inorganicmatter should not amount
to more
than
0*1 per cent., and a portiondiluted and treated with nitrate of silver
solution should give no
discoloration in. ten minutes.
or
turbidity
bo
should
1'262 at 15" 0. (59"]?.)
The specific
and the colour
gravity
somewhat
yellow,
Chemically pure ylyoerim or double distilled glycerineis produced
distilled"glycerine.Every care is taken
once
by redistilling
"

to avoid all fractions which

do not withstand

the nitrate of silver test.

The distillationis very carefully

performedunder strict
The distillate is concentrated and after treatment
and

charcoal

filtrationshould

conform

supervision.
with

animal

to the

requirementsof the
British Pharmacopeia. These
are
specifiedas follows: Specific
It
15*5"
1*260.
should
at
characteristic reaction
G.t
no
yield
gravity
with the tents for lead, copper, arsenium, iron,calcium,potassium,
sodium, ammonium,
or
chlorides,
sulphates. It should contain no
sugars and leave no residue on burning,
Charcoal for Decohrination." The application
Animal
of animal
charcoal for decolorising
purposes dates back a century,and various are
that have been propoundedto explain
its action. Some
base it upon the physical
condition of the so-called carbon
present,and no doubt this is an important factor,coupled with
the views
observers

the

porosity. Others

consider that the

which
nitrogen,

is

present

is essendifficultto remove,
in all animal charcoal and extremely
tial
Animal charcoal should bo freed from gypsum
to the action.
in the burning,sulphurcompounds be formed
last
of
(sulphate lime),

which

would

into the

pans

and
glycerine

contaminate

it.

char" should bo well boiled with water, then carbonate of

The
in sufficient quantityto givean alkaline
or caustic ncxla added
and the
reaction,and again well boiled. The liquoris withdrawn
f"

longer alkaline. The

then separatedfrom the liquorand treated with hydrochloric

charcoal washed
charcoal i"

acid
Some
in

contend

until the

washings

are

no

of acid to be used.
opinionsdiffer as to the amount
that phosphateof lime playssuch an important part

that it should
decolorising

demonstrated

that

not

be

removed, but

this substance

it

after exposure

has, however,
to

heat

has

power.
very littledecolorising
Animal charcoal boiled with four times its weight of a mixture
from
acid (free
of equal partsof commercial
hydrochloric
consisting
free from acid,
arsenic)and water for twelve hours, then washed
of great
dried,and burned in closed vessels givesa productpossessed

decolorising
power

for

use

with

glycerines.

116

SOAP

goodanimal

MANUFACTURE.

charcoal will have a dull appearance, and be of a

and riot in the form of
in fine grains

deep colour ; it should be used

a

powder.

charcoal from the filterpresses is washed free from glycerin"

stances
cleansed from foreignsublyes),
revivifiedby carefully
heatingin
closed vesselsfor twelve hours.
obtained by other Methods of SapomfieatMmi.-^Vn^nch
Glycerine
is the result of concentracandle crude
tion
or
glycerine
saponification
"
and by
in
manufacture
of
stearino
the
of
sweet water
produced
The

(whichis returned to the treated

by the above treatment and

"

"

"

the autoclave process.

a

It contains 85-90 per cent,

glyeerol,
pOHKCHses

and
gravityof Ig240-l'242"
specific

be readilydistinguished
may
the absence of salt (sodium chloride).

glycerine
soap-crude
by
is
refined by treatment
with charcoal.
This glycerineeasily
methods
water
The glycerine
resultingfrom acicl saponification
the
of
the
addition
be
rendered
alkaline
t
o
lime"
sludge
by
requires
to
crude.
the
and
The concentration
is separated,
liquorevaporated
from the

of 32" Tw. (20"

in two stages" firstto a density
11),
performed
the calcium sulphateis allowed to deposit,
and the separated
liquorconcentrated to 48" Tw. (28"B.) glycerine,
testing85 par oont.
be

may

when

and upwards.
glycerol

Yield

Fain and Oifo." The following

represent
should be obtained from tho various materials

from
ofGlycerine

resultswhich
practicable
:"

9 per cent, of 80 per cent.

Glycctrol.

0
2
8

0
0
s

The

^aterials
vary

in

content with the methods

glyeerol

of preparation

is this the case

with tallows and greases,
; especially
Every care should be taken that the raw materials are fresh and

examined to ascertain if any decomposition

they should be carefully
has taken placein the glycerides"
this would
be denoted by the
of free acidity,
and the amount
of glyoerol
presence of an excess
obtainable from such a fat would be correspondingly
reduced.

CHAPTER
ANALYSIS

RAW

Oils"Alkalies

and

Fats

OF

X.

MATERIALS,
and

Alkali

SOAP,

Salts"Essential

AND
Oils"

GLYCERINE.

-Soap" Lyes" Crude

Q-lycerlne.
Materials."

Raw

-Average figureshave already been given in

and VIII. for the more
importantphysicaland chemical
characteristics
of fats and oils,also of essential oils the
following
;
IB an outline of the processes usually
in
their
determination.
adopted
ChaptersTIL

fuller details,
text-books dealingexhaustively
with
should
bo
consulted.
subjects

For

FATS

AND

It is vory undesirable that any

to enter the soap pan without
an

the

tive
respec-

OILS.

of these materials

should be allowed

having first been

analysis

made,

as

oil may
not only have become
partially
hydrolysed,involvinga
loss of glycerine,
contain
albuminous
matter
or
renderingthe soap
the

liable to

but actual sophistication

developrancidity,
may have taken
place).Thus a sample of tallow recentlyexamined
by the authors
contained as much
40 per cent, of an unsaponifiable
which
as
wax,

have led to disaster in the soap pan, had the bulk been used
examination.
After observing the appearance, colour, and
odour of the sample,noting any characteristic feature,the following
physicaland chemical data should be determined.
would

without

of a
Gravity at 15" 0. This may be taken by means
Specific
Westphal balance,or by using a picnometerof either the ordinary
gravitybottle shape,with perforatedstopper, or the Sprengel UThe

tube.

at
picnometershould be calibrated with distilledwater
15" 0.
The specific
vated
gravityof solid fats may be taken at an elebath.
water
that of a boiling
temperature,preferably
Free
2
to 5 grammes
is
estimated
from
out
acidity
by weighing
of the fat or oil,dissolvingin neutral alcohol (purified
methylated
with gentle heat,and titrating
with a standard aqueous or
spirit)
alcoholic solution of caustic soda or potash,using phenol-phthalein
as

indicator.
The

contents

of the flask

are

well shaken

after each

alkali,and the reaction is complete when the slightexcess

causes
a permanent
pink coloration with the indicator.
alkali may

be

N/2, N/5, or N/10,

117

addition of
of alkali
The

dard
stan-

MANUFACTURE.

SOAP

118

of oleic acid (1 c.c. N/10

It is usual to calculate the result in terms
in percentage on
oleic acid),and
0'0282 gramme
express

alkali

the fat

oil.

or

1*8976

Example.
"

taken, and

were

grammes

N/10 KOH
^

5-2

0-0282

ij

\
A

per cent, free

=7*72

expressedas

'f

The

c.c.

of

100

j,

'}

required5'2

solution for neutralisation.

of KOH

the amount

expressedas
milligrammesnecessary
sometimes

acidityis

free

in
of fat

acid in 1 gramme
In the above

...

fattyacids,
oleic acid.

acid

value,which

is

to neutralise the free

oil.

or

example :

"

5*2

"

5*61

i
0
.-,
,
acid
15*3
value.
-

",

1-8976

'"

equivalentis
saponification

The

of fat or oil into

grammes

wide-necked

determined

by weighing 2-4
c.c. capacity),

flask (about 250

neutral alcohol,and

warming under a reflux condenser

the flask is disconnected,50
boiling,
a
semi-normal
alcoholic
of
c.c.
an
fully
potash solution careapproximately
from a burette, togetherwith
few
added
a
drops of phenolphthalein solution, and the boilingunder a reflux condenser
is complete
until saponification
continued, with frequentagitation,
from 30-60 minutes) which
is indicated by the absence
of
(usually
of alkali is titrated with N/l hydrochloric
fattyglobules.The excess
acid.
or
sulphuric
The value of the approximatelyN/2 alkali solution is ascertained
by taking50 c.c. togetherwith 30 c.c. neutral alcohol in a similar
flask,boilingfor the same
length of time as the fat,and titrating
with N/l hydrochloric
acid. The
or sulphuric
saponification
lent
equivais the amount
of fat or oil in grammes
saponifiedby 1 equivalent
561 grammes
of caustic potash.
or
fat required18'95 c.c. N/l acid to
Example. 1*8976 grammes
adding30

c.c.

steam

on

When

water-bath.

or

"

"

"

neutralise the unabsorbed

Fiftyc.c.
25'6

c.c.

alkali.

N/2
approximately

alcoholic

potash solution required

N/l acid.
25-6

18-95

1-8976

6-65

c.c.

N/l

KOH

requiredby

fat.

1000
=

-"

OQ,
285

-01
"*
.Saponmcation
Equivalent.
.

o'oo

The result of this test is often expressed as the

Saponification
Value,"which is the number
of milligrammes of KOH
requiredfor
the saponification
of 1 gramme
of fat. This
be
found
ing
by dividmay
"

56,100 by the saponification

equivalentor
number

of

by multiplyingthe

of

N/l alkali absorbed, by 56'1 and dividingby the

quantityof fat taken. Thus, in the above example :
c.c.

"

-=

196 '6

Value.
Saponification

ANALYSIS

OF

ester

The

RAW

ether

MATERIALS,

value, or

AND

SOAP,

number

119

GLYCERINE.

of

milligrammes of KOH
or
in 1
glycerides
of fat,is represented
by the difference between the saponification
gramme
In the example given, the ester value would
and acid values.
or

requiredfor the

be 196*6

15'3

of the neutral
saponification

esters

181:3.

Matter.
Unsaponifiable

The

"

of the fat

about 5 grammes
alcoholic potash solution

or

usual

method

oil with

50

The
a

of

c.c.

by boilingunder

for about 1 hour.

frequentagitation
basin over
to dryness in a porcelain

adopted is to saponify

solution

steam

N/2
approximately

reflux condenser

is then

with

evaporated

water-bath, and

or

the

When
soap dissolved in about 200 c.c. hot water.
sufficiently
solution
is
the
transferred
to
a separating
cool,
funnel, 50 c.c. of
soap
ether added, the whole well shaken, and allowed to rest.
The ethereal

resultant

layer is removed

to another
ether being added
separator,more
and
The two ethereal
solution,
again
separated.
soap

to the

aqueous
then
extracts are

washed

transferred
separated,

water

of any
soap,
ether distilledoff upon
a

unsaponifiablo
matter/' which

"

deprive them

to

flask,and the
residue,dried in the oven

The

water-bath.
is the

with

to

at 100" C. until

is calculated to

constant,

per cent,

on

the oil.

method, it is very

In this

most
difficultto obtain a
frequently
o
f
and
ether
solution"
intermediate
an
separation
aqueous soap
layerof emulsion remaining even after prolongedstanding,and various

distinct

been recommended
to overcome
this,such
(when petroleum other is used), glycerine,
more
caustic potash solution,or by rotatoryagitation.

have
expedients

water,
A
far

as

or

proceed as
dissolvingthe resulting
soap
better

twenty

or

planis

to

minutes.
thirty

in the
in 200

coal
Slightly

method
and

water
water

funnel

Two

alcohol

of the

grammes
saturated

with

some

fattyacids

are

the whole

dilute sulphuric

clear,wash

with hot

filtering
through

now

dissolved

hot

in neutral

a
solvent,preferably
lightfraction of

benzoline,a quantityof the solvent added

able matter, and

are

as

then boil for

acidifywith

acid (1 to 3), boil until the fattyacids

free from
mineral acid, and dry by

ether,

described

above

water, and

c.c.

tion
addi-

as

of alcohol

boiled under

to take
a

up

the

unsaponifi-

reflux condenser.

