T H E PR IN C I PL ES O F

L EAT H ER M A N U FA C T U R E

“
EM P R 0 F
.
-
. H R O CT ER , D Sc . .
,
FI C
. . .

“
LAT E P R OF E SSOR O F L EAT H ER IN D U STRI ES A T T H E UN I V ER SI T Y OF L E ED S ;
H O N D IR E C TO R O F T H E P R OCT E R I N T ER N AT I O N AL R ES EARCH L ABOR AT OR Y ;
.

H O N MEMB ER O F T H E W O
. R S HI PFU L COMP ANY OF L EA T H ERSELL ER S

E CO N D
'

S E D ] T] 0 N

1ne w 19 0 t h
D . VA N N O ST R A N D CO MP A N Y
8 WA R R EN ST R EE T
 Tfi q a g

E e b ic ab te t o

T HE M EM O RY OF

TH E LA T E PR OFESSO R F . L . KN A P P
GE H EI M EN H O FR A T H , D R . PHIL . A ND D R . IN G .

PIO N EER OF S C I EN T IFI C R ES EA RC H

IN L EA T H ER M AN U FA CT U R E

E RR E R
 P R E FA C E T O SEC O N D ED IT IO N

the eighteen years which have e l a p s e d s in c e th e p u b l ic a

'

IN t io n
‘

Of the first edition not only have great advances been made in
,

the Chemical knowledge on which the manufacture is based ,

but n e w points of View have been gained involving an acquaint ,

ance with physical and colloidal chemistry which is not yet

'

universal among l eather trade chemists and I have felt com -

p e l l e d to enter into ele mentary details of these branches of science

which no doubt in a few years will be among the commonplac e s
, ,

Of chemical knowledge I must therefore repeat the apology

Of the first preface that to some of my re ders much will meces a
sa
,

r il y seem too elementary whil e to others it may prove too ,

di fficult though I have endeavoured as much as possible to

confine mathematic a
, ,

l treatment to notes and append ices I t may .

be pointed out however that the advance of the future will

n e c e s §a
, ,

r il y tend to exact and mathematical methods and that ,

many theories which seem plausible enough when st ated qualita

t iv el y and in general t erms will break down when submitted t o
the rigorous examination o f m a t hem a
'

t ic s
Th e third vol ume o n the Me thods of Lea ther Ma na a a
.

f c t re ,

Which was suggested in the former preface yet remains to be

a
,

writt e n but dvancing age renders such a work impossible t o

,

the present writer and its execution must be left to some Of t he

a
“

young and well trained chemists who r e now d evoting themselves

-

t o the trade .

It is m y pleasant duty to acknowledge much indebtedness t o

Mr F C Thomps on my A ssistant in the P roct er I nt ernational
. .
,

R esearch Laboratory not only for re writing the chapters on the

,
-

Chemistry of Hide and on that Of the Tannins with which he

a
ha
,

s made himself specially familiar but for much general assist

i

nce both in the preparation Of the work and in the reading of

proofs to Mr W R A tkin for his permi ssion to insert the pap e r
on hydrion mea surement which appears in A ppendix D and a
. .

l so ,

for help in proof reading ; and to the various gentlemen who

have given information and a
-

l lowed me to use their blocks a nd

drawings in illustration and especially to Mr A Seymour Jones

P rofessor Mc Ca
-
.
,

ndl ish Mr J T Wood and Mr M C Lamb ,

. .
,
. . .

TH E P R O C TE R I N T E R NA T I O NA L R E S E A RCH LAB O R A T O R Y ,

U N I V E R S I TY O F L E D S E .
 P R EFA C E T o FI R ST ED IT IO N

THE o ri g In of the pr esent work was an attempt to prep are a

second edition of t he little Text boo k of Ta n n in g which the
-

A uthor publish ed In 1 88 5 and which has been long out Of print

, .

Though persevered in for years the work was never brou ght ,

t o completion partly owing to the constant pressure Of other

,

duties b u t still more to the rapid advances which have been

,

made in our knowledge of the subj ect and in the scientific thought
which has been devoted to it Fo r his sh a
,

r e in the initiation
'

of this work much credit is due to Wilhelm Eitner D irector of ,

the I mperial R oyal R esearch I nstitute for Leather I ndustries

a
in Vi enn but the advance he began has been energetical ly
a
, .

carried forward not only in Vienn but in the Tanning Schools ,

a
and R esearch I nstit u tes of Freiberg Leeds London Li ege
Copenhagen B erlin a
, , , ,

n d elsewhere
, ,
n d to a less extent in private
,

laboratories .

U nder the pressure of this rapid growth as it was impossible

to complete the work as a whole the A uthor published an inst a
,

, l
ment dealin g with the purely chemical side of the subj ect in 1 8 9 8
under the title of the Lea ther I n du s tr i es La
bor a
,

t ory B o o k which
"
has been translated into German French and Italian and of , , ,

which the English edition is rapidly approaching exhaustion .

Th e p resent work which should b y right have preced ed the

,

Laboratory B ook ( and which frequently refers to it as

attempts to de a l with the general scientific prin
c ip l e s of the industry without describing in detail its practical
,

methods ( though incident ally many practical p oints are dis '

cussed ) TO complete the subj ect a third vo l u m e o u ght to be

.

writt en giving working details of the various methods of manu

,

facture ; but apart from the difficulty Of the subj ect and the ,

a
”
weariness Of making many books the methods of trade are ,

so fluctuating n d dependent on temporary conditions that

, ,

they have not the same permanent value as the record of sc ien t ific
'

advance .

A s the pres ent volume is intended to appeal both to the

chemist and to the practical tanner it must to a c e rtain extent
fail in both since many matters are included which are a
,

,
l ready
familiar to t h e former and it is to be feared some which may
, , ,
 PREFA C E TO F IR S T E D I TI ON

prove difficult to the latter Fo r these and other imperfections

.

a
the A uthor claims the indulgence Of his R eaders
Th e A uthor must here cknowledge his indebtedness to D r
.

To m Guthrie and to Mr A B Searle for assistance in writing

'

. .

several of the chapters t o Dr A Turnbull and Mr F A Bl o c ke y

. . .

fo r much help in reading proofs and preparing the MS for the .

press and to the many gentlemen who have furnished or allowed

him t o use their blocks and drawings in illustration .

TH E Y O R KS HI R E C O LL E GE ,

LE E D S .
 C O N T EN T S

IN T ROD U CT O R Y AN D H I S T O R IC A L
PR E LI M I NA R Y S K E T C H OF L E A T H E R MAN UFA CT U R E
T H E L I V I N G C E LL
P U T R E F A CT I O N AN D F E R ME N T A T IO N
A N T IS E P T I C S AN D D ISI N F E CT AN T S
O R I G I N AN D C U R I N G O F H I D E S AN D S K I N S
ST R U C TU R E AN D G R O W T H O F S K I N
W A T E R A s US E D I N TH E T ANN E R Y
P H Y S I C A L C H E M I S T R Y OF L E A T H E R MAN UFA CT U R E .

T H E C O L L O I D STA T E
T H E C H E M IS T R Y O F H I D E
—
S O A K I N G AN D S O FT E N I N G OF H I D E S AN D S K I N S
D E PIL A T I O N
D E LI M I N G B A TI N G P U E RI N G AN D D R E N C HI N G
, ,

P I C K L I N G A ND D E P I C K L I N G
A LU M TANNA G E O R T AW I N G
C H R O M E AN D I R O N T ANNA G E S
V E GE T A B L E T ANN I N G MA T E R I A L S
T H E C H E M I S TR Y O F T ANN I N S
S A M PLI N G AN D A NA L Y SIS O F T ANN I N G MA T E R I A L S
P R I N C IPL E S O F TH E V E GE T A B L E TANN I N G PR O C E S S
C OM B I NA T I O N T ANNA G E S
T H E G R I N D I N G OF T ANN I N G MA T E R I A L S
E X TR A C T I O N AN D E X T R A C T —M A K I N G
F A TS S O A PS O ILS A N D W A X E S
, , ,

O I L T ANNA G E S AN D O I LS I N C U RR Y IN G
-

JA P ANN E D AN D E NA M E LL E D L E A T H E R s
D Y E S AN D D Y E I N G
E V A PO R A T I O N H E A T I N G AN D D R Y I N G
, ,

C O N S TR U C TI O N AN D MA I N T E NAN C E O F TANN E R I E S
W A S T E PR OD U CT S AN D T H E I R D ISPOS A L
C O N C LUSI O N

AP P E N D I CE S :

A Th e Me t r ic a
l Sys t e m
t i ad
a
.

B Th e Th e o r y Of Sw e l l i n g o f Gel ne n H id e ( P r o c t e r
ad W il )
.

n so n

C Li ts f C a
o l t aD y o r es now aa
vil a
bl e fo r D ye in g ad
n

St a i i g L a La
-

th n n e er (M C mb )
f Ta L iq ad
. .

D A id it y u o rs (W R A tki n F C
'

. c o n . . n . .

Th o m p s o n )
E . C a ti
us c a t
A l k lin i y o f Lim e L iqu o r s (W . R . ad J
n . t
A kin )
v iii
 THE PR IN CI PL ES OF .

L EA T H ER MA N U FA C T U R E
CH A PTER I

I N TR O D U C TO R Y A ND H I S TO R I CA L

TH E origin of leather manufacture dates far back in t he pre

historic a ges and was probably one Of the earliest arts practised
,

by mankin d The relics which have come down to us from

pa laeolithic times and the experience of the modern explorer a
.

,
l ike ,

tell us that agriculture is a later and a higher stage of develop

“

ment than the life of the hunter and since in the colder regions , ,

clothing Of s om e kind must always have been a necessity we may

‘

conclude that it was first furnished by the skins of anim a

-

1
ls .

While wet skins putrefy and decay dry Ones are hard and
a
,

horn y n d nothing co u ld b e more natural to the hunter than

to try to remedy this by rubbing the drying skin with the fat of
the animal of which he must have noticed the softening effect on
'

his own skin B y this means a soft and durable leather may be
.

produced and this process Of rubbing and kneading with greasy

and a
,

l bum inous matters such as fat brains milk butter and

egg yolks is in use to t his day a
.
, , , , ,

l ike by the Tartars on A siatic

'

, ,

steppes and the Indians on A merican prairies and not only so

a
,

but we ourselves still use the same principle in the dressing of

our finest furs and in the manufacture of ch mois and many
, ,

sorts Of lace and belt leathers

Such a process is described in the I l t a
-
.

d ( xvii 3 8 9 —3 9 3 ) in the .

ac count Of the struggle over the body Of P atroclus

A s when a man
A huge o x hide drunken with slippery lard
-

Gives to be stretched his servants all around ,

Disposed j ust intervals between the task

, ,

Pl y strenuous and while many straining hard ,

Extend it equal on all sides it sweats ,

The moisture out and drinks the unction in

.
.

1
Se e a
l
so G en . iii . 21 .
2 PR IN C IP LE S OF LEA TH ER MA N UFA C T URE

It must a l so have been early noticed that wood smoke which ,

in those days was inseparable from the use of fire had an anti ,

septic and preservative effect on skins which were dried in it ,

and smok ed leathers are still made in A merica both by t he ,

I ndians and by more civilised leather manufacturers To this

m e t ho d zt h e Ps a
.

1
l mist refers when he s ays I am bec ome like a ,

b ottle in the smoke and such bot tles made of the entire skin
o f t he goat are still familiar to travellers in the Ea
,

,
st _ _
.

The use of vegetable tanning materials though prehistoric , ,

is probably less anci ent than the methods I have described and ,

may possibly have been discovered in early att empts at dyeing

an art which perhaps had its origin even before the u s eof clothing
Th e t a n n in s are very widely distributed i n the vegetable kingdom
’

and most barks a

,

nd many fruits are capable of making leather

The e mployment Of a l um and s a l t in tanning w a
.
, ,

s probably

of still later introduction and must have originated i n countries

where alum is found a s a natur a
,

l p roduct Th e art was lost or .

unkn own in Europe till i ntroduced into Spain by the Moors .

Leather manufacture reached considerable perfection in ancient

Egyp t A granite carving prob bly at least 400 0 years Ol d is
.
, a ,
'

pre served in the B erlin Museum in which l eather dressers are ,

-

represented On e is taking a tiger skin from a tub or pit a

. .
-

second is emplo yed at another tub while a third is Working a ,

skin upon a t able Embossed and gi lt leather straps have been

a
.

found on mu mm y of the ninth century and an Egyptian

'

b oat c o ve r o f embossed goat leather as well as shoes of dyed

and painted morocco a r e st ill in c o m p a ra
-

t ive l y go o d preserva
a
'

tion Th e art is Of very early date in Chin and was well Under
.
,

a
stood by the Greeks and In the Grosvenor Museum
t Chester is t he sole of a R oman ca lig astu dde d with bronze
‘

a
,

nails which is yet pretty flexible ; and R oman shoes have been
,

found in other parts of E ngl nd in not much worse condition

“

than those which tr a m ps leave by the wayside A fter the f a

ll .

of the R oman empire many arts were l o s t t o Europe and it was

'

, ,

not until the Moorish invasion Of Sp ain that the art Of dyeing
and finishing the finer kinds of leather was reintroduced .