After

N/2 aqueous KOH

solution,using
of the
phenol-phthaleinas indicator,this figuregiving the amount
total fattyacids present. The whole is then poured into a separating
funnel,when separation
immediately takes place. The alcoholic layer
is withdrawn, the bonzoline washed
with warm
water
(about 32" C.)
followed by neutral alcohol (previously
saturated with the solvent),
cooling,the

is titrated with
liquid

and

transferred

and

the benssolmo

in the flask

are

the

flask cooled
fiable matter.
Constitution

to

tared

flask,which

distilled off.

The

is attached

last traces

to

of solvent

condenser,

remaining

by gentlywarming in the water-oven, and

of unsaponiand weighed, thus giving the amount

removed

Matter."
of the Unsaponifiable

matter
Unsaponifiable

120

MANUFACTUKE.

SOAP

solid alcohols
of cholesterol,phytosterol,

consist

may

ceryl alcohols),or

fats,and

in animal

found

phytosterolis

they give

bloom

or

of animal

to

vegetableoils and

or

alcohols

vegetablefats. Solid
present
which may
oil,but hydrocarbons,
in

sperm
the fluorescence

(cetyland

hydrocarbons(mineral oil). Cholesterol

is frequently

similar

very

stance
sub-

naturallyin
generallyrecognised by

be

occur

the oil,are

not

natural

stituents
con-

fats.

be detected by
phytosterol
may
matter
in acetic anhydride,
unsaponifiable
a
dissolving
drop of 50 per
and adding a drop of the solution to one
blood red
when
a characteristic
acid on a spot plate,
cent, sulphuric
been
It
has
tiate
proposed to differento violet coloration is produced.
their
and
cholesterol
by
melting points,but
between
phytosterol
the crystalline
forms, the former
it is more
reliable to compare
and
presence of cholesterol

The

small

portion of the

in laminse, while
crystallising

shaped

Another

tufts.

and

take its

method

the

latter

forms

of needlegroups
the substance
into acetate,

is to convert

melting point,cholesterol

melting at

acetate

114'3-

acetate at 125'6"-137U C.
114-8" 0., and phytosterol
been recentlyproposed by
have
cholesterol
for
Additional tests
Chem.
1908,
Lifschiitz (Ber. Deut.
252-255), and Golodetz
Ges.,

(Chem. Zeit.,1908, 160).

on

the oxidation

In

that

of cholesterol to

to the

due

former, which
and

ester
oxycholesterol

depends
oxycholes-

dissolved in 2-3 c,c.

are
terol,a few milligrammesof the substance
glacialacetic acid,a little benzoyl peroxideadded, and the solution
boiled,after which four drops of strong sulphuricacid are
added,
when

green colour is produced,if cholesterol is present,

ester, the green to oxybeing due to oxycholesterol
cholesterol.

violet-blue

the violet colour

or

suggested by Golodetz (1) the addition

trated
reagent consistingof five parts of concenacid and three parts of formaldehydesolution,which
sulphuric
cholesterol a blackish-brown,and
colours
(2) the addition of one
Two

of

one

or

two

tests

drops

of

are

drop of

30 per cent, formaldehyde-solution to a solution of the

in trichloracetic acid,when
cholesterol an
with
intense

coloration
Water.
into

is
"

tared

stance
sub-

blue

produced.
From

5 to 20 grammes

fat

of the

porcelainor platinum dish, and

whilst

being

heated

over

gas

or

oil

stirred

flame

at

are

with

weighed
a

mometer,
ther-

100" C. until

bubblingor crackinghas ceased,and reweighed,the loss in weight

In cases
of spurtinga little added
alcohol
representingthe water.
will carry the water off quietly.
To prevent loss by spurting,
Davis
(J.Amer. Chem. SOG.,23, 487)
has suggestedthat the fat or oil should be added
to a previously
dried and tared coil of filterpaper contained
in a stopperedweighing
bottle,which is then placedin the oven
and dried at 100" C. until
constant
in weight. Of course, this method
is not applicableto oils
fats liable to oxidation on heating.
or
Dregs,Dirt,AdiposeTissue,Fibre, etc. From 10. to 15 grammes
of the fat are dissolved in petroleumether,with frequentstirring,
and
'

"

122

and

of
equivalent

c.c.

by 100, dividingthe productby

the

the iodine

pliedby
"

MANUFACTTJKE.

SOAP

solution
thiosulphate
fat taken,

weight of

givesthe-

".

Number

Iodine

of the

Example. 1 c.c. of
equal to 0*0126 gramme
"

sodium

N/10

the

is found

solution
thiosulphate

iodine.
Blank

48'5 c.c. thiosulphate.

requires
40*0 c.c. thiosulphate.
Bottle containingoil requires
of the fat is
40*0
8*5, and the iodine absorption
48*5
0*3187

of fat taken.

gramme

"

8*5

Q'0126

100

33-6.
0-3187

that

Wijs showed
a

is

now

the

of

employment

of iodine

solution

acetic acid reliable iodine

in glacial

monochloride
in

by

obtained

figures

are

and this method

minutes being sufficient,
shorter time,thirty
the
Hiibl.
agent
in much
Wijs' iodine remore
generaluse than
iodine
in
litre
of
1
13
made
is
glacial
grammes
by dissolving

much

passingchlorine

acid and

acetic

iodine

all converted into

in

the

into

exactlythe same
way as
fat is preferably
dissolved in

with

until the iodine is.

solution

process is carried out

solution except that th"

The

monochloride.

Hiibl

the

tetrachloride instead

carbon

form.
of in chloro-

almost
has now
been
supersededby
entirely
absorption
methods.
Thethere
several
the iodine absorption,
are
good
although
method
of Hehner
(Analyst,1895, 49) was employed by
gravimetric
of us for many
one
years with very good results,whilst the bromineand Mitchell
thermal
test of Hehner
1895, 146) givesrapid
(Analyst,
and satisfactory
results. More recentlyMacllhiney (Jour.Amer. Ckem.
Soc.,1899,1084-1089) drew attention to bromine absorptionmethodsBromine

and

interest in them.

tried to rewaken

useful

for

tween
bediscriminating
various oils and fats,and, in conjunction with other physical
and chemical data,affords another means
adulteration.
of detecting
Where
of
have
be
tested
to
number
a great
expeditiously,
samples
the Abbe
be
Zeiss
refractometer
the
or
butyro-refractometer
may
with
recommended
which
of the ease
account
on
lated.
they are manipu-

The

index
Refractive

The
The

Titre

Dalican,
solid fats

and

30
c.c.

the

or

is

as

considerable
One

usual

most

is sometimes

temperature

settingpoint of the fatty acids was

accepted in the commercial
generally
of

gauge

bearingon

firmness,and

the market

in

in

case

of a 25 per cent, caustic soda solution

of redistilled methylatedspirit.The
whole
bath until

is

water,

slightexcess

fattyacids,and

the

of dilute
whole

has

porcelaindish,and
added, togetherwith 50-

c.c.

water

of tallow

shallow

is stirred down

obtained,when

pasty soap
is added, which
redissolves
methylatedspirit
This
again stirred down to a solid soap.
the

the

devised by
of

valuation

value.

of the fat is melted

ounce

is 60" C.

of observations

the soap, and

is then

sulphuricacid

warmed

another

until the

50

c.c.

on

of

the whole-

tilled
dissolved in disadded

to liberate

fattyacids

form

a.

ANALYSIS

OF

BAW

the surface.

clear

liquidon

then

syphoned off,more

of mineral

MATERIALS,

acid

The

SOAP,

added

123

GLYCERINE.

beneath

water

distilled water

remaining,and

AND

the

fattyacids

to wash

out

is

trace

any

againsyphoned off,this process

being
washings are no longeracid to litmus paper, when
the fattyacids are poured on to a dry filter paper, which is inserted
in a funnel restingon a beaker, and the latter placed on the waterbath, where it is left until the clear fattyacids have filtered through.
of the pure fattyacids are now
10-15 grammes
About
transferred

until
repeated

the

test tube, 6" x 1", warmed

through a hole in the cork into
to

until molten, and the tube introduced

flask or wide-mouthed
bottle.
A

very

thermometer, graduated into fifths of

accurate

is immersed
(previously
standardised),
that the bulb is

the

near

as

centre

and
possible,

as

at the bottom
acids justbeginto solidify
The
is stirred round
slowly.
mercury

continued until it
is

very
will
temperature

ceases

to

fall

in the

grade
degree Centifatty acids,so
when
the fatty

of the
will

tube,the thermometer
is.
descend, and stirring
which

further,at

observed.
carefully
rise rapidlyand
finallyremain
It

will

be

point the
found

mometer
ther-

that

the

stationaryfor a
perature
short time, after which it will again begin to drop until the temthe
is reached.
to
of the room
The maximum
which
point
the
titre of the sample.
as
temperaturerises is known
"

"

ALKALIES
be bestowed

AND

SALTS.

ALKALI

sampling of solid caustic soda

late
or
potash as the impuritiesduringthe solidificationalways accumuof that portionmust
in the centre of the drum, and an excess
the
be
will
not
be avoided
or
sample
sufficiently
representative*
to prevent earbonThe samplingshould be performed expeditiously
ating,and portionsplacedin a stopperedbottle. The whole should
broken in a mortar, and brightcrystalline
be slightly
portionstaken
for analysis,
using a stopperedweighing bottle.
Care should

Caustic Soda

and

Caustic

upon

the

Potash.

These

"

accordingto the alkali present in the

form

substances

of caustic

are

valued

(hydrate)and

carbonate.

sample are dissolved in 50 c.c. distilled!

water, and titrated with N/l sulphuricacid,using phenol-phthalein
obtained representingall the caustic
the alkalinity
so
as
indicator,
2 grammes

About

alkali and

one

bicarbonate.
gramme

NaOH

of the

-half the carbonate, which latter is converted into

0"031 gramme
One c.c. N/l acid
Na20 or 0*040
KOH.
and 0*047 gramme
K20, or 0'056 gramme
==

be
the second half of the carbonate
After this firsttitration,
may
determined in one of two ways, either :
(1) By adding from 3-5 c.c. of N/10 acid,and well boilingfor
"

of
expel carbonic-acid gas, after which the excess
acid is titrated with N/10 soda solution; or
(2) After adding two drops of methyl orange solution,N/10 acid
is run
in until the solution acquires
a faint pink tint.

five minutes

to

SOAP

124

'

of c.c. of acid
In the calculation of the caustic alkali,the number
is
divided
subtracted from
in the second
by 10,
titration,
required
in

used

that

the

first,and

"\

sample taken, whence

The
proportionof

(\

amount

Si

by

|t

11

either 0*0031

the

is to

of carbonate

the

present,

before
alkalinity

and

chloride of barium.

of the

indicator.
as
phenol-phthalein
of caustic alkali present,and

|l

portionof

by

by multiplyingthe
by 2, and then

sample are dissolved in water, and

the total alkalinity
determined by titrating
made
up to 100 c.c., and
To another
20 c.c. with N/l acid,using methyl orange as indicator.
chloride solution (10 per cent.)until it ceases
20 c.c. is added barium
to settle,
and the clear
the precipitateallowed
to give a precipitate,
transferred to a filter
supernatantliquiddecanted off,the precipitate
with N/l acid,using
filtratetitrated
and
the
well
and
washed,
paper
7-8 grammes

About

"
"/

determine

of carbonate

|\
**

or

titration

to

alternative method

An

the second

give the amount

K20 respectively.

or

after the elimination

calculated

is

carbonate

0*0047

or

multiplied by 0*031,

or

in
required

acid

N/10

as
Na20
expressed

^1
I

of

this difference

K20 respectivelyin the weight of

Na2O
percentage may be readilycalculated.

of

givesthe amount

0*047
!

MANUFACTURE.

second

titration

givesthe
the two

amount

the pro-

carbonate.

methyl orange
be carried out cold.
When

has

Eeference

!pf

The

the difference between

the alkali

solution is used

already been

made

as

titrations
indicator,

(p. 39)

to

the

must

in

manner

percentage is expressedin English degreesin

ji

which

*.j

case

|(

the neutral
solution with
by titrating
cator.
N/10 silver nitrate solution,potassium chromate
being used as indiOne
0*00585
c.c.
sodium
N/10 AgN03 solution
gramme

of caustic
Chlorides

the

soda.
are

estimated

"

chloride.
The

of

acid

for exact neutralisation

necessary
having
the equivalent
to use
alreadybeen ascertained,it is recommended
quantityof N/10 nitric acid to produce the neutral solution.
be tested for, qualitatively,
with
lead acetate
Sulphidesmay
amount

solution.
Aluminates
2 grammes
ammonia

collected

are

determined

in
gravimetrically

the usual

dissolved in water, rendered acid with HC1,

of aluminium
added, and the gelatinous
precipitate
are

on

filter paper,

manner;
excess

of

hydrate

washed, burnt, and weighed.

Carbonated
Alkali (Soda Ash)." The total or available alkali is,
of course, the chief factor to be ascertained,
and for this purpose
it
is convenient
to weigh out 3*1 grammes
of the sample,dissolve in 50
c.c.
water, and titrate with N/l sulphuricor hydrochloric
acid,using

methyl orange

indicator.

Each

of

N/l acid requiredrepresents

Na20 in the sample under examination.
A more
of soda ash would
complete analysis
comprise:
Insoluble matter, remaining after 10 grammes
dissolved in
are
as

c.c.

1 per cent.

"

This

water.

';

warm

|
I

weighed.
The

i
rt

OF

ANALYSIS

RAW

is washed

nitrate is made

on

to

SOAP,

125

GLYCERINE.

dried,ignited,
and
filter-paper,

to 200 c.c., and

up

AND

in it may

be determined

)LA

"

with N/l acid the filtraje

from the
soda,by titrating
resulting
g,

Caustic

of 20

treatment

MATERIALS,

Car bonate."

c.c.

Titrate 20

gramme) with barium chloride solution. T

with N/l acid,and deduct the amount

to
(equal,

c.c.

e
^

requiredfor the Caustic.

\
-::
Chlorides." Twenty c.c. are exactly
with nitric acid,and *f:f
neutralise^,
titrated with N/10 AgNO;i solution,using potassium chromate
inas
of acid

|
1

dicator.

Sulphates."Twenty
barium
with
precipitated
filter paper,
calculated

washed,
to

c.c.

are

acidulated

with

HG1,

and the

sulphates-

chloride ; the precipitate

is collected
dried, ignited,and weighed, the result

on

being

Na.2S04.

Sulphides and Sulphites."Th" presence of these compounds is

denoted
by the evolution of sulphurettedhydrogen and sulphurous
the sample is acidulated.
when
acid respectively
Sulphidesmay also
with lead acetate
be tested for, qualitatively,

sodium

or
solution,
test-paperof

nitro-prusside.

The
total quantity of these compounds may be ascertained
by
with N/10 iodine solution,
with acetic acid,and titrating
acidulating
usingstarch paste as indicator. One c.c. N/10 iodine solution 0*0063
Na2SO,j.
gramme
of sulphidesmay be estimated by titrating
the hot
The amount
=

soda solution,to which

silver nitrate

Na2S.

ammonia

solution, 1

As the titration

c.c.

has

been

added, with

proceeds,the

slightopacity. The presence

dropproducesonly a
hydrate,or carbonate
The

does

ammoniacal

not

Carbonate

of

Potash

until

of chloride,
sulphate,

interfere with

the

accuracy

of this

silver nitrate solution is

of pure
grammes
and
ammoniaa
fortis,
liquor
18*345

c.c.

ammoniacal

correspondsto 0'005 gramme

is filtered off,and the
precipitate

silver solution to the filtratecontinued

addition of ammoniacal

method.

an

of which

solving
prepared by disnitric acid,adding 250

silver in pure
to 1 litre.
diluting

(PearlAsh).~The

total

or

available alkali

by
sample, and titrating
with N/l acid directly,
or
adding 100 c.c. N/l sulphuricacid,boiling
the excess
of acid with N/l caustic
for a few minutes, and titrating
each c.c. N/l
soda solution, using litmus as indicator. In this case
in the absence of Na2C08, to 1 per cent.
is equivalent,
acid required,
K2C03.
for the following
Carbonate of potashmay be farther examined
:
2-3 grammes
heated for thirtyminutes in a
Moisture." From
are
crucible over
a gas flame,and
weighed when cold,the loss in weight
the
moisture.
representing
and
Insoluble residue,remaining after solution in water, filtering
well washing.
Potassium
as
potassiumplaby precipitation
may be determined
in a small quantity(say10
tmo-chloride thus :
Dissolve 0*5 gramme
may

be estimated

takiag6*9 grammes

of the

"

"

126

MANUFACTURE.

SOAP

acidulate with hydrochloric

of water, and carefully
o.o.)
acid,evaporate
to
resultant
the
liquor drynessin a tared platinum basin,and heat the
to dull redness.
Cool in a desicator,
residue gradually
press
weigh,and exmixed chlorides,"
i.e.chlorides of soda and potash.
the result as
To the mixed chlorides add 10 c.c. water, and platinic
chloride in excess
of the mixed
ides)
chlor(thequantitymay be three times the amount
and evaporate nearlyto dryness; add 15 c.c. alcohol and allow
to stand three hours covered with a watch-glass,
givingthe dish a gentle
is decanted through
occasionally.The clear liquid
rotatorymovement
well washed
and the precipitate
with alcohol bydecana tared filter,
transferred to the filter,
dried and weighed. From
tation,and finally
the weight of potassium platino-chloride,
K2Pt016,is calculated the
of potassiumoxide K20 by the use of the factor 94/488*2or
amount
"

019254.

Chlorides,determined

N/10 silver nitrate solution,and

with

culated
cal-

to KOL

estimated
Sulphates,

as

barium

Carbonate, found

Sodium

to the actual

and
sulphate,

potassium as determined

with
Iron, precipitated

calculated to

K2SO4.

by deducting the K2C03 corresponding

of

excess

above, from the total alkali.

and
ammonia, filtered,
ignited,

weighed as Fe203.
SODIUM
This

should be examined

Actual

(COMMON SALT).

CHLOBIDE
for the

using neutral potassiumchromate

estimated

following:
"

N/10 silver nitrate solution,

solution as indicator,
or, preferably,

Chloride,either titrated
silver
as
gravimetrically

with

chloride

with
by precipitation

transferred
solution,the precipitate

nitrate

washed, dried

and

tared

ver
sil-

filter paper,

weighed.

Insoluble matter,
This
filtering.

to

remaining

on

dissolving5

grammes

in

water,

and weighed.
washed, dried,ignited
5 grammes
Moisture.
are
weighed into a platinum crucible,and
heat gentlyapplied. The
temperature is graduallyincreased to a
for a few minutes, the dish cooled
dull red heat,which is maintained
in a desicator,
and weighed.

and

is

"

Sulphatesare estimated
"calculated to Na2S04.

as
by precipitation

barium

sulphateand

This
be determined
by convertingthe salt into
may
sulphateby the action of concentrated sulphuricacid,igniting
until
and sulphuric
to drive off hydrochloric
acids,and fusingthe mass
"constant in weight,weighing finally
as
Na2S04.

Sodium.

orange
correc'

Le

20" C.

"

sodium

Or

20" C.
Re

detem
So

POTASSIUM

CHLOBIDE.

requis:
for
may

sodium
This should be examined, in the same
as
chloride,
way
insoluble matter, moisture,and sulphate. The potassium
chloride,
be determined

carbonate

of

as

potash.

described
as
potassium platino-chloride,

under

with

alcoho
run

in

opales

ANALYSIS

OF

RAW

MATEKIALS,

SILICATES
The

OF

SOAP,

SODA

127

GLYCEBINE.

POTASH.

AND

important determinations

most

AND

for these

are

total alkali and

silica.

Total alkali
and

water,
as

is estimated

2 grammes
in distilled
by dissolving
with
cold,
N/l acid, using methyl orange

when
titrating

indicator.

be determined
Silica may
1 gramme
in distilled
by dissolving
the
solution
acid
with
water, rendering
HC1, and evaporatingto complete

dryness on the water-bath, after which the residue is moistened

and again evaporated,this operationbeing repeated a third
residue is then heated to about
The
time.
150" C.,extracted with
hot dilute HC1, filtered,
thoroughlywashed, dried,ignitedin a tared
platinum crucible,and weighed as Si02.
HC1

with

ESSENTIAL

already stated,these

As

are

OILS.
liable to adulteration,
and
desirable,while in the case of

very

of all kinds of oil is

examination

an

the

expensivevarieties it should never be omitted.

Gravity. As with fats and oils,this is usuallytaken at
'Specific
15" C., and compared with water at the same
temperature. In the
and
of
wood
of
otto
solid
rose
are
oil,however, which
case
guaiac
observed
at this temperature,it is generally
at 30" G. compared with
more

"

at

water

15" C.

taken in a bottle or U-tube, but

specific
gravityis preferably
is
if sufficient of the oil is available and a high degree of accuracy
it may
be taken either with a Westphal balance, or
not necessary,
of a hydrometer.
by means
OpticalRotation. For this purpose a specialinstrument,known
and use
of
details of the construction
is required,
a polarimeter,
as
here.
that
of
it
mention
perature
temto
be
would
out
Suffice
which
place
of the optical
plays an importantpart in the determination
and
the
of
lemon
in
of
certain
essential
case
oils,
notably
activity
Hoffmann
the
and
For
oils.
these
Gildemeister
following
give
orange
The

"

"

corrections

"

oil,below 20" G.

subtract

9' for each

degree below, above

20" G. add 8' for each degree above.

Orange oil,below 20" C. subtract

14' for each

degree below, above

Lemon

20" C. add 13' for each degree above.

is
This figure
RefractiveIndex.
"

determined

with

an

"

This

is found

by running alcohol
measured

volume

requisitestrengthfrom a burette into a

until the oil forms a clear solution
with constant
agitation,
the quantityof alcohol added, it
noted
alcohol.
Having
,

|f,

run

in

small

opalescence
or

further

is best

refractometer, at 20" C.

Abb6

in Alcohol.
Solubility

useful,and
occasionally

quantityof alcohol,and

cloudiness appears.

observe

of the

of the oil
with

the

is well

whether

to

any

128

MANUFACTURE.