England was Very backward in this manufacture up t o the

.

end Of the eighteen th century owing to the fossilising influence

Of much patern a
,

l legislation and Of certain excise duties which

were only repe a
-

, ,

l ed in I 83 o Since this time the art has made

__ .

rapid strides especially in the use of labour saving machinery

,
~
-

and England may at the present moment be considered fairly

abreast Of any other country as a whole though in some special
1
Ps . c x ix . 83 .
 IN TR OD U C T OR Y A ND HIST OR I CA L 3

manufactures we a r e surpassed by the Continent and b y A m e rica I .

In making comparisons of this kind it must however be remem

“

bered that especi a

, , ,

l l y in sole leather tannage t he most rapid

,
- -

progress has b een made during the last few years in those countries
which were more b a c kvV ard an d t ha t therefore our superiority
’

'

is much less p ro n o un c e d t h a
,

n formerly and in a few years may

'

cease to exist unl ess marked improvements are introduced in

a
the methods of production The past twenty years have how .
,

ever been m rked by very considerable advance and the applica

, ,

tion of science to the manufact ure has been very noticeable .

In the sketch Of the development Of leather manufact ure

which has j ust been given it has been implied that its Obj ect is ,

to convert the putrescible animal skin into a material which is

permanent a
.

n d not readily subj ect to decay while retaining ,

sufficient so ftness or flexi bility for the purposes for which it is

intended A s these range from boot soles to kid gloves there
.
- -

are wide di vergences not onl y in the processes employed but

al so in the materi a
, ,

ls used and in the principles of th eir appli cation .

Th e most important method Of producing leather is still by

the use Of vegetable t anning materi a l s and this is perhaps the
'

only one which is re a l ly entitled to be c a

,

l led tanning though ,

the dist inction is not very strictl y adhered to It includes t he

whole range from Sole leather through strap , h arness a
.

nd ,
-

dressing leather to calf and goat S kins and the various sumach
, ,

tannages whi ch yield morocco and its imitati ons All Of these .

products but the first and the l ast undergo after tanning the , ,

further processes Of currying Of which the most important ,

Operation consists in stuffing with 0 i and fatty matters ,

”

both to increase the flexibility and to confer a certain amount

Of resist ance to water Sumach tanned skins are not st rictly
.
-

curried but usually receive a certain amount of Oil in the

,
-

”
process of finishing
With the vegetable tans we may include St ia
.

sn y s synthetic
’

organic tannins Ne r a do l D and others p roduced by con

densation of form a
, ,

l dehyde with phenolsul phonic acids ( see also

p. which produce a perfectly white leather when used
alone and can be combined with other tans to give a paler
,

leather and to quicken tannage .

Next in importance to the vegetable tannages are those pro

d u c e d by s a l ts of chromium and a l uminium including a l l the
va
,

rl o u s ch rome leathers and the tawed or white

'

leathers used for whip lashes belt laces and aprons as well a
_ ,
_

for c a
- -

, , , ,

l f and glove kid -

.

Connecting links between these and the vegetable tannages

4 P R IN CIP LE S OF LE A TH E R MA N UFA C T UR E
”
are found in green leather D ongola and other combination ,

tannages in which alum and salt are employed in c o njunction with -

vegetable materials and in semi chrome and other leathers -

in which chrome salts are used instead Of those of a l umina .

Formaldehyde also is becoming of importance as an adj unct to

other tannages
In the production of cal f and glove kid in addition to a
a
.

l um
and s a
-

lt lbuminous and fatty matters such as egg yolk Olive

, ,
-

Oil and the g luten Of flo u r play a considerable part and are thus
linked both to the primitive methods in use by the Indians a
, f
, ,

nd

Kalmucks and to those by Which crown a nd H elveti a

leather a
,

nd many other forms Of belt and lace leathers are now

,
-

produced by treatment with fats and albumens -

.

Fr o m t h es e again the step is a short one to the chamois

'

and bu ff leathers and the German f ettga , r

”
leathers in “
,

which Oils and fats only are used .

In an attempt to View all these complex processes from the

scientific standpoint the r e a d e r sh o uld co n stantly re a
,
l ise that ‘

the present methods Of leather manufacture are the results Of

"

tens Of centuries of experience and of innumerable forgotten ,

failures and must not therefore expect that they can be easily
,

superseded Science must follow before it can lead and its first
.
,

duty is to try to understand the reasons and principles Of our

present practice for we can only build the new on the foundation
Of what has b een a
,

l r eady learned A nother fact which is

scarcely understood by the practic a l ma
.
,

n in his demands on
science is that in leather manufacture every question which is
,

raised see ms to rest on the most r e c o n dit e p r o b l e ms Of chemistry

'

and physics ; the chemistry Of some of the most complex of

organic comp ounds and the physics Of solution Of osmose and
of the structure of colloid bodies— problems which a
, , ,

r e ye t far
/

from completely conquered by the highest science of the day

Many of these problems are ho we ve r r a
.

p idl y yielding to investi

a a a
, , .

a
g t io n and
,
we may anticipate that science n d especi l ly ,

chemistry will pl y a constantly increasing part in the technology

,

of leather manufacture .

It may seem bold to attempt the scientific treatment of such

a subj ect at all ; a nd indeed it must be admitted t h at our
, ,

knowledge is still inadequat e for its complete accomplishment

but much h a
,

s been done in the last twenty years and this can ,

at least be summarised and arranged in an available form The

subj ect f a l ls natur a
.

l ly into two sections i n the first of which the ,

processes of manufacture would only be described in general

terms and with sufficient fulness to enable the r e a
.

,
d e r t o under ,
 INTR OD U CTOR Y A ND HIS T OR I CA L 5

stand t he scientific considerations on which they are based a nd ,

the methods of investigation which can be applied to th em ;

while in the second an e ffort should be made to give working
details Of the various processes sufficient to enable those with a
general knowledge Of the trade to experiment successfully in its
various branches It w . a s at first intended that these two sections

should be published in one book as a second edition to the Author s ’

Tex t boo k of Ta
-
n n t ng b u t owing to the long delay in it s publication
‘
, ,

it was decided to p ublish the first sectio n under the present title
The P r in cipl es of Lea ther Ma n uf a ctu re leaving the latter section

P r o cess es of Lea ther Ma n uf a

,

ctu re to a later date It is improbable .

that for the present writer this date will ever arrive but the
, , ,

work has been to some extent done by others and especially by

B ennett in his Ma n uf a c tu r e of Le a
,
,

ther ( Constable Co London

while the more strictly chemic a l portion has a
.
, ,

1 909 ) l ready
appeared in the Lea ther I n du s tr i es La bor a t ory B o ok frequently ,

referred to in the following pages under the abbreviation

and in the Lea
,

ther C hemi s ts P o cket B o o k

’

Wh ere quantities a
,

n d details are given they must not be taken as ,

recipes to be blin dl y followed or even in every case as the best , ,

known methods but rather as mere guides to experiment which ,

must be modified to suit varying conditions and requirements It

a
.

is the special virtue Of the scientific s opposed to the merely

tradition a
,

l way Of looking at such questions that kno wing the

, ,

c ause and effect Of each part of the process it can so adjust ,

them as to get over di fficul ties and to suit novel conditions ;

although much time m a
,

y be wasted in Useless experiments if

approximate a n d p ra c t ic a
,

_
l quantities and methods are not known .

”
It is nee dl ess to add that many methods are j ealously preserved
as t rade secrets and full d et a
,
il s are frequently unattainable ,

though this is less the case than formerly .

A fter what has j ust been said it may be well to emphasi se

,

the great importance of practical knowledge and experience to

,

the leather manufacturer Even in trades which have reached

.

a
the highest scientific development such for instance as the
manufacture of the co a
, , ,

l tar colours the sm l l experiments of the

-

laboratory are not transformed into manufacturing operations

without experience a n d sometimes even failure and this must
still more Often be the case in a trade like that of leather making -

where our knowledge Of the actu a

,

l changes involved is so in
complete On the other hand the cost Of experiments on a
manufacturing sc a
.
,

l e is usually so heavy that the least scientific

must admit the advantage of learning a l l which the laboratory
can t each before venturing further ; while even our present
6 PR IN C IP LE S OF L E A TH ER MA N UFA C T UR E

i mperfect knowledge Of the chem ical changes involved often

warn us Off hopeless experim ents and give us hints of the dir ec
,

tions in which success may be at tained A knowledge Of

.

chemistry will certainly prove at least as important to the future

Of our trade as that O f mechanics has been in the past
.
 CHA PTE R II

I N TR O D U C TO R Y S K E T CH OF L EA TH ER M A N U F A C T U R E

THE j ect Of tanning has been stated to b e the rendering of

Ob
-

animal skin i mputrescible a n d plia ble but as we now rarely

require leather with the hair on prelimin a
,

-
ry processes are neede d
,

to remove it and to fit t he skin for tanning and the nat ure of “

these processes has great influence on the s rib se qu en t character

of t he l eather produced .

The first step i s usually a washing Of the skin to remove blood -

and dirt while where it has be e n s a l ted or dried a m o re thorough

soaking is needed t o remove the salt a
, ,

n d to restore the skin to ,

its original soft and permeable conditi on .

The hair is then loosened by softening and partial solutio n

O f t he epidermis structures ( see p 49 ) i n which it i s rooted
This is most gener a
. .

l ly accomplished by s oaking for some days in

milk of lim e which is usuall y assisted by the addition of a l kaline
sul phide s When the latter a
,

. r e used in concentrated solution ,

the hair itself as well as the epidermis tissues is softened and

, ,

In the course Of a few hou rs The lime n ot only serves

_destroyed
.

to lo os en the h air but swells and splits up the fib r e bun dl es Of

,
-

which the hide tissue is composed and so fit s it to receive the ‘

tannage ( 075 p 58) and the process is always complicated and

assisted by b a c t é r ia
. .

l activity .

Fo r some purposes a regulated putrefact ive process is i ndeed

substituted for the liming t he hides or skins b e ing hung in a
moist a n d warm chamber ( see p I 66) when the soft mu c ous layer .
w ,

which forms the inner part o f the epid ermis is disintegrated ,

partly by direct putrefaction partly by the action Of the ammonia

,

a
evolved so that the hair can be scraped o ff In this case the
,
.

hide fib r e is not swollen and the necessary swelling h s to be

-

Obtained by subsequent processes .

In whate ver way the hair has been loos e ned it is either scraped
O ff with a blunt a n d somewhat curved t wo h a
,

n dl e d knife on a ~

sloping rounded beam Of ~wo o d or met l or removed by a a ,

suitable machine this Operation being termed unhairing

,

( see p
This is generally followed by
.

fl e shin g , which is pe rformed

on the same beam with a somewhat similar knife which how , ,
8 P R IN C IP LE S OF LEA TH ER MA N UFA C T URE
ever is two edged and sharp In this operation portions of
,
-
.
,

flesh and the fat and loose tissue which underlie the true skin
,

( see p are removed by scraping and cutting Machines for

. .

fl e shin g are also largely in use ( see p

a
.

Fo r sole leather the hide after some washing in soft w ter Or

‘

, ,

treat ment with weak acid solutions to cleanse from lime is then ,

ready for the actual tanning process but for the softer leathers
more thorough treatment is needed to remove the lime, and to
still further s o ft e n t h e skin by solution and remova
a l Of a portion
r

Of the cementing subst nce and of the elastin fibres

a
‘

This treatment was generally of a ferment tive or putrefactive

nature and the most common form was th t known as bating
which consists in steeping in a fermenting infusion of p ige o n l or
”
a ’
,

hen — dung The theory o f its action is not yet thoroughly under
.

stood but the effect is largely due to the unorganised hydro '

lysing ferments produced by the ba ct er i apresent while a

,

t .

the same time the lime is neutralised and removed by the weak
a
“

organic acids and s l ts Of ammonia which a re produced and ,

t he fibres which had been plump and swollen wit h lime becomes
extremely relaxed and fla This p rocess a
, ,

c c id n d that of puering
.
_

have been largely superseded by the direct use Of t ryp st ic fer

a
“

ments derived from the p ncreas of animals in conj unction with

ammonium chloride to remove the lime ( Chap X IV)
a
.

I n the lightest leathers such s kid and lamb skins for gloves
,
-

and goat and sheep for moroccos and the like dog dung is sub ,
-

stituted for that Of fowls and the process is then called puering
,

( see p .

These processes are often followed by drenching which ,

sometimes indeed takes their place the skins being soaked in a ,

fermenting bran infusion I n this the small quantities of acetic

a
.
,

n d lactic acid formed by fermentation are the active ag ents

neutra
,

l ising and dissolving the lime and cleansing and slightly ,

plumping the pelt ( see p .

In recent times these unpleasant processes have been largely

supplemented and in some cases superseded by purely chemical
, ,
.

means which are safer and more economical

, .

Th e tanning process which follows consists in soaking the

pelt in infusions of various vegetable p roducts c o n t a mm g bodie s
of the class known as tannins which have the power of com ,
‘

bining with skin fib r e and converting it into leather

-
.

If at first strong infusions were used they would act too ,

violently on the surface Of the skin hardening and contracting it ,

so that the subsequent tannage of the interior woul d be impeded ,

and the grain or outer surface would be drawn and “

 S KE T CH OF LE A TH ER M A N UFA C T URE 9

wrin kled This is avoided by the use at fir st of very Weak in

.
»

fusions which have already been partially exh austed on goods

in a more advanced Stage In the later part of the process much
“

stronger solutions are emplo yed and the hides are frequently
dusted in them with ground t a
, _

n n I n g material
-

In the case of sole leather these proc esse s ma

.

y require from
tW
,

f
O to twelve months for completion ; after which the leather I s

dried smoothed a
,
n d compressed by mechanical means
,
and i s
then ready for use Th e time Of tannage is now oft en shortened
.

by drumming and other processes of agitation

D ressing leathers ranging from c a
.