BOAP

values
Acid, ester, and saponification
fats and

under

described

value
saponification

the

the

by

the number
multiplying

of

c.c.

linalylacetate,the

as

multipliedby

and

0*196

exactly as

expressingthe

percentage

result as
of ester, calculated

by

be obtained
may
alkali
N/l
absorbed in the saponification
of the ester.
Thus, to find the

of

molecular* weight

the

of

important ester present,

most

in

by
percentage

Instead

number,

or

of the

form

oils.

determined

are

number

100, and

of

absorbed would

c.c.

divided

by

these,if

the

the

be

oil

weight of

taken.
"

acid, the

with

potash,

to

much
liberate

the excess
neutralising
of alkali
washed
into a separatingfunnel with
water,
anhydrous sodium sulphate,and is then ready

oil is

separated,dried

oil contains

alcoholic

after

alcohols,and

combined

the

saponifiedwith

first be

it must

ester

of

estimation

the

For

Alcohols.

with

for the alcohol determination.

only a small quantityof ester present, this preliminary

;s unnecessary.
saponification
estimated by conversion into their acetic esters,
alcohols
The
are
with standard
then saponified
alcoholic potash, thereby
which
are
If there is

furnishinga
Ten

c.c.

of the oil is

anhydride,and 2
gentlyboiled for an hour

acetic

is
"

added,

and

of alcohol

of the amount

measure

the

placedin

of

grammes
to

hour

an

equal

an

anhydrous sodium
and

of the

contents

esterified.

flask with

half.

After

flask heated

acetate, and

cooling,water

the

on

of

volume

water-bath

thirtyminutes, after which they are cooled, transferred

separatingfunnel, and washed with a brine solution until the

for fifteen to
to

oil
The
givean acid reaction with litmus paper.
sodium
1-2
dried with
is now
and
anhydrous
sulphate,filtered,
flask
and
into
with
a
alcoholic
saponified
weighed
potash
grammes

washings cease

as

to

of ester

in the determination

The

is

calculation
to make

value.
saponification

or

little

complicated,but

example

an

may

it clear.

perhaps
A geranium oil containing26 '9 per cent, of ester, calculated
as
a
fter
to
liberate
the
was
acetylated,
saponification,
geranyltiglate,
of the acetylatedoil required
and 2*3825 grammes
combined geraniol,
its
for
9'1 c.c. of N/l alkali
saponification.
of
196
Now
geranylacetate presentin the acetylated
grammes
every
of geraniol,
that for every
196
so
oil correspond to 154: grammes
serve

of ester
grammes
to its weight,and
the

weight of

it is therefore

oil taken

the number

of

c.c.

of

c.c.

necessary

to

absorbed

of

been

added

deduction

from

correspondsto 0*196

be deducted

is found

for

this,

gramme

by multiplying
"

geraniol
=

have

the formula
for
by 0'042 gramme,
becoming in the example given :
91

cent,

grammes
to make

to allow
saponification

alkali absorbed

estimation of total alcohols thus

Per

oil,42

final

for the

N/l
geranylacetate,the amount

and since each

of

the

present in

now

0-154

100

!2'3825-(9'1x 0*042)

70*2.

the

130

MANUFACTURE.

SOAP

10 per

water-bath,the shaking
neutralised
until

by

continued, and

acetic

more

acid, the
is

further red colour

no

flask

The

acetic-acid solution.

cent,

any

process

produced.

way
with the sodium

solution,the volume
sulphite

011 read

the

off,and

is again placed in the

further alkali liberated
being continued in this

The

flask is then filled

unabsorbed

of the cooled

percentage of aldehydescalculated

CongealingPoint."

Point, or
Solidifying

fennel

and

of anise

in the examination

This is of

oils,and

before.

as
some

ance
import-

is also useful

be
suitable apparatus may
will
fit
which
made by
sizes,
inside the other, and fixingthorn together in this way
one
through
with
filled
then
the oil,and a sensitive
The innermost
corks.
tube is

in the

of otto

examination

obtainingthree

thermometer,

test

similar to that
its bulb

suspendedwith
and

of

rose.

tubes,,of different

described under

completelyimmersed
with

fennel,the oil is cooled down

starts

the Titre tost for fats,

in the oil. With anise
until
stirring

constant

it

just

is interrupted,
the stirring
and the maximum
rises
noted.
This is the solidifythe mercury
ing

when
crystallising,

temperature to which

point.
In the

of otto of rose, the otto is continually

stirred,and
is
is
observed
first
the
usuallyregardedas
crystal

case

point at which

the
the

congealingpoint.
of the
MeltingPoint. This is best determined by melting some
solid oil,or' crystals,
and sucking a small quantityup into a capillary
tube,which is then attached by a rubber band to the bulb of the
oil,etc.)
thermometer, immersed in a suitable bath (water, glycerine,
and the temperature of the bath graduallyraised until the substance
in the tube is sufficiently
melted
to rise to the surface, the temperature
this takes placebeing the meltingpoint.
at which
The "Belting
pointof otto of rose is usuallytaken in a similar tube
the
to
setting
point,and is considered to be the pointat which the
last crystal
disappears.
Iodine Absorption. In the authors7 opinion,this is of some
value
in conjunctionwith other data in judging of the purityof otto of rose.
It is determined by Hiibl's process as described under Fats and Oils,
"

"

except that only

"

10
chloroform,

O'l to 0*2 gramme

of pure alcohol

c.c.

is

taken,and

instead of 10 c.o. of
The rest of the process

added.

are

is identical.
SOAP.

analysisof soap, it is a
determinations should
the
all
that
In the

sample

of the soap,

otherwise

obtained.
Soap very
of the
interior
the
while

are

and the best way

portionsfor
unmilled

is to

very

or

cake

remove
carefully

analysisfrom the centre.

toiletsoap, it is

should all be

weighed

out

importance

uniform

and average
misleadingand unreliable figures

rapidlyloses
bar

of considerable

matter
be made

on

its moisture
may

be

the outer
In the

the

surface,
comparativelymoist,

case

on

edges and take

the

household

or

of

for analysis
imperativethat the quantities
other
as
as
quicklyafter each
possible.

OF

ANALYSIS

HAW

MATERIALS,

SOAP,

AND

131

GLYCERINE.

of the soap are rapidly

Fatty Acids, Five grammes
weighed into a
and
the
beaker
small beaker, distilled water
added,
heated on
the
water bath until the soap is dissolved.
"

slightexcess

of mineral

acid

is

now
added, and the whole
heated until the separatedfattyacids are
clear,when they
perfectly
tared
filter
collected on a
with hot water and
are
paper, well washed

dried until constant

in

weight.

The

result

multipliedby 20 gives
percentageof fattyacids in the sample.
A quicker method, and
which gives accurate
one
results when
is bestowed upon it,is to proceedin the manner
described above
care
far as the decompositionwith mineral
as
acid,and to then add 5 or
the

of stoaric acid or beeswax

to the contents
10 grammes
and heat until a clear layer of fattymatter
collects

of the beaker

the acid

upon

liquor.
Cool the beaker,and

when

the

cake

of

is

a
by moans
spatula and dry
carefully
the portionsadhering to the Hides of the
weigh.

it

hard, remove
sufficiently
on

filtering
paper,

beaker

to

of stearic acid or
weight, lens the amount
by "20 gives the, percentage of fattyacids.
multiplied

The

Care

bo taken

must

that the cake does not contain

The renal is of those methods

returned

the

add

cake, and

beeswax

added,

enclosed water.

fattyacids,but are
insoluble, fatty acids,tho soluble fattyacids being generin reality
ally
in soaps made
from cocoa-nut
and palmdisregarded. However
kernel oilH (which contain an appreciable)
quantityof soluble fatty
acids)
with other,and, after evaporationof the
the acid liquorin shaken
of fattymatter
left is added to the result
ethereal extract, tho amount
alreadyobtained as above, or tho other method described below may
be advantageouslyemployed.
am

an

the H""ap under examination

contains mineral
matter, the
be dissolved
in ether.
Tins
is best
separatedfatty acids may

Where

performed in

an
elongated, graduated,stoppered tube, the total
other, after subsidence,carefullyread, and an aliquot
part taken and evaporated to dryness -in a tared flask, which is
100" C. until the weight is constant.
at
placedin the oven

of tho

volume

In

verted
complete analysm,the figurefor fattyacids should be conof
tenra
fattyanhydridesby multiplyingby the factor

into

0*9675.
In this test the resin acids contained

fattyacids,but
deducted from

the former

be

can

in the soap are returned as

estimated,us described later,and

the total.

of the
is to incinerate 5 grammes
and
in
dissolve
the
residue
boil
a platinum dish,
filter,
water,
served
making the volume of filtrate up to 250 c.e., the solution being reTotal Alkali." Tho

best method

soap in

for the
as

subsequentdetermination

of

and
salt,silicates,

phates,
sul-

detailed below.

Fiftyc.c.
orange, and

of the solution

are

titrated with

in terms
the result expressed

of

N/l acid,to methyl

Na2O.

132

MANUFACTUBE.

SOAP

of

Number

fattyacids,if

of
solution has
back

the

equalthe

Na^O,

for

decomposing the

strength known,

its

soda

normal

per cent. Na20.

terminati
in the filtratefrom the de-

usuallyexpressedin

the

soap

by titrating
ence
the differ-

solution,when

of total alkali in the

amount

total alkali is

The

and

of acid with

excess

will

the acid used

measured

been

100

also be estimated

total alkali may

The

0*031

requiredx

c.c.

quantitytaken.
case

of hard

soaps

as

in soft soaps as K20.

caustic alkali is estimated

and

of the
by dissolving2 grammes
ing
washwell
gentleheat, filtering,
soap, in neutral pure
and titrating
the filtrate with
the filterwith hot neutral spirit,
N/10 acid,to phenol-phthalein.
Free

alcohol,with

Number

Na20,

of

0*0031

requiredx

c.c.

50

per

caustic.

as

Alkali

Carbonated

Free
the above

residue

The

"

with hot

is washed

determination

on

filter paper from

water, and the aqueous
the

N/10 acid, using methyl orange as

generallyexpressedin terms of NaaO.
of c.c. requiredx 0'0031 x 50
per cent,

indicator.

filtrate titrated with

The

result is
Number

Alkali.

phthaleinof
it

analystsdetermine

Some

"

the alcoholic

free alkali

as

free

alkali

carbonate.

Na20, as
Free

alkali

free

cent,

soap

the

to phenolalkalinity
without
and express
filtering,
alkaline
salt having an
any

solution

carbonates,or
(caustic,

reaction)
.

Combined

Alkali.

"

total alkali and

difference between

The

free

together)representsthe alkali combined

also be directlydetermined
figure may
by

and
alkali (caustic

carbonate

with

fattyacids. This
with N/2 acid,the alcoholic solution of soap after the free
titrating,
caustic estimation, using lacmoid as indicator.
be separatedby the method
The potashand soda in soaps may
of potassium in Pearl ask (page 126).
described for the estimation
The potassium platino-chloride
is calculated to potas(K2Pt Cl(.)
sium
ducted
chloride (K Cl) by using the factor 0*3052, and this figuredefrom the amount
of mixed
chlorides found, givesthe amount
of sodium

chloride (Na Cl),from

obtained

the sodium

which

by multiplyingby
potassiumchloride (K Cl) is converted
(K20) by the use of the factor 0*63087.

The
oxide

oxide

(Na20) is

of

potassium

0"52991.

Salt may
be determined
of the incinerated soap, by
with N/10
titrating

potassiumchromate

of the filtered aqueous extract

acid and
with normal
exactlyneutralising

Number

of

c.c.

in 50

c.c.

silver nitrate solution,using a neutral

indicator. The finalreaction is more
as

observed if a little bicarbonate

.

into terms

of soda

requiredx 0*00585

is added
x

100

solution

of

distinctly

to the solution.

percent,

of

common

salt,NaCl.
Chlorides
aqueous

may
extract

measured

volume

also

be

being rendered
of* N/10 silver

method, the
nitric acid, a
added, and the

by Volhard's
slightlyacid with

estimated

nitrate

solution

ANALYSIS

OF

RAW

titrated back

excess

alum

iron

using

MATERIALS,

with

N/10

133

GLYCERINE.

AND

SOAP,

thiocyanate solution,

ammonium

indicator.

as

These

by evaporating 50 c.c. of the

filteredextract from the incinerated soap, in a platinum dish with
hydrochloricacid twice to complete dryness, heating to 150" 0.,
adding hot water, and filtering
through a tared filterpaper.
residue is well washed, ignited,
The
and
and
weighed as Si0.2,
Silicates.

"

estimated

are

this silica is calculated the sodium

from

silicate.

be determined

the silica estimation

in the filtrate from
Sulphatesmay
with barium
chloride solution,and weighing
by precipitation
barium
the
sulphate,after filtering,
and burning, expressingthe result
in terms
of Na2S04 by the use
0*6094:.
of the factor
This is simply estimated
Moisture.
by taking a weighed portion
at 105" C.
in small shavingsin a tared dish,and drying in the oven
to lose weight. From
thus found is calculated
until it ceases
the loss
"

the moisture
Free

percentage.

Uncombined

or

extraction

Fat.

an

ethereal

; the

ether

of

This

"

is

the

solution of

aqueous

solution,after washing

evaporatedto drynessand the

be recommended
good method, which can

traces

^where

determinations

many

have

be

to

of soap in 50 c.c. neutral

grammes
phthalein with N/l acid. Add 3-5

acid, neutralise

carbonic
10

in excess,
titrate with

figure and

the amount

denotes

N/l

drops

The

requiredfor

the amount

Examination

for

performed, is
and

alcohol

solution
under

test

with

of the fattyacids

as

10

remove

weighed.
employment
dissolve 10

phenolexpel

boil to

and
a

add

reflux

actly
exdenser
con-

this latter

between

difference

blank

to

to

and

of alkali absorbed

peated
by repetroleum

titrate to

HC1

alcoholic KOH

acid.

water

residue

boil for fifteen minutes

c.c.

and

KOH,

with

with

soap

with

is

of soap,

determined

usually

c.c.

alcoholic

fat.
by
guide to the probablecorn-

position of the soap :

[From the data obtained

the uncombined

"

"

titre,"iodine number,
by estimatingthe
saponification
equivalentof the mixed fatty and rosin acids,and
rosin content, a fairly
good idea of the constitution of the soap

and
the

be deduced.

may

The

titre,iodine number,
in

exactlythe

and

same

mined
equivalentare detersaponification

manner

as

described

under

Fats

and

Oils.
The

Storch

presence

fatty

acids

solution

in

acetic

drop of

produced
by the method

with

804)

which

Two
20

rosin

no

be

detected

by

the

Liebermann-

consists in

dissolvinga small quantityof the

adding to a few drops of this
A violet coloration is
sulphuricacid.

anhydride,and

50 per cent,
acids. The

devised

amount

of

rosin

by Twitchell (Journ. Soc.

out

thus

of the mixed

may
Ghem.

be estimated

Ind., 1891,

"

fattyand rosin acids are dissolved in

alcohol,and dry hydrochloricacid gas passed through
is absorbed, the flask being kept cool by means
of cold

grammes
more

may

rosin

is carried

absolute

c.c.

until

of

reaction,which

134

MANUFACTURE.

SOAP

prevent the rosin acids being acted upon.

"water to

to stand

is allowed
disconnecting,
when

its contents

hour

one

transferred to

are

The

flask,after

to ensure

bination,
complete comPhilips'
beaker, well

that the volume

is increased about
so
water
five
boiled until the acid solution is clear, a fragment of
zinc being added to prevent bumping.
The heat is removed,
granulated

washed

with

out

and

times,

and

shaking,the
the

and

acid

cool, when

to

thoroughlyrinsed

the beaker

until

with water

liquidallowed

the

separator,and

liquoris withdrawn, and

free from acid.
Fiftyc.c.

N/l

with

titrated

solution

it is

poured into

with

out

neutral

KOH

layerwashed

alcohol

are
added,
solution,the

NaOH

or

After

ether.

the ethereal

being calculated from its combining weight.

the combining weight of rosin,but 330
as
approximation.

percentageof

rosin

Twitchell suggests 346

is

closer

The

method

be also carried

may

case

beaker

separator. The

the

into

The

c.c.

II
M:

This

"

is

of cotton-seed

absence

or

the

then with

c.c.

acids

partsof the fattyacids,amyl alcohol,and a

heated in a
are
sulphurin carbon bisulphide,

tion
solu-

tated.
agi-

The

resinate
dried
collected,

specialtest to determine
fattyacids in mixtures.

oil

the

water, and

separated.
resin

the

out

off, and

run

and

water

alcohol in 50

and
solution is withdrawn, acidified,
and weighed.

Halphen'sEeaction.

liquor is

and
saponified

is thus

rosin

acid

first with

petroleumether layerwashed
and
of -|gramme
KOH

in which
gravimetrically,

out

74" C. is used for washing

petroleumether,boilingat

the presence

Equal

1 per cent, solution of

test-tube placed in a

until effervescence ceases, then in boilingbrine for one

are
longerwhen only small quantities
present. The presence

water-bath
hour

or

of cotton-seed

The reaction is
by a pink coloration.
rapid,accordingto Bupp (Z. Untersuch. Nahr.
flask.
Genussm., 1907, 13, 74),by heatingin a stoppered
it is occasionally
Other bodies which
to test for or
necessary

rendered

oil is denoted

much

determine

more

in soap include

Carbolic acid.
and

20 c.c.
treated with

of 10
an

"

of the soap are dissolved in water

The
solution is
caustic potash added.

Fiftygrammes

"

per

cent,

and
of brine,the supernatant liquorseparated,

excess

the

with
washed
to
brine, the washings being added
precipitate
This
is then evaporated to a small bulk,
liquorwithdrawn.
placed in a Muter 's graduated tube, and acidified with mineral
the

acid.
The

volume

of

separatedphenols is observed and stated in percentage

the soap taken.

on
Or the alkaline layermay

distillateis made

up

to

be rendered acid and steam

known

volume, and

distilled ; the

portiontitrated by

the

Koppeschaar method with standard bromine water.

of soap are dissolved in water, decomposed
Glycerine. Five grammes
with dilute sulphuricacid,and the clear fattyacids filtered and
"

washed.

The filtrateis neutralised with

barium

carbonate,evapor-

RAW

OF

ANALYSIS

MATERIALS,

50 c.c., and the glycerolestimated

Crude
Glycerine.
detailed under
ated

by

to

Starch

be

may

gum

or

examining the residue 011

the blue coloration
readilyrecognisedby

potassium

in

iodine

Sugars

soap

filter paper.
it giveswith
a

the

method

in

alcohol,

Starch

is

solution

of

iodide.
of Pehlings'solution, in the liquor
by means
fatty acids,after first boilingwith dilute acid to

the

cane

any

bichromate

tested for

are

separatedfrom
invert

the

the
detected by dissolving

and
filtering,

135

GLYCERINE.

AND

SOAP,

will

sugar.
be revealed

precipitateproduced whei^.
to the liquorseparatedfrom the fatty
hydrogen
sulphuretted
estimated
be
off this precipitate
tareci
on
a
by filtering
acids, and may
in
then dried and weighed.
Gooch's crucible, which
Mercury

by

black

is added

Borax

berates

or

acid, and
in

in

is dissolved

This

boric

on

faintlyacid

with

in alcohol.

dilute

chloric
hydro-

stripof turmeric

for a few minutes

paper immersed
dried in the water-oven, when
if any

is then

liquid.
acid compound
the

for in the residue insoluble

water, rendered

This

the

tested

are

is

present,

which

paper,

brightreddish-pinkstain
blue on moisteningwith

is turned

is duced
prodilute

alkali.
of the boric acid radicle may
be determined
ating
by incinerof noap, extracting
with hot dilute acid,filtering,
5-10 grammes
solution
this
to
methyl orange, and boilingto expel
neutralising
amount

The

After

dioxide.

sufficient
cooling,

neutralised

glycerineis
added to form
volume,
liquidtitrated
with
N/2 caustic Hoda solution,using phenol-phthaleinas indicator.
solution correspondsto 0*081 gramme
of N/2 NaOH
Each
c.c.
lised
crystalboric acid, HTBO,5, or
0"0477 gramme
crystallisedborax,
carbon

one-third

of the

pure

and

total

the

Na.3B40710H2O.
LYES.
The

determined

present are
and

of cauHlic

amounts

Alkali

grammes,
the

The

Salts.

alkali (ifany),carbonated
alkali,and salt
manner
already described under Alkali

in the

is ascertained

glycerolcontent

by taking 2 "5

without increasing
adding lead Bubacetate solution,and filtering
than
is absolutelynecessary ; the solution is conmore
centrated

bulk

to

about

sulphuric acid

25

and

c.c.,

conducted

as

the

oxidation

described

in

with

the

bichromate

examination

and

of Crude

Glycerine. The solution,after oxidation,is made up to 250 c.c., and.

titrated against standard
ferrous ammonium
sulphate solution,the
formula
for the calculation
:"
being
Per

where

cent,

equals the

the ferrous ammonium

of

number

glycerol
-

of

c.c.

?-?j
j"'26
x

of oxidised

sulphatesolution.

40

lyes requiredto oxidise

136

SOAP

MANUFACTURE.

CRUDE

in this
glycerol

of actual

estimation

The

and

considerable importance,

of

which

GLYCERINE.

methods

Hitherto, however, only two

purpose.

adopted,viz. the

acetin

obtained

results

the

includes

which
latter,

and

the

bichromate
do

these

by

all oxidisable

of the

should

be

of time

considerable amount
sufficient in

found

for

as

use

ester

Method.

with

acetic
This

alkali,the
of

check

Acetin

formed.

been

generally
ately
Unfortun-

value.

suggested that,
and

it will

trouble,and

the

average
involves
a

This

generallybe
glycerolby

laboratoryto determine
ordinarycourse, reservingthe other process
of disputeor doubt.
in case
This consists in convertingthe glycerolinto its
triacetin being
or
acid, the acetic triglyceride,
then saponified
with a known
volume of standard
works

the

is

excess

"

of which

calculated
glycerol

from

is titrated with
the amount

From

of the
1 to 1*5 grammes
flask of about 150 c.c. capacity,7

togetherwith
whole

as

it has

true

been

only in the

method

one

the

and

matter

invariablyagree, the
times
glycerol,
giving some-

by both methods,

made

considered

results

two

have

processes.

not

matter

considerably
higherresults,and
determination

a
necessarily

of processes,
very largenumber
to, have been suggested for the

constantlybeing added

are

is

about

boiled

on

3 grammes
sand-bath

of

acid,and

the

percentage

of alkali absorbed.

is weighed into a conical

glycerine
8 c.c. of acetic anhydrideadded,
or
anhydrous sodium acetate, and the

under

reflux condenser

for

to

one

hours,after which it is allowed to cool,50 c.c. water

dissolved by shaking,and gentlywarming, the
added,
reflux condenser
stillbeing attached as the acetin is very volatile.
The solution is then filtered from a white flocculent precipitate,
which
of the impurities,
contains most
into a largerconical flask,of some
500-600
c.c.
capacity,and after cooling,rendered just neutral to
of N/2 caustic soda solution,the exact
phenol-phthalein
by means
tint ;
point beingreached when the solution acquiresa reddish-yellow
the
of
and
25 c.c.
solution is then added,
a strong caustic soda
liquid
boiled for about fifteen minutes, the excess
of alkali beingtitrated after
acid.
A blank experimentis
cooling,with N/l or N/2 hydrochloric
carried out simultaneously,
with another 25 c.c. of the soda solution,
nishes
and the difference in the amounts
of acid requiredby the two, furto
the
of
alkali
a measure
required saponifythe acetin formed,
the amount
and hence
be
of glycerolin the crude glycerinemay

one

and

half

and

the ester

calculated.
after treatment
crude glycerine,
Example. 1'4367 grammes
acetic anhydride,and neutralising,
with 25 c.c.
was
saponified
"

10 per cent, caustic soda solution.