,
l f skins to harness hides - -

rece ive a much shorter tannage and a subsequent treat ment with
fats a
,

n d Oils which together with mechanical manipul ations

, , ,

constitute currying The thi n fil m Of grease distributed over

.

the surface of the fibres renders th em supple and to some extent ,

waterproof .

Th e lighter fanc y leathers such as morocc o are dyed and , , ,

u ndergo many complex processes to fit them for their required

purp oses and I mprove their appearance .

a
Many skins such as calf glove and glac é kid are not tanned
but t wed by a solution Of a
,

l um and salt which 1 s Often sup

, , .
,

p lem
,

en t e d wit h mixtures of flour and egg yolk to fil l and soften

“

the leather .

Salts o f chromium are n ow largely employed in plac e of alum

and s a
-

l t and pr oduce an equally soft but more permanent

“

and enduring l e ather a

, ,

n d the process is also applied to the

“

, ,

production of the firmer leathers required for soles and beltings .

Last l y wash leather or s o called

-
chamois and bu ff leather
- -

a
, , ,

are produced by fulling the prepared pelt with fish or whale o il

.

which converts the skin into leat her by subsequen t oxid tion ,

during which aldehydes are evolved .

 CHA PTER I I I

TH E L I VI N G C ELL
'

TH E larger part o f the materi a l s employed in l eather m a n u fa

c
“

ture are organic in t heir origin and the skin itself is an organised
.
,

structure while the life processes of putrefact ion and fermentation -

So m
,

play a large p art in the tann ery e knowledge therefore “

.
, ,

of biological structures and processes is necessary to a full under

stan di ng Of much which follo ws a n d a few words a r e not out Of ,

place with regard to the foundations of l ife its elf

'

Th e bricks of which a
.

l l living structures are built are the .

living cells and their products and these first eleme nts di ffer ,
-

little if at all whether the life is animal or vegetable the dis

, ,

tinction being produced rather b y the w y in which they are put

together than by di fferences in the cells themselves This is so
a .
,

much the case that it is Often diffiOul t to decide in which Of the

two classes to place the Sim p l e st o rga n ism s since many Of these

forms are capable of active movement a

,

n d their mod es of ,

nutrition and reproduction are common to both kingdoms

I n its simplest form the cell whether anim a
.

l or veg etable
is strictly speaking not a cell at a
, , ,

l l but consists merely of a ,

minute mass of living j ell y or protoplasm Such is the am oeba .

found in water and damp soil such are the lymph cells and .

,
-

White blood corpuscles of our bodies and such also some stages
-

at least Of the lowest forms of fungi like the E tha

,

liu rn septicuin ,

Which is sometimes found on old tan he aps as a crawling mass

,

If a drop of s a
-

Of yellow slime l iva be examined with the micro

.

scop e under a cover glass with one sixth obj ect ive and small -

,
-

opening of diaphragm a few scattered semi transparent Obj e cts 1

will be found of the apparent size Of a lentil or sm a

-

, l l pea and ,

of rounded form These are lymph corpuscles ( fig 1 ) Their.

-
.

contents are full Of small granules and if they be Obser ved quic kly , ,

or if the slide be kept at about the warmth Of the body it will ,

be noticed that these are in constant streaming motion If the .

warmth can be kept constant which is difficult without special

apparatus and the cells c a
,

, n be Observed from time to time it ,

may be seen that they lose their circular form and put out pro ,

1
F o r d e t il sa Of m ic r o sc o p ic m aip l a
n ti u on in t hi s ad
n t h e f o l l o w in g
ch a
—t
p e r se e L . I . L . B .
pp .
41 1 e t s e q" ad L C P
n . . . B .
pp . 1 99 e t se q .
1 2 P R IN C IP LE S OF LE A TH ER MA N UFA C T URE

These cells like all living things f eed on the nutriment which
, ,

surrounds them and even enclose small particles of solid food

which are gradu a
,

l ly dissolved and dis ppear In this way the a .

,

white blood corpuscles are said to feed upon and destroy the still
smaller organisms which gain access to the blood a
-

n d which ,

might otherwise cause disease and to absorb and remove dead ,

tissues The matter which cells consume is not of course de

. , ,

stroyed but simply converted int o other forms so m e of which

,
‘

are useless or even poisonous to the cells and which like the
, , ,

FI G . 2 .
— Ye at
s -
c e ll s , a
m u c h m g n ifi e d .

secretio ns Of higher animals are discharged into the surroun ding ,

fluids while others are retained and contribute to the growth

of the cell Thus most vegetable cells secrete cellulose or pl nt
.

tissue w hich forms a wall enclosing the protoplasm and so

,

,
a
, ,

j ustifies the name Of cell If to warm water and a little sugar .

a
we add enough yeast to r e n de r it slightly milky and examine
'
‘

it like t h e saliv we sh a
,

l l have before us typical vegetable cells

,

of the simplest form ( fig The r e is the same granular proto .

plasm and there is the nucleus though it cannot be se e n wit ho u t

, , _

special preparation the rounded spaces which look like nuclei -

being simply fil led with transpar ent fluid and c a

,

l led vacuoles ,
.

There is however no motion as in the case of am oeba for the

, , , ,

cells are enclosed in a tough skin of cellulose which will be evident ,

if they are crushed by putting some folds Of blotting paper on the -

cover glass and pressing it with the handle Of a needle or a

-

rounded glass rod when the protoplasm will be forced out and
'

,
 TH E L I VIN G C ELL 1 3

the skin re main like a burst bladder This will be more Obvious
if t he cells a
.

r e previously treated with iodine or magenta which ,

will stain the protoplasm but not t he membrane It is easy to , .

o b serve the multiplication of

t h e ye a
_

s t cells which is some

'
-

what di fferent to that of the

c o r p u s c l es I nstead Of e n l arg

ing as a whole a
I

nd d ividing ,

into two equal cells a small

“

.
,

bud appears on the sid e of the “

parent cell and enlarges till it

-

, .

becomes itself a parent cell -

with buds of its own These FI G —Ep it h l iu m c e l l s (R a

.

n vi r )
~

k ; g g au l a
3 e e

ma
-

. . .

do not break away at onc e

.

p t opla
p e ss u , r re r s ,
r n r

and hence chains and group s sm ro .

of attached cells are form ed

which are easily notic ed in gro w mg yeast if a microscope be
employed Th e pri ncipal nutriment Of yeast is grape sugar or
a
-

and much more of this is consum d h n i s needed t o

'

g l i i c o se e t
produce the cellulose wall and the sub
stance Of new cells ; j ust as in the
animal sugar starch and fat are con , , ,

sumed to give heat and energy In _ .

the yeast this extra sugar is sp lit up ,

into carbon dioxide which escapes as “

ga
,

s and to which yeast owes its

pow er Of r a
,

I SI n g bread ; and into

a l c ohol which in too large proportion ,
’

is poisonous to the yeast itself .

I n examining the saliva for l ymph

cells it is probable that some much ,

larger Obj ects may have been noticed

of irregular polygonal outline and
with a well m arked nucl eus These -

are cells from the lining ep itheliu m of

the mouth and o n l y/d iffer from those ,

of the ep idermis Of skin in their form

and size ( fig Note the markings .

FI G 4 — P e i ci l li u n gl a
n u u in caused by the pressure Of o verlapping
r e

ac o m m o n g e e m o u l d cells In these cells the wall is formed

.
,

r n .
.

'

Of keratin or horny tissue which ,

takes the place of th e cellulose of the yeast

Othe r simple forms of cell are those of S a ccha
.

r omy c es my c o

der m a or t or ul awhich forms a skin on the surface of Ol d liquors

, ,
1 4 P RI N CI P L ES O F LE A TH ER MA N UFA C T URE

and which much resembles a small yeast and Of the various

ferments which are found in liquors bates and drenches which
, ,

will be more ful ly described in the chapter following .

Many of these such as the acetic and lactic ferments which

like a ll other bact er i a
, , ,

multiply by divisi o n do not separate but

remain connected in chains or Chaplets like a
, , ,

s tring of beads
-

.
,

From these the step is not a long one to the hyp hw or stems of
,

the higher m o irl ds which are too frequently found on leather

,

which has been slo wly dried and which consist simply of tubular
cell s which elongate and divide by the formation Of sep ta
,

or cross
a
partitions and thus build up a c o m p lic t e d p l an t s t i u c t u r e ( fig
’

A s we proceed higher in the sc a l e of plant and anim a

-
.
,

the forms and products of the cells become more varied n d

instead of one sin gl e c ell fulfilling a
l l t he functions of the plant
l life
, a
or anim a
,

l each class Of cell has its own pecul iar duties and
,

properties while all work tog ether for the maintenance of the
,

complex structure of which they form a part .

 CHAPTER IV

P U TR E F A C TIO N A ND F ER M E N TA TIO N

TH E chemic a l changes produced by the unicellular plants Such

as yeasts and bacteria to Which a
,

l l usion has been made in the

last chapter are known as f ermentation and putrefaction a
,

n d are

a
, ,

of such importance to the tanner both for good n d evil that the , ,

subj ect must be treated in some detail NO scientific distinction .

exists between fermentation and putrefaction though it is ,

customary to restrict the latter term to those decompositions of

nitrogenous animal matter which yi eld products Of disagree ble a
smell and taste
Th e organisms which a entation a
.

r e the cause of both ferm nd

putrefaction are known by the genera l term of ferments This
t erm h a s a
.

l so been e x t en d e d in recent years so as to include the

'

so ca
-
l led unorganised ferments ( enzymes zymases) which are , ,

active digestive products secret e d by bacteria and other livin g

organisms and which are constantly increasing in both sc 1 e n t ific
,

and technical importance .

Th e organised ferments are again divide d into three classes

1 . Moulds .

2 . Y easts ( Saccharomycetes ) .

3 . B acteria .

mem bers of one class are distinguished from those of

Th e
another by their form and more especi a , l ly by the substances
, ,

they produce during their life— history All three classes are .

now considered to be fungi .

A ll enzymes possess the following three properties

1 They a
. re nitrogenous bodies .

2 They are unstable i e they are destroyed by heat

’

chemic a
. . .
, ,

l s etc
3 A relatively sm a
.
,

. l l quan tity of the ferment is capable Of

producing great changes in the substances upon which
it acts especially if the products of the change can be
removed as they are formed In these qu a
,

l ities they .

resemble the substances known as catalysts In

chemistry and their action must be regarded as a

'

, “

species Of cat alysis .

 1 6 PR IN C IP LE S OF L EA TH ER M A N UFA C T URE

g eneral character of fermentation wil l be best understood

Th e
by a closer st udy of the yeast cell which has already been de -

a
-

scri b ed ( p n d its life history briefl

.
y sketched It has been -

shown t h at it is a growing plant of a very simple type belonging ,

to the fungi These are d evoid Of the green col ouring matter
. .

which enables the higher plant s t o utilise the energy of sunlight

in assimilating the carbonic acid Oi the atmosphere exhal ing it s '

oxygen and employing its carbon for the building up Of tissue

,

and they must therefore like animals have their nutriment ready , ,

formed and capable Oi supplyi ng energy by its oxidation Fo r

, .

yeast as has been stated the appropriate nourishment is glucose

, , , _

”
or grape sugar
'

This is broken down in the main into the

-
.
, ,

simpler compounds alcohol and carbonic acid while a small , ,

porti on is utilised for the building up Of the cell and the forma
.

tion of s econdary products The main reaction is represented .

by the following equation

C, H , , o 6 2 C2H6 0 z oo 2
Gl u co s e A l c o ho l C ab
r on d i o x i de

cannot directly ferment ordinary cane sugar ( C1 2H 220 1 1 )

Y east -

but secretes a substance calle d I nvertase which so acts on the

sugar as to break it up wi t h a
,

bsorption of one molecule of water

into two molecules o f fe rm en t a
-

b l e g l u c o se ( dextrose a
, ,
,
'

n d levu
1
lose) which serve as nourishment for the yeast This invertase .

is a t yp e o f the series of bodies which we have spoken of as

unorganised ferments enzymes or zymases di ffering from the , , ,

organised ferments in being simply chemical products without

life or p o Wer Of reproduction but c apable Of breaking up an ,

unlimited quantity Of the bodies on which they act without ,

th emselves su ffering change Th e way in which this is done is .

not clearly understood but some parallel may be found to it in ,

the action Of sulphuric acid on alcohol Of which it will convert ,

an unlimited quantity into ether without itself su ffering any ,

permanent change Th e action Of enzymes is limit ed t o breaking

.

down complex bodies into simpl er forms Often with absorption ,

of Water as in the case Of sugar while some Of the products Of

'

, ,

living ferments are Often co mplex a part Of their nutriment ,

being broken down into simple products such as carbonic acid ,

-
,

marsh gas and ammonia to supply the necessary energy to

, ,

elaborate the remainder .