The blank experiment required111*05
Flask

containingacetin

Hence,

the

acetin

formed

,,

from

c.c.

75 '3

c.c.

35*75

c.c.

the

with
of

acid.
N/l hydrochloric
,,

,,

"

"

present in
glycerol

1*4367

so^p

138

MANUFACTURE.

is calculated,
and
glycerine)

to O'Ol gramme
responding
solution run into
glycerine

becomes

complete.
then
percentage of glycerol

of the

formula for the calculation

The

the oxidised

this until oxidation is

:
"

{0'25
~

of

Percent,

where

glycerol
=

equalsthe

number

of

to oxidise the ferrous

Example

of oxidised

c.c.

glycerinesolution
sulphatesolution.

ammonium

quired
re-

"

experiment20

In the blank
required9'8

tion
sulphatesolu-

ferrous ammonium

c.c.

strengthbichromate solution,so that

20*4 c.c. ferrous solution would
equal 10 c.c. bichromate.
20*4 c.c. ferrous solution required27*8 c.c. of oxidised glycerine
solution before it ceased to give a blue coloration with potassium
one-tenth

c.c.

ferricyanide.
(250
0'01)\soo
j"'25
(
27*8
)
x

"~

Therefore,per

cent, of

glycerol
==

Other methods

80*04

have been

per cent.

suggestedfor

oxide, silver carbonate

and
caustic potash, but
copper sulphate
results.
with care gives satisfactory
e.g., silver

Other determinations
of salts and
proportion

include

those

chloride,and

and
the

of

tion,
preliminarypurifica-

the

lead
lead

subacetate, and
alone

subacetate

alkalinity,
specific
gravity,
metals,arsenic,sulphur

tests for

compounds, sugar, and fattyacids.

gravityis determined at 15" C., and may be taken in a
Specific
gravitybottle,or with a Westphal balance or hydrometer.
specific
It usuallyranges from 1'3 to 1*31.
which is usuallysodium
what
carbonate, and may be someAlkalinity,
considerable if the soap has been grainedwith caustic alkali,
is
after dilution with
determined
water
by titratingwith N/2 acid,
indicator.
as
usingmethyl orange
5-6
be determined
Salts. These
by gently incinerating
may
of
the
with
the
carbonaceous
mass
glycerine,
extracting
grammes
distilled water, filtering,
and
evaporatingthe filtrate on the water
bath.
The dried residue representsthe salts in the weight taken.
Chloride of sodium (common salt)may
ing
be estimated
by dissolvthe total salts in water, adding potassiumchromate, and titrating
"

with

N/10

silver nitrate solution.

Copper,lead, iron, magnesium,

and

calcium

may

for in the salts,

by ordinaryreactions.
Arsenic is best tested for by the G-utzeit method.

placedin

arsenic,and

10

the tube covered

times

with

few

test-tube,a

an

c.c.

dilute

with

also be tested

About

fragments of granulatedzinc
hydrochloricacid added, and the

small

filter paper,

alcoholic solution

moistened

of mercury

c.c.

is

free from
mouth

of

three successive

bichloride and

dried.

After
stain

minutes

the

will

observed

if

be

These

hydrochloric
a

the

starch-iodine

blue

the

Thiosulphates

trace

mere

the

arsenic

by

the

washed
starch

in

water,

added',

paste

disappearance

sulphite

any

and

when

of

becomes

lead

acetate

and

adding
the

in

phate
sula

few
of

presence

cloudy.
for

testing

soluble
hot

formed.

solution

causes

in

with

gradual

precipitating

with

chloride

weighed.

with

recommends

sulphide

Any

yellow

precipitate

well

solution,
the

when

barium

and

filtering, acidifying,

bichloride

mercury

test.

first

Lewkowitseh

Sulphides."

is

by

permanganate

thionulphate,

of

ignited,

together

proved

detected

with

chloride

solution

chloride,

potassium

of

drops

are

barium

with

dried,

compound

139

GLYCEBINE.

examined,

precipitated

precipitate

is

sulphite*

of

presence

AND

present.

barium

iodine

of

drops

few

is

paper

way,

the

If

acid.

SOAP,

is
be

may

with

give

Sulphites

filter
arsenic

usual

the

in

solution,

and

MATE1UALS,

thirty

Sulphates."
acid

EAW

OF

ANALYSIS

paper

blackening

of

these
in

the

by

placing
re-

the

Gutzeit

lead

acetate

paper.

Sugars
with

may

be

tented

for

solution,

FehlingH*

both

before

when

no

and

reduction

after

inversion,
should

take

by

ing
boil-

place,

if

pure,

Fatty
diluted

acids

glycerine

detected

are

is

acidified.

by

the

turbidity

they

produce

when

the

XI.

CHAPTEE
OF

STATISTICS
the

UNTIL
this

country

1853

year

the

duty, and

the

during

last

8,000,000 owt.
The

duty, the

soap

300, and

fifty-five
years,

per

followingfigures,taken

century prior to that date, show

industry during that period :"

about

the

the

half

"1,000,000 per annum,

productionexists,but it is estimated

reached
the

repealof

INDUSTRY.
soap
produced annually in
the official returns
collected

from

readilyobtainable

was

the

of

amount

for the purpose of levyingthe

at intervals of ten years for the
the steadydevelopment of the

Since

SOAP

THE

from

revenue

accurate

no

being

now

of

means

that it has

which

had

gauging

nearlyquadrupled

some

7,000,000

or

annum.

of soap manufacturers
in the United
of capitalinvested in the
the amount

number

Kingdom is nearly
industry is roughly

approach "20,000,000 sterling.

and value of soap
figuresare still available for the amount
annuallyimported and exported to and from the United Kingdom, the
for the last eightyears being:"
returns
estimated

to

Official

Imports.

Household

and
1

toilet soaps

Including

were

soap

not

given separately prior to

powder and
140

soap

stock.

1903.

STATISTICS

The
are

TfiB

OF

INDUSTRY.

SOAP

last three years for which

from the following
:
sources

importsduringthe

obtainable,

came

completefigures

"

Household

Toilet

Soap.

Soap.
1905.

1906.

"

"

8,516

3,001
5,1)19

5,773
1,861
7,638

8,145

5,794
1,283
78,382

255

74,516
147

196

93,701
4,411

97,670
8,225

98,112

100,895

Exports.
Kingdom duringthe past eightyears

The exportsfrom the United

have been as follows :
"

Total1

\i

Value.

"

989,510
999,524
1,126,657

1,148,061

1 ,208,712

1,284,727
1,809,556
1,459,118
Household

and

toilet soaps

were

'incr "no.r"

not

givenseparatelypriorto

"nnwrJoT1 cmrl

arna/n

aihc\r"'b'

1908.

SOAP

142
The

exports

MANUFACTUEE.

for the last three

available, consisted

of the

years

for which

following :

Household

"

Soap.

complete figuresare

m
STATISTICS

OF

THE

Toilet

SOAP

INDUSTEY.

143

Soap.

following statistics extracted from official consular reports,

the extent
of the soap
industry in other parts of the

The

etc., show
world.

According to the Oil, Paint and Drug Report

clusive
production of soap in the United States during 1905, exin establishments
of soap products to the value of $1,437,118 made
of other
products,
engaged primarily in the manufacture
in
the
of $68,274,700, made
manner:
a value
following
up

United

States.

"

the total

reached

"

144

SOAP

France.
value

"556,000,

of

The

This

"

chief

MANUFACTURE.

country exported common

than
"8,000 more
or

in

during 1906

soap
1905.

to the

industry is Marseilles, which, with

about fiftysoap factories,produces annually some
3,000,000 cwts.
in
1905
and
Germany imported
perfumery to the value of
soap
"3,032, that exported amounting to "15,361
In Saxony there are
eighty soap factories.
Eussia.
There
are
fiftylarge soap factories in Eussia, the annual
of

centre

the

soap

"

output

from

which

Boumania.

soap,

This

"

and

large soap
there

is about

being only
this

In

cwt.

about 230 small and eighteen

country possesses
of which
factories,most
produce only common

candle

soaps.
Denmark."

2,250,000

firm

one

in

"

country

Bucharest

there

"

which

200

some

are

milled

makes

small

soap

factories.
Australia.

According

"

to

of Trade
(a Board
factories in Australia

ninety-eightsoap

and

1,568 hands, and

producing 495,036

candle

"

an

output valued

Hong-Kong.

employing

twenty-one

employed,

were

were

and

soap

having

"86,324.

at

There

"

in 1905,

of soap.
contained

cwt.

In 1905
this country
Queensland.
and candle
142
hands
works, in which

report, there

about

are

twenty-four soap

factories

this

on

island.

Japan.
now

some

"

Swiss

fifty soap

monthly.
Fiji Islands,
from

which

consular

is 9

"

These

report

works,
possess

states

producing
only

daily.
The
following table, compiled from
official returns, shows
the quantity and
different countries
and places during the

one

that

in

Japan

there

are

about

15,000,000

tablets'

soap

factory,the

output

cwt.

various

consular

value

of

years

1905-7

and

other

imported

soap
:

"

into

"

146

SOAP

MANUFACTUBE.

Exports.

APPENDIX
COMPARISON

OF

DEGREES,
ACTUAL

(From

The

Oil and

A.
TWADDELL

AND

BAUME,

DENSITIES.

Colour

147

Trades

Journal

Diary.)

WITH

APPENDIX
COMPARISON

OF

B.
THERMOMETRIC

DIFFERENT

(From Soaps, by G. H. Hurst, published by Scott, Greenwood

148

SCALES.

"

Son.)

APPENDIX
TABLE

OF

THE

SPECIFIC

CAUSTIC

C.

GRAVITIES
SODA.

149

OF

SOLUTIONS

OF

150

APPENDIX

(From Soap,,by

G. H.

C.

Hurst, publishedby Scott,Greenwood

"

Son.)

APPENDIX
TABLE

OF

OF

STRENGTH

D.

CAUSTIC

POTASH

SOLUTIONS

AT

60" F.

(From

Soaps, by

G. H.

Hurst, publishedby Scott,Greenwood

THE

END.

151

"

Son.)

154

INDEX.

Boric acid in soap, Determination

Borneo tallow,32
Brine,39
Bromine
absorptionoi oils and
Windsor

Brown

Butter goa,

soap,

of, 135

Coumarin, 108
113, 136-139
glycerine,
Tutehing soap, 63
'ureas oil,33
'urd mottled soap, 52, 53

Crude

fats,122

78, 98

Curd

33

soaps, 52

Cuttingand stamping

kokum, 33
shea, 31
Butyricacid, 10
"

toilet soap, 85

"

D.

Butyrin,8
acid,10
Deeolorisation,
Glycerine,115
Decomposition of fats by bacteria,18Detergent action of soap, 4, 5

Daturic

Calico-printer's
soap,

93

Cananga oil,98
Candle-nut
oil,33
Capric acid,10
Caprin, 8
Caproie acid, 10
Caproin, 8
Caprylicacid, 10

7
Diglycerides,

Distearine,7
114
Distillation,
glycerine,

distilled

Double

in soap, Determination

115
glycerine,

Dregs in fats and oils,Determination

120, 121
of,
Drying soap, 71, 78-80

134

of?

115
Dynamite glycerine,

soap, 88

Carbolic

114
glycerine,

Distilled

Doeglic acid,11

Carapa oil,32
Caraway oil,98
acid

soaps, 66

Disinfectant

Caprylin,8

Carbolic

fat,36

Dika

potash, 39, 125, 126

soda, 39, 124, 125
Carnaubic
acid,10
Cassia oil,98
Castor oil,30
Caustic potash, 39, 123
soda, 39, 123
Cayenne linaloe oil,99
Cedarwood
oil,98
Cerotic acid,10
Charcoal,Animal, 115
Chinese vegetabletallow,31
Cholesterol in unsaponified
matter, 120
Cinnamon
oil,98
Citral,108
Citronella oil,99
108
Citronellal,
Cleansingsoap, 60, 61

Carbonate

E.

"

"

Close-piling
soap,
Clove

71

oil,99

of oleic acid

soap,

Elseostearic acid, 12
Enzymes, Action of,15-18

acid, 11
oils,96-107

Erucic

Essential

Examination

"

"

Ester
Ether

"

"

"

"

of,127-130

value, 119, 128

soap, 90

Eucalyptus oil,100
112, 113
Evaporation to crude glycerine,
F.

Fat, Bone, 30
Dika, 36
Maripa, 34
Marrow, 30
Niam, 34

74, 76

into solid acids.

"

"

Tangkallah,37

"

of bone, 43
Treatment
Eats, Decomposition by bacteria of,18
of animal, 43
Treatment
Waste, 30
of acid value
Determination
Fats and oils,
of,118
of bromine
absorptionof,
"

""

"

"

"

"

122

Coprah oil,25, 26
Cotton-seed

soap, 59

"

oil,25, 26
Cohune-nut
oil,34
Cold process soap-making, 46, 47
Colouringsoap, 66, 80, 82
Compressing soap, 83, 85
Concrete orris oil,100
of oils and fats,6, 7
Constitution
Cocoa-nut

11,12
Cooling

productionof
Elseomargaricacid, 12

Electrical

"

Coal tar soaps, 88

Conversion

reaction,12

Elaidin

oil,27, 42

Eefining,42
soapstock,40
stearine,28

"

__

"

"

."

"

__
.

"

of

dregs,etc.,
in,120, 121

of free acidityof,117
of iodine absorption of,

121, 122

155

INDEX.

Fats

of saponificaGoa-butter, 33
equivalentsof, 118
Graining-out,"50

oils,Determination

and

tion

"

of

saponification value, Grease, Animal, 30

118
Bone, 30
of specific
gravity of, 117
Kitchen, 30
of titre of, 122, 123
Skin, 30
of unsaponifiable matter
Guaiac
wood oil,101

"

"

"

"

____

___

"

"

"

"

"

"

in, 119
of water in, 120

"

Yield

"

"

of

H.

glycerinefrom,

116

Heliotropin,108

Classification of, 10

"

combination

Direct

"

"

Halphen's reaction,134

31

Fatty acids, 9-13,

with alkali

of, 45, 46
"

"

"

"

"

"

Hyaenic acid, 10

Determination

in soap,

Preparation by

of,131

of, 133, 134

Examination

"

"

Hempseed oil,29
Hyacinth, 108

acid

Hydrateclsoaps, 48, 49
Hydrolysisaccelerated by

process,

19-21
"

"

"

"

"

by
by

"

"

"

"

"

process, 16
Twitehell's
process,

"

Fennel

11

"

"

oil,100

Fish

oils,30

in

Free
"

"

"

88

of oils and

fats,13-23

of soap, 3

soap,

88

soap,

soap, 89

lonone, 108
Isolinolenic acid, 12
Isovaleric acid, 10

66

alkali in soap, Estimation

of,132
66
caustic in soap, Neutralising,
Determination
fat in soap,
of, 133

"

with acid, 19, 21

15-18

"

90, 91

Formaldehyde
Framing soap,

fatty acids, Determination

Isovalerin,8
J.

of, 117
Jasmine, 109
Jecoric acid,12

G.

Geraniol, 108
oils,101

K.

Geranium

Geranium-sur-rose

oil,101
oil,101
Glycerides,7, 8

Ginger-

"

"

"

"

"

"

pure,

"

115

Lard,

dynamite,

Laurie

in soap,

115

Determination

of,134, 135

"

25

Lavender

soaps, 89
Yield of, from

Lemon
fats and

bichromate

"

in

method, 137, 138

lyes,Estimation
of,135

acid,10

Laurin,

manufacture, 111-114
saponification, 116

136
"

33
butter,

L.

oils,116
Glycerol determination, acetin method,
"

Kastilis,"88

Kokum

Crude, 113, 136-139

decolorisation, 115
distillation,114
Distilled, 114

"

"

Kananga oil,98
Kapok oil,32

grass

Glycerine,Chemically
"

of chemical

Ichthyolsoap, 89
Inoy-kerneloil,37
Iodine absorptionof rose
oil,130
absorptionof oils an d fats,121,

65

"

Fluorides

use

Hypogseicacid, 11

process

Fitting,"51
Floating soap,

tricity,
elec-

preparation of fatty

for

acids, 16
Ferments, action of, 15-18
Ficocerylicacid, 10

Fillingsoap,

by

accelerated

Enzymie,

"

Saturated,

and

19-23

Unsaturated, 11

Ferment

accelerated

ferment

20

"

heat

14, 15

101
oils,
Lemon-grass oil,102

oil,102
Lignoceric acid, 10
Lime
oil,102
saponification,22
Linaloe oil,102
Linalol,109
"

agents,
re-

INDEX.

156

Oil,Bay, 97
Bergamot, 97
Bitter almond, 97
Bleaching palm, 41

Linalylacetate, 109
Linolenie acid,12
Linolic acid,12
Linseed oil,29
Lipase, 18
Liquoring of soaps, 64
Lyes, analysisof, 135

"

Candle-nut, 33

"

in, 135
glycerol

Evaporation

Carapa,32
Caraway, 98

"

"

of,111, 112

soap, 89

Cassia, 98
Castor, 30
Cayenne linaloe, 99
Cedarwood, 98
Cinnamon, 98
Citronella,99
Clove, 99
Cocoanut, 25, 26
Cohune-nut, 34, 35

"

"

M.

"

"

tallow,35
by,22
Magnesia, Hydrolysis
Maize
oil,28
Margaric acid,10
Margosa oil,35
30
Marine
animal oils,
Mafura

soap,

"

"

"

"

"

"

Maripa
Marjoram oil,103
Medullic

"

Eucalyptus,100

"

Fennel, 100
Geranium, 101

"

Melissic acid,10
Melting point,130
Mercury soaps, 87

"

101
Ginger-grass,

"

Guaiac-wood, 101

"

Milled toilet soaps, 78

Hemp-seed, 29
37
Inoy-kernel,
Kananga, 98
Kapok, 32

"

Milling soap, 80, 81

soap-base,54, 78

"

"

"

Mineral

58, 59
oil,saponifying,
oil or nitrobenzene, 109

Mirbane
8
Mixed glycerides,
7
Monoglycerides,

Mottled

"

Lemon,

"

Lemon-grass,102
Linaloe, 102
Linseed, 29
Maize, 28

"

soaps, 52, 53

"

Margosa, 35
Marjoram, 103

"

"

Musk

"

Mowrah-seed,

"

109
(artificial),

Neroli

"

Myristicacid,8
8
Myristin,

"

Palm, 27, 41
Palm-nut, 26

"

"

oil (artificial),
109
free caustic in
Neutralising

'

"

Peppermint,103,

"

soap, 66, 80

Niam
fat,34
Nigre, 56
Nigres,Utilisation of,56
Mobe
oil or ethylbenzoate, 110
Nitrobenzene,109

0.

104

Persimmon-seed, 36
Peru-balsam, 104

"

"

104
Petit-grain,
Pongam, 35
Eefiningcotton-seed,42

"

"

"

"

Rose, 105

"

Rosemary,

105

Safflower,33,

"

34

Sandalwood, 105, 106

Saponifyingmineral, 58, 59

"

Oeillet,10
Oil,Andiroba, 32
Arachis,28
96
Aspic (lavender
spike),
Baobab-seed, 36

Palmarosa, 103
Patchouli, 103

"

"

Bigarade,103

27
Olive-kernel,
Orange, 163

"

Naphthol soap, 89
Neroli Bigarade oil,103

31

Olive, 26

"

N.

102

Lime, 102

"

Pickling,54
Moulds, Soap,72, 85, 86
Mowrah-seed
oil,31
"

"

"

Monostearin, 7
Moringicacid,11

26

Cotton-seed,27, 42
Curcas, 33

"

soaps, 86-90
acid,10

orris,100

Coprah, 25,

"

fat,34

Medicated

Concrete

"

49

Femelle, 99

de Eose

Cananga, 98

"

of,112

Treatment

Bois

"

of

"

Lysol

"

Determination

"

"

"

"

"

"

"

"

"

"

"

Sassafras,106
Sesame, 28, 29
Star-anise,96

Sunflower,29

INDEX.

Oil,Thyme,

106

'otassium

Verbena, 106
Vetivert, IOC

"

"

107

Wild

Wintergreen,

"

Ylang-ylang,107

107

R.
.

fats, Constitution

of,6, 7
Examination
of,117-123
Hydrolysisof, 13-22
Fish and marine
animal, 30
Lavender, 101
Refractive Index of,122
treatment
of vegetable,43
Oleic acid, 11
into
solid acids, Conversion
of, 11, 12
Olein,8, 9, 31
"

"

"

"

Rancidity,18, 24
iapic acid, 11

"

"

leaningcottonseed oil,42
Refractive index

of oils and

"

Smelted

"

"

Cocoa-nut, 31
Palm-nut, 31

"

"

Oleodidaturin,8

fats,122

soaps, 77, 78

"

"

of, 126, 132

'owders,Soap, 94
'syllostearylic
acid, 10

36

mango,

"

Oils and

126
chloride,

Determination

"

Wheat, 36

"

"

157

ilesinate of soda, 43, 44

iUcinoleic acid,13
8
iUcinolein,
oil,105

Rose
"

110
(artificial),

"

Rosemary oil,105
Rosin, 37, 38, 43, 44, 55

Bleaching,43

"

8
Oleodipalmitin,

"

Oleoclistearin,8

"

Determination

of,133, 134

treatment, 43,

44

8
Olcopaimitostearin,

Olive-kernel

oil,27

S.

Olive oil,26

Open-pilingsoap, 71
Opticalrotation,127
Orange oil,103
Orchidee, 107
Orris oil,concrete, 100

Safflower oil,33, 34

Determination

"

Palm

oil,27, 41
Bleaching, 41
Palmarosa
oil,103
Palmitic acid, 10
"

Patent

textile soaps, 94

Pearl-ash, Analysisof,125, 126

Peppermint oil,103, 104
Perfumer's
soaps, 77, 78
Perfumes, Artificial and synthetic,107

Soap, 95-110

Perfuming soaps, 94
seed oil,36
Pern-balsam
oil,104
Petit-grainoil,104
Phenols, Determination
of, 129
Physetoleicacid, 11
Phytosterol in unsaponifiable
matter, 121
Pickling mottled soap, 54
Pisangcerylicacid, 10
Persimmon

Polishingsoaps,
Pongam oil,35

94

Potash, Carbonate, 39, 125, 126

Caustic,39, 123
"

"

14,

accelerated

"

and

electricity,

15

by

use

of

chemical

agents,
re-

19, 23
accelerated

with

Twitehell's

20
"

"

"

"

"

"

"

"

Acid, 19, 21
Aqueous, 14

by

ferment

process, 20

equivalent,118
116
Glycerine,

Lime,

22

under

pressure, 47

value, 118,

128

Saponifyingmineral

110
"

Saponiiication,
13-22, 49
accelerated by heat

"

Palmitodistearin,8
Palm-nut
oil,26
49
Pasting or saponification,
Patchouli
oil,103

oil,105, 106

Santalol,110

"

Palmitin, 8

of, 124, 125, 126,

132

Sandalwood

P.