V ery many diff erent unorganised ferments are known to exist ,

as they are not only produced by yeasts and bacteria but are ,

1
Co m p a O Sul l i aad
re
’
v n n T h o m p s on , j o u r n Chern
. . S oc r 1 89 0 , p
,
. 83 4
1 89 1 , p 46. .
 P U TREF A C TI ON A ND FERME N TA TI ON 1 7

formed by the cells of high er plants and anim a l s ; th us the

digestive pr inciples pepsin trypsin ptya l in are Of this character
— ptya
, , , ,

l in like diastase converting starch into sugar and such

bo di es ful fil many functions both in anim a
, ,

l and vegetable
economy In fermentation as in di sease it is Often di fficult to
.
, ,

di stinguish what is due to the direct action of bacteria and what

a
to the unorganised ferments which they pro duc e and the question ,

is further complicated by the fact that in most natur l fermenta

tions more th a n one ferment organism is present Sometimes -
.

the action of the unorganised ferments may be distingui shed

by the fact that the addition of chl oroform has little effect on
their activity whil e it paralyses that of the living organism By
,
.

exposure to high temperature both are destroyed the bacteria , ,

yeasts and moulds being killed and the unorganised ferments

,

coagulated like whit e o f egg and so rendered inoperative Many

l

antiseptics a
.
,

l so destroy the activity of both organisms and

enz ym es ; but others like chloroform have no action on the
latter In many cases as in that of inverta se the actu a
, ,

l zymase
can be precipitated by a
.
, ,

l cohol from it s aque ous solution fil t ered ,

Off and restored to acti vity by transference into water

, Wood .

found that the enzym es so separated from a puer liquor were

still active after fou rteen years Since both classes Of ferments .

are destroyed by high temperatures all fermentation processes ,

-

are completely and permanently arrested by exposure to suffi

cient heat and subsequent preservation in vessels so closed that
,

no n ew ferm e n t germs can gain access

’
-
A familiar instanc e is .

that Of tinned meats All fully developed bacteria are destroyed.

by a very short exposure to a boiling temperature and most "

but m a
,

by 60 to 7 0 °
ny species pro duce spores which are
°

extremely difficult to destroy The thermophil ic bacteria

discovered by Globig a n d further investigated by R a
.

b in o wit s c h 1

thrive at a t emperature of 60 C A bout eight species of these °

.

are known and they take part in the heating of hay and similar
,

fermentations where high temperatures are involved and are

therefore presumably present in spent t a
,

n .

The spores of the anthrax bacterium the cause of the mali gnant
pust ul e a
,

nd Of wool sorters disease are extremely resistant -

’

both to heat and to di sinfectants ( Cp p . . .

Fo r absolute st er ilisation it is therefore necessary either to boil

under pressure so as to raise the temperature to say 1 1 0 C °

a
.
, , ,

or to heat repeatedl y for a short time to temper tures of 80 to °

C at successive interva
“

l s Of twenty four hours in order to

°
1 00

a
-
.
,

l low the spores to develop This process is frequently per .

1
n . a
Ce tr B l tt f u r B ht a .
, I I Ab t h
. vo l . i p
. .
5 85 .
 1 8 PR IN C IPLE S OF LE A TH ER MA N UF A C T URE

formed for bacteriologic a l Observation in flasks or test tubes -

merely stopped with a plug Of sterilised cott on wool which has -

been found to filter efficiently the g erms from the air which enters
through it ( see p 440
-
pp 2 0 9 et s eq) . . .

The ferment organisms cannot thrive and multiply unless

"
-

they have proper nourish ment and conditions of growth the ,

amount of moistur e and t he temperatur e being two of the most

important Of t he latter Us e IS made of this i n the pre servation . _

of many articles of food et c l since by ensurin g that at least one of

the conditions n ec e ss a f y for growth sh a
, ,

l l be absent these sub .

,

st ances are prevented fro m decomposing Fo r instance hides .

,
.

are preserved by drying th em the absence Of sufficient moisture

hindering the growth of any organisms in them so long as they
are dry but as soon as they become somewhat damp putrefaction
“

, ,

commences again S imilarly foods are preserved by chilling or .

,

freezing .

The waste produ cts Of Organisms are Often poisonous to them

selves and for this reason fermen tations frequently c ome to an
,

en d before the whole Of the substance is fermented Thus .

n either beer no r Vinegar can be Obtained of more than a certain

strength by direct fermentation the alcohol or acetic acid chec k ,

ing the growth Of t heir r espective ferments A solution of glucose .

set with t he lactic ferment of sour milk will only p roduce

lactic acid to the concent ration of about one h a l f p er cent but
a
-
.

if chalk be added the lactic cid will be neutralised as pro duced

a
, ,

n d the fermentation will go on till the whole of the glucose

is converted into insoluble calcium lactate 1

Wh en this is a ccom .

p l ish e d the lactic fer ment dies from want Of nutriment and its ,

place is taken by another organism Of which some germs are sure

to be present which ferm ents the c a l cium lactate into c a
,

,
l cium
butyrate If the nourishment fails or the Conditions become
.
,

less favourable for one ferment than for som e other which exists
even in small quantity in liquid the former is qu ickly over a ,

grown and killed and t he latter takes its place Thus the , .

ordinary ferment Of the bran drench will die out rapi dl y u nl ess
constantly transferred to fresh bran i nfusions .

Many Of the products of bacteria ( like those of some of the

'

higher plants ) are intens ely poisonous both to ani mals and
man Many of the severe symptoms Of disease are caused
.

by these poisons produced in the body Thus the tetanus

,
.

bacteria produc e a poison similar in its e ffects to strychnine ,

1
Fo r t he p r at i a
c l p c aa
re p ti f la
r ti aid on O c c c t he so l u t io n a
m y c o n t in a
7 1 to 1 1 p er cent O f gl ad m it g
u c o se n so e n ro en o us n o u r ish m e n t Th e
lig h t l y a
. .

s o l u t io n s h o u l d be s id S cj S . ee ou r n . oc . Che m I n d .
,
1 89 7 , p 51 6
. .
 LE A TH ER MA N UFA C T URE
“

20 PR IN C IPLE S OF

liquors a characteristic sour taste as a consequence of which

liquors cont a ining acetic and lactic acids are usu a
,

ll y known in
”
the tannery as sour liquors .

It is doubtful whether the action of fungi is completely stayed

even by the drying process The heating of leather in the sheds
.

is due to bacteria and the higher moul ds and Eitner consid ers ,

their grb wt h one Of the causes of the spueing or gumming

of curried l eathers .

From what has been said it is 0 b V1 0u s that with regard to , ,

fermentations a double problem is presented to the leather

“

manufacturer since he desires to utili se those which make for

,

his advantage while controll ing or destroying those Which are

,

inj uri ous The first step to a solution of these problems is a

.

more complete knowledge of the organisms which serve Or injure

us that we may as it were discriminate friends and enemies
, , ,
.

We may then approach the question in two ways Taking t h e .

drenching process as an example we may on the one hand intro , , ,

duce a pure culture of the right f erment i n to a sterilised

bran infusion and so induce only the one fermentation which we
,

require or on the other hand as di fferent ferments are affected

in varying degrees by antiseptics we ma
, ,

y perhaps choose such ,

as permit the growth of the organism we want while killing or

discouraging the rest We m a
,

y also arrange the nutrim ent

.
,

tem perature degree of acidity and other conditions so as to

, ,

favour one organism rather than another A ll three methods

a
.

have been applied I n brewing with go od results .

Some in ro r m t io n on the technique of bacteriology may be

found In chaps xiv and xv Of L C P B
. . . . . . .
 CHA PTER V
A N TI S EP TI C S A ND D I S IN F E C TA N TS

A NTI SEP I I CS are often defined a

’ ‘

s substances which check

putrefaction without necessarily destro ying bacteria and their
spores while di sinf ectants are poisonous to ferment
organisms and actu a
,

,
l ly destroy them but though great differ
en c e s exist in the extent of their sterilising power the whole ,

di stinction is one rather of degree than Of kind and has little

practic a Thus common s a
,

l value . l t is incapable of kil l ing most

bacteria even in concentrated solutio n though it holds putre
faction in check both by wit hdr a win g w a
, ,

t e r from the hide and by

directly p reventing the mul tiplication of bacteria If the s a lt
"

be washed out of the hide putrefaction is at once resumed by

,

the organisms present Hides on the other hand which have

.
, ,

once been Sterilised by powerful disinfectants s uch as phenol ,

carbolic acid or mercuric chloride do not again putrefy till ,

the organisms which are killed are replaced by f resh ones from
‘

outside The action of so di um sulphate and many other s a

. l ts , ,

is similar to common salt in this respect while a large proportion ,

of the aromatic compo unds are permanently disinfectant though ,

their efficiency varies with the Species Of bacteria involved

B iernacki a
.

n d others have shown that some disinfectants wh en

extremely di luted actually stimul ate a l coholic fermentation e g ,

.

m ercuric chloride 1 in salicylic acid 1 in 60 0 0 and boric ,

acid 1 in 800 0 and this is probably true Of other ferments and in

, ,

many cases organisms become habituated to antiseptics in doses

which woul d at first ha ve proved fatal
a
'

The number of antis eptics available is now so gre t that it is

impo ssibl e to give a detail ed account of all but the f ollowi ng ,

are among those which are best known and have been practically
employed :
Lime possesses so me antiseptic properties and is largely used ,

in the preservation of fleshin gs before they are sent o ff to the

glue factory They are most conveniently stored i n a large va
. t
filled with a strong and fresh milk of lim e Dilute solutions Of
caustic a l ka
.

l ies have an effect sim ilar to that of lime On e per .

cent solution of caustic soda is practically sterile for most bacteria

.
,

but when lime liquors have become charged with dissolved

21
22 PR IN C IPLE S OF LE A TH E R MA N UFA C T URE

a
org nic matter they support bacteri a
“

l life and this is probably

true of other a l ka
,

l ine solutions
C ommon s a lt so di um chl oride Na
.

Cl acts to a certain extent

by its solubil ity and its dehydrating effect on a n Im a
, , ,

l tissues
which removes water from hides and other materi a
,

l s which it
is used to preserve Probably the latter characteristic has a
.

good deal to do with its effect in checking the development of

b acteria since many species thrive quite well in weak salt
,

solutions and some even in brine and the dehydrating e ffect of

the s a l t enables it to hard en many anim a
, ,

l tissues if used in su ffi
cient qu a ntity the water they contain r u n n In g away In the form
,

o f brine .

Th e very considerable antiseptic and dehydrating effect of

neutral salts like sodium chloride n d sulphate on the hide seems a
at first sight somewhat inexplicable and though in the case Of
the dry sul phate much water is removed as water of c r yst a ll isa
.
,

tion this does not apply to common sal t and especi a

,
ll y when it ,

is used in the form of brine sin Ce st r o n g soluti o ns have rather ,

a Swelling than a dehydrating e ffect on neutral gelatine and , ,

presumably on hide fib r e Th e explanation is probably that in

,
-
.
, ,

the early stages after slaughter the skin is always acid from the
production of sarcolactic and perhaps other acids but as putre
faction proceeds it become s alk a
,

l ine from the evolution of

ammonia The result is that on the acid skin a slight pickling
.

e ffect is produced ( p NO doubt a similar e ffect but much

less marke d may be produc ed by the Nao n the a l ka
.
,

l ine ski n
’
, ,

but this explanation if correct points to the importance of early

salti n g and it may be suggested that if the skins are a l r eady
'

slipping and a l ka
,

l ine a more preservative e ffect and probably

an economy of s a
, ,

a
l t would be obtained by the addition of say
, , ,

2 to 3 per cent of ground nitre cake ( hydric sodium sulph te )

.
-

to the salt to rest ore the acid condi tion

Ordi nary rock s a
.

l t frequently contains ferric oxide and some

times chloride ; and iron either originally present in the sal t or , ,

a
derived from the action of the l atter upon the iron contained in
the blood is one of t he causes of what is known as s a l t st ins
These are sometimes Visible on the flesh of s a
-
.
,

l ted hides but show ,

little during the liming of the hides unless sulphides are used , ,

when stains appear of a greenish black from the formation of “

sul phide of iron ; and when the hides come into the t a
-

n ning

liquor b lack or bluish stains are produced by the action of the

tannin which are parti a
,

l ly removed by the acids of the liquors

during the tanning process but genera
,

l ly show to some extent ,

in the finished hide There are other species of salt stains not
.
-

,
 A NTIS E P TI C S AN D D ISIN FE C TA NTS 23

apparently d ue to iron but to the colou ring matter produced by

fungoid or bacterial growt h which it is practic a
,

l ly impossible to
remove and which a
,

r e stated to be so metimes caused by the ri se

of Ol d s a l t wit h which hides have been previ ously s a

,

l ted I ron
'

a
'

st a
.

i ns r e most readily recognised by t he use of a Solution of

potassium ferrocyanide slightl y acidified by hydrochl oric acid .

If this be applied to the leather the stains will be changed from ,

a blackish to a blue A more absolutely conclusive proof is to .

lay a piece of fil ter paper so aked in dil ute hydrochloric acid upon
the s tain and then to test for iron upon the paper with ferro
cya
,

nid e or thiocyanate The freedom of the paper itself from

iron must be ascert a
.

i ned before use Iron stains produced in

the s a
-
.

l ted state are more difficul t to discharge than those which

are c aused later in the tanning process since iron s a l ts have ,

di stinct tanning power and attach themselves firmly to the ,

untanned fibre On the Continent where common salt is heavily

taxed a l um carbolic a
.
,

, c I d naphthal e n e and other materials are

, ,

frequen t ly added to it to denaturise or render~it incapab le of

being used as food and these additions are Often the cause of ,

trouble to the tanner So di um carbonate seems on the whole

the best denaturising materi a
.

l
S odium s u lpha te Na
.

z SO4
has little if any disinf ectant power
, ,

in di lute solution but if use d in the calcined form ( anhydrous

,

sodium sulphate) as proposed by Eitner 2 as a substitute for

common s a
,

l t in preserving hides it with draws water from the

hide and cryst a
,

l lises w ith 1 0 A q ( about 5 6 p e r cent ) This does 1

.

not run away like brine b ut remains in the hide which retains
its Weight , a
, ,

n d remains plump and swells well in the limes and

“

liquors as the sulphate is partially con verted into cau stic soda
,

by the action of the lime 1 0 to 1 5 per cent on the weight of the .

hide is sufficient while salt must b e used in nearly double this

,
'

quantity Care must be taken that the sulphate used is free from
bisul phate Na
.

HSO4 Which has a powerful swelling e ffect upon

, ,

the hide fib re like sulphuric acid The neutral sulphate does

-

, .

not redden m ethyl orange or litmus ’

The s tr ong er min er a l a

.

ci ds have considerable antiseptic p ower

even when very dilute and a r e of course especially f a

,

tal to such
ferments as thrive best in alk a
,

l ine solutions The use of sul

p hu ric acid in pic kling skivers has a
.

l ready been alluded to and ,

a very dilute solution applied without salt to raw hides prevents

putrefaction though the principal Obj ect in using it is to plump
,

the hides and produce a fictitious weight and substance which

1
For af u rt h er d is cu s s io n of s a
lt t a
i -
s n s se e a
Ch p t e r V I p . .
36 .

2
G er b e r ,
1 8 80 , p . 1 85 .
24 PR IN C IPLE S OF LE A TH ER MA N UF A C T URE

d isappear on tanning Such hides of course have a powerful

acid reaction to litmus Sul phuric acid in sm a
.

. l l quantities has
been used wi th advantage in soaking E I kips A very small . . .

excess Of hydrochloric acid will sterilise putrid effluents and no

doubt nitric or sulphuric acid woul d ha
,

Ve the same e ffect Th e

powerful effect of mineral acids on anim a
. .

l fibre and their solvent ,

action on cements and iron preclude however their general use

, , ,

as ant iseptics .

More imp ortant is the use of sulphurous acid and sulphur

“ ‘

t : s c

FI G .
5 .
— Su l p h u r o us aid a
c ppaat r us .

di oxide which from their m ild acidity and great antiseptic

, ,

powers are capable of a variety Of useful applications Consid er

, .

able doubt has been raised as to the germicide power of sul phur
dioxide and it is certain that the dry gas is l ess effective on dry
obj ects than when applied in solution or to moist mat eri a
,

l s as
'

is a
,

l most invariably the case in the tannery It may possibly .

be more efficient in its action on some moulds and putrefaction

ferments than on the pathogenic bacteria which have been most
frequently used to test the power of disinfectants but in practice
it is found extremely useful in the brewery and in gelatine manu
facture and there is no reason that it should be less so in the
,

tannery .

The gas is most conveniently produced by burning sulphur ,

which produces double its weight of sulphur di oxide If used for .

stoving drying rooms and other p laces infested with mo ul ds ,

 A N TIS E PTI C S A N D D ISINFE C TA N TS 25

care mu st be t a ken to avoid risk of fire A sh a ll ow cast iron

pot set on bricks o r sand is genera
-
.

l ly the most suitable vessel ,

and the sulphur may b e ignited by a piece of red hot iron or a -

rag which has been previously dipped in melted sulphur It is

corrosive to met a
.

l work and bleaches many colours but does

-

, ,

not produce any marked injurious e ffect on leather though the ,

sulphuric acid formed by o xidation may if not removed ulti , ,

mately make it tender

For many purposes a solution of the ga
.

s is required and this ,

is most easily made by burning the sul phur in a smal l metal or

fire b ric k stove from which the fumes are sucked through a
scrubb er which on a sm a l l sc a
a
l e is conveniently made of large
, ,

g lazed san i tary pipes p ck ed w ith coke or broken earthenware 1

over which water is a

, ,

l lowed to trickle Th e lowest pipe has an

a
.

Opening for branch pipe which is connected with the stove and, ,

rests on three bricks in a trough or tub which collects the acid

solution and forms a water se a
a
,

l to prevent the escape of gas

a
-
.

A bove the i nl et for the gases is fixed wooden gr ti ng on which ,

the cok erests The scrubber may be 1 0 to 1 5 feet in height and

.
,

connected at the top with a chimney or steam ej ector 2 to produce

the draught The arrangement is illustrated in fig 5 A nother
. . .

method is to burn the sulphur in a closed cylind er and to force

the products through water with an air compressor and this is -

necessary where the gas is used as 1 5 now commonly done in ,

reducing bichromate solution for chrome tanning ( see p .

In place of using a scrubber the fumes may be blown by a ,

steam inj ector direct into a tank This Is a very good arrange
ment for w ashing and bleaching h a
.

i r etc but where large ,

.
,

quantities of solution are r equired is inferior to the scrubber

I nj ectors of hard lead or regulus met a
.

l sho ul d be used and are ,

less acted on by th e dry gases than by the very dilute moist

exhaust from the scrubber ( see p
B isu lphites have a
.

l so strong antiseptic properties Eisul .

p hit e of soda ( hydric sodic s ul phite ) solution may be made by

supplying the scrubber with solution of soda ash or washing soda ,

bisul phite of lime by using milk of lime or packing the scrubber

With ch a
,

l k or limestone ( free from much iron ) 1 n place of the coke .

In either case a much stro nger solution is obtained than with

water a l one .

1
Co ke co nt a
i
nsag ood de l af o ir o n , wh ic h wil l co nt a
mi a
t n e t he aid
c

fo r so m e l it t l e t im e B r o k en p u m ic e is f r e e f r o m t h is d e f e c t
a a
. .

2
Th e j
e e ct o r m u st b e o f r e g u l u s m e t l t o r e sist co r r o s io n Th e ir

a ab la
t d by ab i k p l ad i
.

d m it t ed t o t he st o v e c n e re gu e r c ce n fr o n t of t he
o p en in g .
26 PR IN C IPLE S OF LE A TH E R MA N UFA C T URE

B o ke sa metab isul phite of soda

’
is a very convenien t 1

source of sulphurous acid when the latter is wan ted in small

quantities It is an a . n h yd r o s u l p hit e and contai ns ,

67 4 per cent of its weight of 8 0 2

-
. On e molecule of the salt .

requires one mol ecule of H z SO4 to set free the

a
a
whole of the sulphurous acid Fo r m ny purposes the sulphate
of sod formed may be neglected and the acidified solution used
direct .
.

Fo r analysis of sul phites and sulphurous acid solution see

p 7 3 and . p 13 , . .

If bisulphites are used in tanning liquors t heir e ffect in bleach

ing a reds ( p hl o b a
,

nd making soluble t he p h en es ) present In

many tanning materials must not be overlooked This action .

improves the colour of the leather but at the sam e time ,

diminishes its solidity and weight though it probably assist s in ,

the more complete utilisation of the tannins In most bleach .

ing extracts bisulphites are present in large excess and not ,

only keep the reds of the extract itself in Solution but di s

solve those Of other liquors with which they are mixed a
,

n d of the ,

leath er itself thus rendering it more p orous

B ori c a bor a and other bora tes a
.
,

cid x ,
re not very powerful
,
.

disinfectants They have no inj urious action upon the skin but
.
,
'

to b e e ffective require to be employed in pretty strong solutions ,

say 1 per cent and their comparatively high cost u n fit s them for
, ,

general u s e as antiseptics in the tannery though boric ( boracic ) ,

acid is very useful as a drenching and deliming agent ( see p .

20 5 , , p .

M ercuri c chl o r ide corrosive sublimate Hg Cl z is an extremely

, , ,

powerful antiseptic preventing the growth of some speci es of

,

bacteria in solutions so dilute as I in ( Koch ) 1 in .

is disinfectant ( Miquel ) but its power varies very much upon ,

di fferent organisms ( JOr g en se n states that 1 in 400 is required

to kill P en icilliu m gl au c u m) and it is unsuited for most purposes ,

in leather manufacture both from its extremely poisonous char ,

acter and because it is rendered inactive by various substances

,

present in the materials used In conj unction with formic acid .

,

however ( Seymour Jones p it is extremely effective in

-

,
.

the dest r uction Of anthrax spores and can be employed in ,

solutions so dilute as to be quite harmless to the workmen .

Mer cu r ic i o dide dissolved in iodide of potassium solution

was patented by Messrs Collin and B enoist as an antiseptic in
tanning but it is expensive and has the same defects as mercuric
, ,

chloride ; although under favourabl e circumstances it is even

1
a
P t e n t e d b y B o k e s , Lt d a .
, a
St r t f o r d ,
Lo n d o n ,
E .
28 PR I N C IPLE S OF LE A TH E R MA N UFA C T UR E

inj urious effect on the hide but the pres ent price of glycerine
is prohibitive .

An aqueous solution containing 1 per cent of carbolic acid is .

sufficient for mere steril ising of hides but if it be desired to , .

preser ve them for a long period stronger solu t ion s ( up to 4 per ,

cent ) may be employed

. .

Quantities so small as 1 part per 1 0 0 0 control t he fermenta

tion of liquors and prevent the formation of moulds on the
,

surface economising tannin and preserving vegetable acids

a
, ,

a
l ready present but at t he same time l essening their production
by fe 1 m en t a
,

t io n and ther efore sometime s le di n g t o difficul ties

,

in the early stages of tanning Carbolic acid is not strictly

a
spe king an acid but rather of the nature of an alcohol a
.
,

, , l though ,

it forms weak combinations with bases It does not swell hides

but is a powerful narcotic poison a
.
,

n d if dropped on the ski n

“

in a concentrated form it produces severe burns which a

,

re b e s t
'

treated with oil while in cases o i poisoning oil and ch a

,
'

, l k must
be administered internally but if the quantity of carbol ic acid ,
-

taken has been large are not likely to be effective From its , .

cheapness and efficiency carbolic acid is likely to be increasingly

used a ,
l though fO r special uses some of the newer antiseptics have

great advantages
Cr ea
.

so t es and c r e s ol s can be dissolved in oils and stu ffing greases ,

and act as antiseptics though less p owerfully than in aqueous

'

solution Eu d e r m in
. is a preparation made for this purpose .

R osin oils and turpentine have al so antis eptic properties

C r ea
.

” ”
h eavy coal oil or dead Oil is a complex mixture
'

so t e , , ,

of hydrocarbons phenols and cresol s obtained by distill ation of

co a l tar heavier than water a nd a
, , ,

,
l most insoluble in it It is , .

largely used as a preservative for timber Carbolineum is

a
.

an oil of this class boiling t over 3 0 0 C and intended for

,
°

application to wood On e or more coats are applied to the dry.

wood at a temperature of 80 C The workman s hands must be °

.
’

protected by glo ves as the hot creasote raises painful blisters

,
.

Eitner recommends its use for preserving pits posts and other
1
, ,

woodwork in tanneries Wood creasote is a somewh at similar .

-

product Obtained from wood tar -

.

Th e heavier cresols are so little solubl e in water as to be value

l ess as antiseptics in their ordi nary form b ut severa l preparations ,
” ” ”
are mad e under the names of Creolin Jeyes fluid Lysol ,
’

, ,
”
I zal Soluble phenyl etc in which they are treated with
additions of soap or a
.
, , ,

l kalies which cause them to emulsify or

‘

dissolve in water genera

,

l ly as milky l iquids which are powerful

, ,

1
G erb er , 1 8 89 , p . 1 83 .
 A N TIS E P TI C S A N D D ISIN FE C TA N TS 29

germicides a n d have the advantage over phenol of being non

a
,

p oisonous O I to O 5 per cent

. solution of creolin will sterilise . .

hides after bating so that no putrefaction t kes place in the

liquors Mr J T Wood specially recommends creolin for the
genera
. . .

l p urposes of the tannery di sinfecting pits and tubs and

for checking the action of puers a
, , ,

n d drenches on goods which

h ave gone a little too far by throwing them into a 0 2 per c ent ,
-
.

solution
Sa licyli c a
.

cid o r t h o hydr O x yb e n z o ic acid C6H 4 OH ( COOH) is

now arti ficially prepared fro mphenol It is m u c h less poisonous
, , ,

than the l att er and has no smell which makes it valuable for ,

certain purposes b ut is too dear for most technical applications

Man y bacteria appear to become gradu a
.
,

l l y habituated to its
action and the same is true of phenol to a less degree
,
.

Salicylic acid is closely related to protocatechuic and gallic .

acids and lik e these gives a blackish colour W

, ,
ith iron salts ,
It .

is freely soluble in h o t water but very sparingly l n cold The

addi tion Of 1 t o 2 % parts of sodium phosphate sul ph ate or p o t a
.
,

s , ,

sium n 1 trate to each part of salicylic acid greatl y i ncreases its

so lubility It is more powerful in preventing the development
o f bacteri a than carbo l ic a
.

cid a solution of 1 part of salicylic

acid in 666 of water is said to be equal in this r espect t o 1 part
'

of carbolic in 200
B en z oic a
.

a
ci d C6 H 5 GOOH though not much employed except
, ,

a
in medicine is a still more powerful disinfectant and h s the
, ,

advantage of b eing n on poisonous t o hum n beings

A n ti ca
-

l ciu m
.