Safrol,110
Salt,39, 126

oil,58, 59
oil,106
Saturated acids,11
Scouring soaps, 92, 93
Sesame
oil,28, 29
Settled soap, Treatment
of, 60-76
Shaving soaps, 91
Shea butter,31
Sassafras

Silicate of soda in soap, 65

Silicates of soda and potash,127, 138
Silk scouring soaps, 93

dyer'ssoap, 93, 94
Slabbing soap, 68
in, 90
Soap, Albumen
Analysisof, 130-35
"

"

agent,
re-

INDEX.

158

Soap, Sulphur,89
Terebene, 90

Soap, Bar, 54, 55

Barring, 68
-base, Milling,54, 78
Biniodide,87

'""

"

"

90

Thymol,

"

"

Birch-tar, 88
Boras, 88
Boric acid in, 88

"

"

"

"

"

Soap-making, 45-59

Determination, 135

"

Transparent, 57, 58
Treatment
60-76
of settled,
Yellow household, 54, 55

"

"

Cleansing,60, 61

"

"

"

Cold

"

"

Combination

51
Boiling-on-strength,"

"

"

Cooling,74-76
Crutching,63
Curd, 52
Curd mottled,53
Definition of, 1, 2
Detergent action of,4, 5

"

"

"

"

"

134
"

_of
"

"

"

"

in,134, 135
glycerine

of total alkali in,131

"

"

of fattyacids in,131
free alkali in, 132
of

of water

"

in, 133

Drying,71, 78-80
Electrical production
of,59
Ether, 90

"

of

fatty acids

133, 134
"

"

"

"

"

"

"

"

"

"

"

frame, 66

"

"

"

"

framing, 66
fattyacids,45, 46
Glycerine,89
Hydra ted,48, 49
Hydrolysisof,3
Ichthyol,89
Iodine,89
Lysol,89

Open

"

"

"

"

"

"

"

"

"

"

and

"
"

"

"

Pasting

or

saponincation,

49
"

Soft,48
Transparent, 57, 58

"

"

"

under

"

pressure, 47

93
Soaps, Calico-printer's,
Disinfectant,66
Floating,90, 91
Liquoring of,64, 65
Medicated, 86-90
MiUed
toilet,78
Miscellaneous, 94
Perfumer's, 77, 78
Polishing, 94
of,
Bemeltecl,77, 78
Scouring, 92
Shaving, 91
65
Silieating,
Silk dyer's,
93, 94
Textile,91-94
Toilet,77, 78
"

"

"

"

"

"

"

"

"

close

"

"

Woollen

"

92
dyer's,

Soap-stock,40
Soda
"

ash, 89, 124, 125

Caustic,39, 125
Carbonate, 39, 124, 125
Caustic, 39, 123
Resinate, 43, 44
"

"

"

"

Soft

Monopole, 94
Mottled,52, 53
moulds, 72,85, 86
Naphthol, 89
Neutralising,colouringand
66, 80, 82

"

Hydrated, 49

"

"

formaldehyde,88

Marine, 49
80, 81
Milling,

"

50
"

"

in, 90

from

"

acids

"

65
Filling,
Fluorides

"

fatty

"

Examination

"

"

"

"

of free fat in, 133

"

"

"

of carbolic acid in,

Determination

"

"

of

alkali,45, 46

Curd, 52
Curd, Mottled, 53
"Fitting," 51
"
Graining-out " or separation,

"

"

46, 47

process,

with

Cold process, 46, 47

Compressing, 83, 85

"

grey mottled, 53

"

"

Coal-tar,88

"

and

Blue

"

"

"

Carbolic, 88
Classificationof,45

"

71
piling,

perfumes, 95-110
Picklingmottled, 54
powders, 94
of,2
Properties
Salicylic
acid,88
Settlingof,55

soap-making,48
130
Solidifying-point,
Specificgravity, Determination

of, 117,

127

Stamping

soap, 71, 72, 85, 86

of,121, 135

fuming,Starch, Detection
per-

Steapsin,18
Stearic acid, 10
Stearin, 8, 9

Stearins,Cotton-seed,28
8
Stearodipalmitin,
Determination
Sulphides and sulphites,

of,125

Sulphur

soap, 89
oil,29

Slabbing,68

Sunflower

Soft,41

Superfattingmaterial,83

Stamping,71, 72, 85, 86

Syntheticperfumes,107-110

159

INDEX.
T.

ristearin,
7, 9
witchelTs

Table
"

of caustic potash
of
soda
caustic

22

process,

151
solutions,

solutions, 149,

150
of comparative densities,147

"

of thermometric

"

Tablet

148
equivalents,

soap, 55

"

119,

Constitution

of,

120

Determination

"

"

Talc, 65
Tallow, 24
"

matter,
rnsaponifiable

of,119

Jnsaturated

acids, 11
Jtilisation of nigres,56

Borneo,

32

Chinese

vegetable,31

V.

Mafura, 35
Tangkallah fat, 37
"

Vanillin,110
of,43
Vegetableoils,Treatment
tallow,Chinese, 31
Verbena
oil,106
Vetivert oil,106

acid, 12
Telfairic acid, 12

Taririe

"

Terebene,

110
90

soap,

"

Terpineol,110
Textile

soaps,

Patent, 94

"

"

Violet soap, 54
Volhard's method

91-04

acid, 10
oil,100

Theobromic

Thyme

Thymol soap,
Tiglicacid, 11

W.

90

fats, 30

Waste

test, 122, 123

Toilet soaps, 77, 78
Titre

Water,

"

"

"

___

____

"

"

Transparent
Treatment
"

"

__

__

"

"

"

"

"

"

Compressing, 83, 85
Milled, 78
Milling, 80, 81
Stamping, 85, 8(5
soups, 57, 58
of animal
fats,43
bone

fat, 43

39
in

"

"

for chloride determination,

132

fats,Determination

in soap,
oil,36

"

Wheat

of, 120

Determination

oil,36
mango
Wintergreen oil,107
Wool
scouring soaps, 92

Wild

Woollen

dyer'ssoap,

92

lyes,111, 112
Y.

rosin,43
settled soap,

00-76

vegetable oils,43

Ylang-ylangoil,107

Trefie, 107
7, 8
Tripflycerides,

Z,

Trilaurin, 9
Zinc

Trioleiu, 9

Tripalmitin,9

"

THE

ABERDEEN

UNIVERSITY

oxide,Hydrolysisby, 22.
soap, 87.

PRESS

LIMITED

of,133

^
#/

391

6.4

STRONGEST

AND

FASTEST

SOAP

COLOURS"
OIL

shades,

all

In

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BROS. "

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TEXTILE

SOAPS
Handbook
of

on

the

OILS.

AND

Soaps

the

Preparation, Properties and

Analysis
Oils used
in Textile
Manufacturing,

and

Dyeing

and

t*

Printing.

*"?

BY

GEORGE

H.
of "Soaps,"

Author

"

HURST,

Lubricating Oils, Fats

F.C.S.,
and

Greases," etc.

CONTENTS.
of Soap
to
Soaps"Relation
Soaps" Special Textile
Making
and
Vegetable
Industrial
Purposes" Soap Analysis" Fat in Soap" Animal
Oils.
Fats-"
Textile
and
Oils
Glycerine"
Vegetable
Soap.
Fats
of

Methods

Water

Oils

"

Price 5s. net (PostFree,5s. 4d. Home; 5s. 6d. Abroad).

Published

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and

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oo

CHEMISTRY

THE

OF

Essential Oih

^Perfumes
JZrtifieial
BY

B.Sc,(Lond,),
ERNESTJ, PARRY,
F.C.S,
F.I.C.,
Revised and
552 Pages. Second Edition,

Enlarged.Demy 8vo. 1908.

CONTENTS.
Free

of

Alcohols,

V.
Absorption Processes.
of
the
Essential
Oils.
Study
the Gyrnnosperms,
Tabulated
Angio"

Systematic
Oils

of

(I.) WOOD

spurms.

OILS."

Cedar

nene,

chene,

penenc,

monene,

ampene,

Turpentine, American
Turpentine, German,

en-

Phellandrene,

Sylvestrene, Carvestrene,

ditto, Table

Oils, Oils

of
Oil of
Swedish
and
Juniper Wood

Turpentine, French

of Activities

Russian,
of same,

Terpinolene, Terpinene and Thujene. 2. SKSCadinene,

Caryophellene, CedQUITERPENES
"

rene,

Ledene,

Clovene, Humulene,

Patchoulene,

Indica,
Sesquiterpene trom Oils of Cannabis
(after Schimmel).
ANGIOSl'KKMS"
Table, b.p.,sp.-gr., opt. Rot., etc., of same.
(II.) OILS OF THE
(I.) MoNOCOTVUiTHE
CAMPHOK
SERIES
DONS.
Borneol, Isoborneol,
(II.) DICOTYLEDONS:
(a) MONOCHLACamphor, Fenchyl, Alcohol, Fenchone, Thujyl MYDK/I-:"
(/;) GAMOPRTAL.-I;"
(c) POLYPKTAL.-K. \
'
"VI.
Alcohol, Thujone, Terpineol, Cineol, etc., etc.
Terpeneless Oils.
Terpeneless Oil of
CITRONELLOL
Tables
GROUP
of sp.-gr. and
AND
Lemon,
Rotn.
(III.)THE GERANIOL
of several
Coriandrol, Nerolol,
Rhodinol,
Geraniol,
Terpeneless Oils, Terpeneless Oil of Orange,
Linalol, Citrenellol, etc., Table, b.p., pp.-gr., Ditto of Caraway, of Lavender, Table of sp.-gr. :
Ref. Index, etc.
COMPOUNDS"
and Rotn. of Commercial
(IV.) BENZENE
Samples of Oils.-" VII. j
The
of
Cymene, Phenols and their Derivatives, Phenols
Artificial
Chemistry
Perfumes.
with Nine
Carbon
Phenols
with
Ten
Atoms,
Vanillin, Coumarin,
Aubepine or
Heliotrqpin,
Carbon
Atoms, Alcohols, Aldehydes, Ketones,
of
lonone,
Patents
Hawthorn,
Specification
for
COMPOUNDS
Acids, etc.
(V.) ALIPHATIC
Preparation of lonone, for Artificial Violet Oil,
Artificial Musk, Specificationof Patent of Musk
Alcohols,Acids, Aldehydes, Sulphur Compounds,
etc." III. The
Preparation of Essential Oils.
Substitute, Artificial Nerpli,Artificial Lilac,
of
Artificial
Expression, Distillation,Extraction, Table
Lemon
Hyacinth, Artificial
Oil,
Artificial Rose
Percentages." IV. The Analysis of Essential
Oil, Niobe
Oil, Bergamiol,
Oils.
Tube
Artificial
SpecificGravity,Sprengel
Method,
Jasmin Oil, Artificial Cognac Oil.
OpticalMethods, Melting and SolidifyingPoints, Appendix.
Table
Constants
of the more
on
Point
and
Boiling
Distillation,Quantitative Important Essential Oils. Index!
Estimations
of Constituents,the Determination

and

"

"

"

"

"

Price

12s.

6d.

net

13s.

(Post Free, 13s.

6d.

Home;

Abroad).

~~"

PUBLISHED

BY

SCOTT, GREENWOOD
"

BROADWAY,

LUDGATE

HILL,
164

"

SON,

LONDON,

1E.C.