1
Is a solution of mixed sul phonic acids derived

from cresols and has considerable disinfectant powers It

,
.

also removes li me very e ffectively but from its acid ch aracter ,

.

somewhat swells the skin

CT coa
( l tar ) bate is a grey crystalline pasty mass with a
'

tarry smell a d is chemically very similar to a n t ic a

. .
,

n l c iu m if not
identic a Many other c o a l ta
, ,

l with it r s ul phonic acids have

.
e

similar properties These preparations have not much im .

portance for deliming but may be useful where an antiseptic

action i s a
,

l so required
Na
.

ph tho l s C H 7 (
O H ) These bo di es which have the same
—

relation t o naphth a
1 0 , _ ,

l ene as the phenols to benzene are powerful

a
,
,

a
antiseptics and naphthalene itself appears to h ve antiseptic
power n d is occasion a
, l l y used for denaturising s a lt There .

are two naphthols varying in the position of the OH group in

the molecul e and denominated aand B Of which anaphthol is
,

, ,

the more powerful antiseptic and the less poisonous though B , ,

1
G erb e r ,
1 89 5 , p . 1 33 .
30 P R IN C IPLE S OF L EA TH ER MA N UFA C T URE “

a
being cheaper is the common commercial article It is said that
qu ntities so small as 0 1 to 0 4 gram of anaphthol per liter are
.
,

-
.

suffi cient t o prevent the development of microbes while of B ,

-

naphthol about ten tim es that quantit y is required

Naphthols are not very expensive but their va
.

l ue is diminished ,

by the fact that they are insoluble in water though soluble in ,

alkalin e solutions but their compounds with bases are of much

lower antiseptic va l ue and the same is true of their a
,

a
, l coholic
solutions ; when n alcoholic solution is added to water the
naphthol is precipitated ; but if an addition Of soap or camphor
be made t o the alcoholic solution the naphth o l remains in a very ,

finely divi ded condition if not dissolved , .

A dopting a suggestion of Eit ne r s with regard t o oxynaphthoic

’
1

acid hides may be sterilised by the naphthols and other diffic ul t l y

,

a
soluble aromatic antiseptics by treatment first with a weak
alkaline solution of the antiseptic a nd fterwards wi th a weak ,

a
acid to remove the alkali Hides treated in this way are p e r
ma a
.

n en t l y sterilised and c nnot be unhaired by sweating n d

, ,

woul d probably lime with some difficulty

Ca
.

r bon di su lphide — Moret has suggested an aqu eous solution

of this compound as an antiseptic and it seems to have consider

able sterilising powers b ut from its in fla a
,

mm b il it y poisonous
, ,
,

character and unpleasant smell it is not likely to come l argel y

, ,

into use It is sometimes u seful for preserving putrescible

.
“

matter in the laboratory

Fo rma
.

ldehyde COHz in aqueous solution containing about 40

, ,

per cent o f formaldehyde tog ether with a little formic acid is

.
,
”
sold under the nam es of formalin formol etc I t has , , .

great disinfectant powers and is valuable in various processes ,

of leather manufacture but has a hardening and tanning effect ,

on hide fib r e and gelatin ous matters so that in very dilute

The vapour o f form a
-

solution it will produce leather 2

l dehyd e -

or Of its condensation product paraform m a

.
,

y be employed to
-

harden microscopic preparations On e part of formaldehyde

and consequently 2 ; parts of form a
.
,

l in in 1
parts of
water is said to sterilise and forms a good disinfectant solution
, ,
.

Even in considerably larger proportion than the above it is not

poisonous and thus poss esses the bactericid a l power of sublimate
without the latter s poisonous propert ies Form a
,

l dehyde has
’
.

another advantage over most if not all other antiseptics in that , , ,

it may be used as well in the gaseous as in the liquid state and on ,

that account it is largely employed in the disinfection of rooms

1
G e rb e r ,
1 8 88 , p 1 0 1
. 1 88 9 , p p 9 9 e t . seq . Se e a
l so p . 20 6 .

2
G er b e r ,
1 8 9 7 , p 6 7 ; i bi d , 1 8 9 9 , p p 1
. . . 01 ,
205 , 2 1 8 .
 A N TIS E P TI C S A N D D ISIN FE C TA N TS 31

or of articles which wo uld be spoiled if they were to b e wetted

as the gaseous form a
-

l dehyde though thoroughly disinfecting ,

‘

them will not injure th e colours of materials of the m ost delicate

,

fabrics .

On account of its power of renderi ng gelatinous matters hard

and insoluble in water form a l dehyde requires to be employed
,
‘

with great caution in leather manufacture but 0 2 to 0 3 per cent -

may be successfull y used in admixture with egg a

.
,

l bumen in the -

preparation Of seasoning in the finishing of morocco leather .

It is also used commercially to produce di fferent varieties of white

leather for soldiers accoutrements and similar purposes ( pp 459
’
.
,

and for fixing hides in a swollen condition prior to tanning .

Tr if ormol ( tri oxymethylen e paraform is a p roduct of

“

the polymerisation of form a l dehyde and is prepared by e va

-

po ,

rating a solution of the latter to dryness on the water bath It is -

.

more powerful than formal in in its antiseptic properties but has ,

n o t entered very largely into use as a disinfectant though con

s id er a fix bacteria in g el a
,

bl e use is made o f it to -

t in e for
bacteriological purposes
Ca mphor a n d ess en tia
.

l oil s as well as oil of turpentine are

a n tiseptics and the cheaper essenti a
, ,

,
l Oils such as those of wi nter ,

green black birch sassafras and aniseed are frequently em

plo yed especi a
, , , ,

l l y In A merica in preserving pastes finishes and

, ,
,
,

seasoni ngs and at the same time covering o ffensive odours The
, . .

odour of essential Oils becomes much more powerful as they are

diluted and very sm a
,
l l quantities su ffice for the purposes men
t io n e d. Birch tar oil such as is used to give the scent to R ussian
-

leather ( p is antiseptic and prevents the attack of insects

A rtificial methyl salicylate is n o wmade which is chemic a
. .
,

l ly
identi ca
,

l with oil of winter green though from the presence of

-

some impurity it has a different but not unpleasant odour It

has considerable antiseptic powers and is much used as an extern a
.
, ,

l
rheumatism remedy The essenti a
,

. l oils of cloves and pimento

are also good antiseptics .
 CHAPTER VI

TH E O R I G IN C UR I N G H ID E S A N D S KI N S
“

A ND OF

A proportion of the hides and skins used in

CONSI D E RA BLE

leather manufacture are those of anim a l s killed by the butcher

a
"

for food and these are frequently employed by the t nner with
,

out any preliminary curing DO esti o hides and skins are

now genera l ly sold by auction in we eld y markets in the principal
.

towns after sorting and classification in weight and qu a

,
l ity .
1

This is in many respects an improvement on the old method of

purchase dir e c t fr o m the butcher but it Often leads to delay In
.
,

delivery and in ho t weather hides su ffer from putrefaction In

‘

.
,

FI G . 6 — Me t h o d
. of m aki r ng we ig h t on h id e s 9 7 1b .

most cases the damage is not sufficient seriously to a ffect the

durability of the leather but the delicate membrane of the ,

grain is inj ured and t he hide or skin un fit t e d for coloured

leather or any purpose where sm a
,

l l damages to appearance are

imp ortant B utchers are averse to the use of sal t b ec a
,

. u se it , ,

withdraws water from the hide in the form of brine and so ,

causes it to lose weight but much injury would be saved by

a light s a
l ting and al l hides or skins on which the h ir is
ping shoul d be regarded as damaged for fin e leather m a
,
slip
nufacture
a
Sheep ski ns are not usu a
.

-
l ly bought direct by the tanner but ,

by the fellmong er who removes the wool and as this is of much

,

1
Th e w e igh t of a d it d t t h b t h i
E n gl is h m ak r et h id e s s cre e o e u c er s

at h t a t w it h a
-

u su all y m a k d th dg
r ef th b tt
on il b y
e e e o k if e u ne r e cu s n e,

th m d
e fo m a ti
e o b i g nu ffi i t l yer plai d b y F ig 6 i w h i h
on e n su c en ex ne h c
-

ta ah p 1 b t ha t a
.
,

t i g t h h iz
c u s c ro s s n l li e tor on b it 1bne e c re r e se n 20 o ve 1 0

a t a d i R m afi g
. .
, ,

w h il l e m e ss p o un s re ex re s s e n o n ur e s

t w ig h t a a f ha lf a
.

O th C ti
n e on ll y g i
nen i p de sk il re u su ve n n o un s o o

gra m (5 k il =0 1 b E gli h )
os I Pa
1 1 0i th ma ki g i n th ta il s n r s e r n s on e

ad i a
. .
,

n l s h w fig 6
so s o n on . .
 o R I GI N A N D C UR IN G OF HI D E S A N D S KINS 33

greater va l ue than the skin the latter is frequently han dl ed very

carelessly and it s quality sacrificed for the s a ke o f re a
,

l or fancied
'

improvement to the wool In very many cases the skin is .

sweated or staled by hanging in a warm and moist

chamber h eavily charged with ammoni a ,
derived from the putre
faction Of the skin until the wool is sufficiently loosened to be ,
.

”
pulled If this treatment is conducted with extreme care
.

the skin may escape serious injury but in most cas es the grain
is weakened a
,

n d the foundation is laid of damage which makes

, ,

1
itself felt throughout the tanning process
The best method is t h a t ge n e r a
.

l l y employed by the freezing

“

companies and t o some extent by the more modern fellmongers

, ,

in which the skins after thorough washing are painted On the

flesh side with a thick milk of lime to which is a
.
, ,

dded 2 5 to 3 0 ,

per cent of sul phide of sodium on t he weight of the lime employed

.
,

t aking care that none of the s olution touches the wool The .

skins are then piled flesh t o fle sh for twenty four hours when _
-

the wool will be fou nd ready t o ; pull An Older method is to use .

-

milk of l ime only and in the case of shearlings where the wool , ,

is not of s o much value the skins are laid flesh to flesh in shallow ,

pits and covered wi th water Fo r further details see Chapter .

X I II on depilation . .

On e of the great causes of inj ury to the pelts is their collection

b y the fellmonger In what are calle d gathering limes where ,

they remain till taken by the pelt sorter These limes are .

frequently very old and stale and swarming with putrefaction

bacteria If kept in limes at a
,

. ll these should be fresh and fr e ,

quently renewed but even fresh sweet limes dissolve the cement ,
.

ing substance of the fibres , and increase the naturall y loose

text ure of the sheep skin if the treatment is lon g continued In -

the A merican stockyards the skins are only limed for the time
necessary to swell and differ entiate the fibre and are then at
_ ,

once dre nched and preserved by pickl ing ( p .

Where hides or skins cannot be used at once in the fresh state .

there is probably no better method of preserving them than the

use of s a lt A lthough s al t is not fatal to bacteria it so slo w
. s ,

bacterial growth partly by its direct antiseptic effect on many ,

organisms and partly by withdrawing water from the skin

, ,

that wel l salted skins can be kept in good condition for an almost
-

unl imited time Wh ere it is only required to preser ve goods for.

a week or two a mo derate sprinkling on the flesh side is efficient

, ,

but if they are to be preserved for a length of time more thorough ,

1
A s t o t he u se of a
mm iaga aa on s s su b s t it u t e fo r pu t r e f a
c t io n se e

p . 1 66 .
34 PR IN C IPLE S OF LE A THER MA N UFA C T URE

a
tre tment is necessary It is said that however carefully hides
are s a
l ted they deteriorate if kept in this condition above twelve
.

months It is advantageous to wash and well drain hides before

salting a
-

s by this means most of the blood lymph and dung

are removed which a
, , ,

re the most putrescible constituents of t he

“

hide
Th e method of s a
.

l ting employed in the Chicago stockyards

for packer hides may be taken as a good type of a thorough
«

salting The hides are first trimmed from useless switches

and any large portions of adhering fat a
.
,

r e removed The curing

takes place in large and c o o l c ell a
.

rs with co n cre t e fl o o r s Th e
‘

detail is well given in the fo ll o win g e x t r a

c t from the S ho e a
.

nd
'

a
a
Le t her R ep ort er
Great care is taken to m ke the sides of a pack higher than
"

the middle so that the brine which is made by the j uices of

the hide coming in contact with the s a
,

l t will b e retained T he
brine can only esc a
.

pe by percolation and hence the fibre of t he

hides is thoroughly cured The floor of a hide cellar is usu a
,

l ly .

of concrete and a pack is from 1 5 to 20 feet long and as wide as

'

the sp a
.

, ,

é e between the posts which support the floor above Th e

a
.

sides of a pack are built first to a height of from 4 to 6 inches ;

the cross layers are th en put on genera
/

l ly three on e ch side , ,

two being inside and one having the butts drawn out to the .

edge In a pack 20 feet long the side layers will contain about
.

2 5 medium sized hides each and a cross layer 1 2 or 1 4 To

begin a pack a truck load of hi des is run a
- -
.
,

l ong to the front of

-

the place selec ted one spreader grasps the butt and his partner
,

the head of a hide and tog ether they carry it to what is to be

, .

the rear of the bed Th e hide is then dropped so that the folded
.
,

back is parallel to and from 1 5 to 2 0 inches from the inside line

of the posts the h ead a trifle closer than the but t Th e front
man takes the dewlap a
.
,

n d front shank in his left hand and

extends his right a
_ ,

l ong the belly of the hide as far as is nec essary

to raise the edge the rear man holding the flank with one hand
,

and the hind—shank with the other They keep their legs well
out of the way of the s a
.

l t thr o wer who with a single thro w .

,

covers the whole hide being particular that enough salt strikes ,

against the edges held by the men to make a pronounced ridge

when they are lapped down A little salt is thrown on the hair
surface and the butt folded over bo ut a foot The folded edge
is then drawn out even with the outer line of the pack More
.

a .

hides are placed the same way until the corner is high enough .

A fter this each hide is put further forward to make a level

,

surface from rear to front the heads at the front corner being ,
36 PR IN C IPLE S OF LEA THER MA N UFA C T URE

salt as it accumulates and trucks it to the salt bins where it

.
,

is mixed with new to be used again A horse made of a ’

a
, .
,

network of scantling about 3 1; feet wide by 6 feet long and stand ,

ing 2 & feet from t he flo o r is placed in front of the p ck on this '

a
,

the hides flesh side down are shaken to remove the salt that is
, ,

clinging to them This process requires four men one at e ch

.
,

corner The hide is brought down heavil y on the horse twice ,

"

and then spread on the floor flesh side up for examination by

the inspectors of w hich there are two one representing the
, ,

hous e and the other the buyer of the hides Th y sweep o ff

e
.

any salt that may be left and examine for cuts s o res brands
ma
, , , ,

nure and grubs They al so see that the hide is properly

, .

weighed and classified If the contract calls fo r a special trim .

a
it is now done Two men then roll the hide begi nning by
a
.
,

lapping over the shanks he d and neck Then the sides r e , , .

folded over and lapped again leaving the roll 1 5 to 1 8 in ches ,

wide The en ds are thrown inward slightly overlapping each

. ,

other ; a final fold is then given and the hide is ready to be ,

tied R ope the size of clothes line 1 s used for tying and 1 s cut
.
-

into lengths of about seven feet I t t akes three men to tie for .

a
a gang such as we have described After tying the neat bundles .
,

are weighed and loaded on the c rs for shipment A small tare

is a
.

”
ll o wed the buyer .

Ab o ut 2 5 per cent of salt on the green weight of the hide is .

required for thorough curing R ock salt merely crushed is .

, ,

frequently used but this is very liable to contain iron in the form
,

of f erric oxide Which is said to be the cause of t he peculiar marbled

or m a
,

p like markings
-
known as salt s t ains These certainly -

.
“

contain I ron as is shown by their brownish yellow colour when

,
-

the hides are unhaired from a white l ime their dull green
from sulphide limes and the fact t ha
,

t t h e y turn black or ,
.

p urplish in tan liquors and give the ordinary blue with ferro
“
'

and ferricyanides and it is certainly better to use cryst a

,

, l lised
salt but its use does not always prevent them and their
, ,

cause is probably more complex and not unconnected wi th ,

bacterial action In 1 9 1 2 it was the subj ect of considerable

“

investigation by Dr Ab t P rofessor B ecker ; and others the resul ts , ,

of which will be found in the volume of Coll egium for that year ,

but unfortunat ely these authorities do not altogether agree in

their conclusions and it is possible that they were not dealing
,

with the same defect as probably various stains of different ,

origin are confused under the general name Ab t found that

the stains which he ex a
.

mined ap peared to originate on the

flesh side and spread through t o the grain H e attributed them .
 OR I GIN A ND C URI N G OF HI D E S A ND S KI NS
‘

37

to the small sp hero crys t a l s of double sulphate of calcium and

sodium ( Sc hl o t t s grains) which occasionally occur in salt and
’

which he sometimes found adhering to the spot Where the stains

originated The stained parts did not usually contain more iron
:

than t he rest of the unstained skin b u t singul arly had a large , , ,

excess of phosphoric acid which is not contained in the salt H e , .

produced similar stains artificially by placing on the flesh side

grains of calcium sulphate with crystals of ammonium phosphate
and their appea
,

rance was favoured by the addition of traces of

iron salts He a ttributes the pho sp horic acid ( probably in the
.

form of ammonium phosp hate) to bacterial action on the nuclei

of the epidermis and hair sheaths and the iron may be derived
in sufficient quantity from the h a
-

em oglobin of the blood left in

the skin H e adm its that the colo ur—reactions with sul phides
.
,

tannin etc are due to iron but cannot exp lain why the unstained
, .
, ,

parts which contain sensibly as much iron do not stain He

found no microscopic evidence of b acteria in the stains a
.
, ,

nd ,

attempts at culture gave negative results .

B ecker on the other hand found in the ochre yellow stains

, ,
-

co cc i of about 1 5 diameter which he c ul tivated easily on meat

°

p .
,

broth pe ptone gelatine and which were aerobic ( required oxygen )

, ,

and liquefied the gelatine and gradually liquefy hide H e also , .

detected co ccu s bacteria in the red and orange stains but these ,

did not liquefy gelatine or attack hide and may be considered ,

harmless to the tanner They were also cultivated on bouil lon .

‘

peptone gelatine but with considerable difficulty requiring a

, ,

somewhat high temperature and a long time ( about six weeks)

for their development With all three bacteria B ecker found
a toru l a
.

or yeast with which they appear to be symbiotic The

, .

red and orange bacteria co ul d be cultivated alone on raw hide

containing blood and lymph but not on pelt from which these , ,

liquid nourishments had been removed by the wet work but

developed on the latter when associated with the tor u l aof which
-

the dead cells furnished them with nourishment B ecker con .

s id ere d that salt alone is not sufficiently antiseptic to prevent

the growth of bacteria but found that an addition of not less than
4 per cent on the weight of the salt of c a
,

lcined sodium carbonate

rendered it practically sterile H e also found that so a
.

k ing the .

hides in a 0 2 5 per cent solution of zinc chloride for two hours .

,

or in a 0 5 per cent solution for half an hour previous to salting

.
,

had a Similar effect H e stated that 1 5 per cent addition of

. .

sodium perborate to the salt would sterilise but swelled the

hides and recommends so a k ing for an hour previous to salting
in a
,

0 2 5 per cent solution of artificial mustard oil but points

.
-

,
38 PRIN C IPLE S OF LE A TH E R MA N UFA C T UR E

out that the hands of the workmen must be protected by india

rubber gloves .

The wri ter has from time to time examined many salt stains -

of the map like kind which appear on the grain but has never
-

paid much attention to the flesh nor seen sign s of serious inj ury ,

there These marbled or map like stains whatever their original

cause always owed their colour to iron a
-

.
,

, nd gave the usual iron ,

reactions In th is connection attention may be drawn t o the

.

case of plaster kips mentioned on a later page A lthough much

-

iron was contained in the salt earth Which constituted the cure -

serious staining only took place after the kips had been kept
through a winter in a damp London warehouse and the I ron ,

tannage of the grai n was then so bad as to render the unhairing

very difficult and imperfect In this case there was little doubt .
‘

that the iron was derived f rom the cure but the writer has also
-

observed marked iron stains following the course of a vein con

-

taining blood which is quite common in kips which have died

,

from natural causes and which are known as dead in dis

,
”
tinction from slaughtered .

I t is impossible to anyone who has known them to doubt the

ca
a
re accuracy and competence of both Ab t and B ecker as
chemists and b cteriologist s a
, ,

n d it is m rI ch to be desired that
'

some explanation should be found of their differences though it ,

may be feared that the effects o f the war have rendered co

o p er a
t iv e wo rk for the present impossible I t may be that they
'

a
.

were working on distinct kinds of st in but it is not impossible ,

that iron may have accumulated In the spots in consequence of

the presence of phosphoric acid with which ir On forms a very ,

insoluble compound or on the other hand that B ecker s ’

a
, , ,

b acteria owed their colour to iron B acteria are well kn own which .
-

absorb iron The writer has a well on his p r em ises which cont ins
“

a trace of iron bicarbonate together with calcium and a little

“

sodium bicarbonate and its walls are always c overed with a red
,

brown deposit of a special iron bacterium Though Ab t does ~

-

not specifically say so he apparently made his an alyses of the

,

stained and unstained portions from the flesh side of the hi de ,

and it is not im p robable that the iron was simply attached to

the unstained portions in an insoluble form ( oxide or carbonate) ,

while in the spots it had becom e soluble and diffused into the
hide These however are speculations and must wait further
.
, , , ,

investigation .

3
A reddening of the flesh side is Often noticed in hides which
have been kept in salt long or under unsatisfactory conditions
'

and is very frequent in wet salte d South American hides Such -

.
O R I GIN A ND C UR I N G OF H I D E S A N D S KI N S 39

hides a r e said never to p roduce so firm a leather as those which

are sound This may be due to one of B ecker s pigment

.
’

bacteria I t is also conceivable that it may be caused by B

'

a
. .

p r o di gi os s the bacterium which causes red bread etc and

, , .
,

which is known t o attack p ickled skins .

H ides are frequently cured by steeping in salt brine instead

of strewing wi th dry salt This method is principally resorted .

to in order to give fictitious weight B rined hides do not plump .

well in tanning the leather is not so good in quality as from tho se

,

salted with dry salt and t he cure is much less efficient , .

Many hides are not only salted but also dried in order to
preserve them No t much detail has been published with regard
.

to the methods used which no doubt vary much in different ,

p laces , but probably in some cases the hides are salted in pile
and in others by brining and then hung up to dry The principal , .

obj ect of drying is to economise weight and cost of transport ,

but it makes the hides much more difficult to wash and soften .
,

for tanning ( though e asier than hides dried without salt ing ) and “

p robably the crystallisation of the salt has a weakening effect

”
o n the fibre Hides cured in this way are s t yled d ry salted
.
- -

A large num b er of the hides of the small native cattle of

I n di a are im p orted into this country in a dry salted condition -

The following particulars of their cure are taken from a pap er by

the A uthor and Mr W Towse
a
1
. .

Dry salted or as they r e commonly called plaster cures

such as those of D acca and Meha p o re , are thickly coated with a
-

, , , ,

white material which in t he first instance is merely the insoluble

,

portion o f a saline earth used in the cure though in many cases

it is applied in larger quantities than necess ry with the simple a ,

obj ect of giving weight The salting is thus described by Mr .

W G Evans who some years ago had considerable experience

. .
,

as a tanner at Cawnpore
The salt used by the natives is a s a lt e a
r t h and is so called ~
,

by them I t is found extensively in the districts of Cawnpore

.
,

A gra D elhi Lucknow P atna etc and has no doubt something

, , , , .
,

to do with the localisation of the hide curing and kindred in -

d u s t rie s in these places Th e mode of procedure used is pretty .

m uch as follows : the salt earth is mixed into a very thin paste -

and this is lightly brushed on to the flesh side one day and the ,

hide allowed to re main over night under cove r Next day for .
,

best hides the same solution is again spread on the flesh side of
,

the outstretched hide and rubbed into it with a porous brick and ,

then for legitimate salting the hide is allowed to dry under

, ,

ja
m S oc Chem I n d 89 5 , p
1 1 0 25
/
n . . . .
,
1 . .
 L EA TH ER MA N UFA C T UR E
“

40 P R IN C IPLE S OF

cover I f for export the saltings may be three or four and the
.
, ,

hides are treated out in the Open subj ect to the intense heat of ,

the sun which accounts for the number of hides which go back
in the soaks in England and elsewhere We had a clause in our .

agreement with hide factors that any hides which did not come
-

down to natural suppleness in two days in clean water were to

be returned Of arsenic curing I know nothing and it is not so
.
,

much in v o gue as formerly There is quite a trade in Cawnpore

.
,

a
Lucknow A llahabad e t c in treating old and inferior hides with
, , .
,

new for export and gre t efforts are made b y native holders to
,

get their stocks down before the rains commence as they say , ,

and rightly I think t hat hides are not worth so much after the
'

rains by 3 0 per cent The peculiar latent moisture of the rains

.

affects them very detrimentally .

Under certain circumstances this mode of cure gives rise to

extensive iron staining of the skins and analyses of the materi l a
scraped o ff D acca and Me ha
-

o r e kips were undertaken with a

p
View to elucidating the causes of t his injury The fo llowing are .

the results of the analyses referred to which were made upon

”

'
,

the residue after the rather considerable quantity of fibrous

organic matter which had been scrap ed o ff with t he cure had
, ,

been destroyed by ignition toget her no doubt with traces of ,

ammoniacal salts
D acca Meh ap o re . .

Entire Cu re Entire Cure . .

Sand and silica 20 5 5 27 3 8 -

Pe z 0 3 2 77
-
1 86
A1 20 3 2 48 -
2 74
-

Mn g O4 o 6o
~
0 40
a
-

C O 2 60 -

37 0
Mg O 33 8
a
N 20 28 97 -
26 -
80
SO3 38 9 0
-

33 7 5
-

Cl 0 22 -
0 1 8
-

H3 P O4 and CO Traces Traces

1 00 4 7 1 00 5 0

The soluble salts of the D acca cure were also analysed separately
with the following result
C O a
MgO
N 20a
SO3
Cl
Moisture
 O R I GI N A ND C UR I N G OF H I D ES A N D S KI N S 41

It thus consisted e xclusively of sulphates with a mere t race of ,

chloride The cu res after ignition were both neut ral to

'
.
, ,

phen olp hthalein but before ignition the D acca was distinctly
,

alkaline in consequence probably of the presence of ammonium

,

salts and both showed considerably larger t races of carbonates

,

before than a fter .

The most strikin g feature of these analyses is the absence of

chlorides ; The cure s are thus practically free from common
salt and owe their antiseptic power to the sodium sulphate
,

which they contain and which indeed forms their principal

constituent Nitrates appear to be entirely a
.

. bsent Sodium .

sulp hate sometimes fo rms large cryst als in pits used for soaking
t hese kips .

The iron staining of hides which has been mentioned ap pears

-

to result only when the hides after cure are exposed for a
lengt hened peri od to a moist atmosp here in which the carbonic ,

acid present probably also plays its part the iron passing into .
,

so lution as hydric carbonate .

The analyses show a striking resemblance to those of the

s oda deposits of Wyoming
1
given by Dr At t fie ld except that , ,

their percent age of sodium carbonate is smaller which is quite ,

intelligible in the light of Mr B runner s abstract on the P robable ’

.

”2
Origin of Natural D eposits of So dium Carbonate which supports ,

the view that the sodium carbonate is derived from sodium sul
phate by the reducing and carbonating action of low organisms .

It may be noted here that the preservative properties of

sodium sulphate are wel l known and the anhydrous sulphate has ,

been recommended as a substitut e for common salt ( see p .

D rying is a v ery common method of preserving hides as well

as other putrescible matters It has no effect in killi ng bacteria .
,

but putrefaction can only go on in presence of a considerable

amount o f moisture As applied to hides it is to the t anner
.
, , ,

one of the least satisfactory modes of cure involving very con

s id e r a
,

b l e difficulties in bringing h ides back to the moist and

swollen condition which is necessary at the outset of his Opera
tions but it is the only practical method in dist ricts far from
,

the coast and with primitive modes of transit both on account of ,

the cost of salt and the lessened weight of the dried hide Grea t .

differences are found in the ease with which dried hides soften ,

according to the way in which the drying has been accomplished ,

the difficulty being greater the higher the temperature which has
been used ( see p The best mode of d rying is to hang in
.

the shade in a good draught of cool air with the flesh side out , .

fa
w Che m I n d 2
1
n . S oc . . .
,
1 89 5 , p .
4 . I bi d .
,
1 89 3 , p . 1 1 6 .
42 PR I N C IPLE S OF L EA TH ER MA N UFA C T UR E

H ides skins dried in a tropical sun are not only difficult to

or

soften but are liable to damaged portions which either refuse to

, ,

soften or bliste r and go to pieces in liming owing to the structure ,

of the hide b e in g dest royed by heat the outer surfac e drying first ,

and forming an imp er vious layer which hinders evaporation from

the inside so that the moist interior becomes melted while the
, ,

outside appears quite sound Such 1 n ju ries are often only to be .

discovered by soaking and liming Very similar damage may .

occur from putrefac tion of the interior after t he outside has

become dry and to get good results the dryin g must be gradual
, ,

but rap id especially in hot climates Sou t h A merican hides

, .

are mostly dried i n the sun suspended by head and t ail from ,

stakes with the hair side out

, .

The risk of injury by putrefaction during dry1 n g 1 s diminished

by the use o f antiseptics Solutions of arsenic h ave been fr e
'

a
.

quently _used for this pu rp ose n d many of the d ried I ndian kips ,
-

are of what are known as arsenic cures alth ough the w riter
has never b e en able to detect ars enic in a
,

a
n y which he has

a
ex mined and its use seems by no m eans general The arsenious
acid is usually dissolved in soda
.
, .

solutions Such solutions h ve

little antisep tic power e ven i f strong a
.

n d are main ly use f u l in ,

preventing the attacks of inse c t s whic h are o ften very d est ru c

tive The larv a of a small beetle Dermestes vu lpi n a
.
,

s frequently
'

.
, ,

devours the whole fibrous tissu e of patches of the hide leaving ,

only the ep idermis .

It may be well here to say a few words about the injuries and
defects to which hides and skins are li able a lthough some of them ,

are not strictly due to the cure The most serio u s and yet pre
ve n t a
.
,

b l e injury is that due to butchers cuts A s the value of the

’
.
,

hide bears only a smal l p ropo r tion to that of the meat many ,

butchers do their work extrem ely carelessly and this is em

co u ra
,

ge d by t he loose classi fication of damaged hides in some

markets There is also an idea that the appearance of the meat
.

is improved by a thin layer of the white skin tissue being lef t o n -

it and for this reason as well as mere carelessness butchers fr e

, , ,

quently score the flanks of the hide wi th shallow cuts which ,

greatly diminish it s value The packer hides of the Unit ed

St ates a
.

nd the product s of the large saladeros b r slau ghtering

,

salting establishments of South A meric a such as Lie b ig s ,

’

show what can be done by skil led work in this respect In the
U nited States much of the fla
.

yin g is done by means of a wooden

,

cleaver instead of a sharp knife Another method to some .

extent in use and which may be recommend ed for calf and sheep
,

skins is to inflate the carcase before skinning with air from a

,
 P R I N C I P L ES OF LEA TH ER
“

MA N UFA C T URE
that the egg was laid on the hair of the back where it hatched , ,

and the minute larv a simply at e its way below the skin In .

a
1 9 1 4 the t r ue life history is believed to hav e been disco vered

simultaneously by C rpent er in I reland Seymour Ha

-

a
dwen in ,
-

Canada and Gl ser in B erlin and is even more ext raordinary

, ,
‘
.

The flies never strike on the back whe re t he maggots are found , ,

but on the fetlock or j oint below the knee anatomically the heel
a
,

of the nimal The H bo vis the more common English spe01 es

lays single eggs while the H lin ea ta
. . .
, ,

.
, ,

more frequent in A merica lays them in ,

sin gle rows but otherwise al most like ,

the grains in an ear o f corn Th e

minut e maggot a
.
.

t]first only about 3 — ,

1
0

inch long bores its way through the ,

FI G 7 — S ao w
c
. f a b l,e skin and wanders t hr o u g t he tissues
h r ,
,
'

s h o wi g g r o wt h o f e p i til l it reaches the S kin of the back

n

d e m is ro u d a
,

r p er t u r e where it passes its final larval st age

n
,

often pausing on the way for a time in

the w all of the g ullet here it I S frequently found from September w
It then bores a
,

to January 1
hole through the skin enlarged to
.
,

obtain air for its sp iracles or breath ing holes which are in the ,

tail As it grows it continues to irrit at e the lower part of the

.

c avi ty with hooked mandibles and lives on the pus and matter ,

so produced It grows to a len g t h of full y {if inch and the c avity

.
,

( fig . situ at ed between the skin and the subcut aneous tissue ,

is often as large as half a walnut It remains in the sac only .

during its larval stage and fal ls out on the ground before com ,

p l e t in g the change to the pupal st ate and seeks shelt er in the soil
or under grass emerging in about six weeks as a fly Gl ser ,
,

. a ,

with characteristic German thoroughness allowed one to bore ,

through his trousers into his leg and finall y recovered it from
his mouth " The H bovis is shown l n fig 8 a nd the H l inea ta
,

. . .
, ,

which is somewhat smaller and the eggs in fig 8A The tail , , . .

P ro f G H C ap t ad t h
r en er n o er s , R ep o r t s on Wa
rb l e Fl ies ; No 4,
a Ja
. . . .

J ul y 1 9 1 0 ; J l N
o ur n o 2, n 1
9 08 9 1 0 No 4 1 NO 1 1 91 5 i D u b lin

ap t ad H wit t S m a
. . . . .
, , , .

C r en er n e o e N e w Obs er v ti on s on the L if e hi s t or y of
Wa
-

bl F li
r e es , Th o m Co Lt d D u b l in 1 9 14
D pa d aH a
aa a ah
. .
, , , .

tme r en t of A gr ic u l t u r e ; C n e lt h of A n im l s B r nc : Dr
a a ad N
,

Se y m o u r H d w e n n d o t h ers B u ll e t in N o
6 9 9 6 1 1 1 2, n o 2 2, 1 1

aa
-
.
, , . .

G o v e r n m e n t P r in t in g O ffi c e , Ot t w
Ca ad iaE t m l gi a
.

n l S i ty R p t N
n 36 9 6
n o o o c oc e e or o 1 1

a a l l t ad w ll il l t a t d a
, .
, .

S ee l so t i l b y A S ym
n ex c e J en n e us r e r c e e our o n es,

Y aB k
- -

L a T a
.

e th der 9 p
r 69 es e r oo 1 21 1

d iffi l t t h am igh t b im agi d at h p a

-

. .
, ,

1
Thi i l s s ess t h i m t ly cu n e ne s e s os

a l at i a ga
,

th ro ugh t h l wh i h e nd m t f t h i t
o o se l reo r ss u e s c su r ro u os o e n er n or ns .
 OR I GI N A ND C UR I N G OF H I DE S A N D S KI N S 45

end of t he former is covered with orange yel low hairs while in

“

the latter they are lemon yellow -

.

As regards p reventive measures the most certain is to destroy ,

the grub before it emer ges either by squeezing it out or extracting

it with forceps and this should be done at intervals from Ma
, ,

,
y to
Au gust The method is n ot very rapid and it took about six
.
,

years to completely exterminate the fly on a small island taken

for experiment on the I rish coast No dip or application yet .

F I G 8 — H yp o de r m a
b o vi s 1 e gg m gn i e d afi ab out 1 2 di am t ;
e ers 2,

a a a afi a) h y al i ad
.
. . , ,

m gg o t ; 4 , Ch r y s l is c s e 6 , fl y , m gn i e d ( B r uer 3 5, C r s s n

aaz a
,

fl y , n t u r l s i e ( B Cl r k ) . .

found seems t o prevent the fly from striking and though some ,

of the washes which have been tried do kill the grub they mostly '
,

injure the skin and destroy the hair The most effective and .

least injurious seems to be a solutio n of nicotine with which ,

the B oard of Agriculture and Fisheries are making further

experiments
In sm a
.

ll numbers the warble seems to do little inj ury to the

hea l th of t he anim al though it must damage its c o n d it io n t o
,
'

some extent and cases have been known where animals have
actu a
,

ll y died of the inflammation produced Some idea of the

extent of the plagu e may b e re a
.

l ised from the statement that an

I ndian kip in the museum of the Leeds U niversity Leather
D epartment has not less than 68 0 warble holes and that almo st -

equ a
,

Warble d
'

l numbers have been counted on English hides .

hides are useless for many of the purpo ses to which leather is
applied and the aggregate annual loss on the hides alone is
,
46 P R I N C I P L ES OF LEA TH ER .
MA N UF A C T UR E

estimated at not less th n A nother way in which a

damage is done is by the state of terror which t he attack o f the
fly causes in herds of cattle c ausing th em to g a d
”
or g a l lop
“ '

aimlessly about This is the more singul a as the laying o f the

,

r
.
,

egg produces no pain and cattle can hardl y be suppos ed to foresee ,

'

its result but the attack o f the fly is very persist e nt and cattle
, ,

are sensitive to touches on the leg Some protection is afforded .

if the cattle can get in the shade as the fly seem s o nl y to strike

in sunshine and cattle a
,

l so take refuge in water W

,
here the fly ,

does not pursue th em, and where the lower part of the leg is
protected
D eer and goats and occasion a
.

l ly horses are attacked by the , ,

warble fly but sheep seem to be exempt though they are subj ect
, ,

to other ill s too numerous t o mention but reference must b e _

made to two which affect the skin— c ockle and colt These can
a a
.

hardl y be s id to be dise ses except from the tanners point of ’

view as they neither cause pain nor a ffect the he a

,

1
,
l th of t he
sheep though they deteriorate the value of its skin
,
.

Coc k le is d e sc ribed by S eymour Jones as a disturbance of 1

the pelt struct u re resemblin g a hard pimple or b oil of a ma

-

r ke d

and well defin e d appearance dark in colour especia ll y a

, .

- -
fter ,
“
,

liming and turning to a deep brownish black in the tan liquors

The a
-
.
,

r ea c overed van es l n di fferent skins ac cording to given

con dit ions Th e markings range in regul ar waves o r ridges

. -

from the spine outwards , commencing in the region of the neck

and shoul der ( t e the heart ) and sometimes covering the whole . .
,

skin but frequently ceasing with t he ribs

, ( The name is derived .

from the shell like form o f the markings ) -

.

A fter depilation the cockle assumes a yellow colour which

a
,

deepens in tint s the operations succeed each other and may ,

easily be taken for a sp ecies of gristle

I n mild c a
.

Se s the wet work treatment will remove the earlier

a
-

forms but when the cockle is of long standing no treatment t

, ,
“

present applied wil l remove them .

Cockle begins to appear about D ecember and increases until ,

the sheep is shorn when it entirely disappears Seymour Jones , .

-

had the right hand side of fifteen sheep shorn and when
slaughtered three days later the cockle had a l mo st d is a
-

p p ea
,

red ,

on the shorn side though it was marked on the other These

sheep were a
, . .

l so su b je c t e d t o di fferent feeding : five fed with

'

extra oilcake and dry foods di splayed cockle in its worst form
five with oilcake a
,

l ternated with mangolds showed it in medium

1
S y m o u J o n e s Th S h ep a
e n d i ts S kin Lea
r th
-
Tr a d s P u b lishi g
, e e , er e n

Co .
,
1 9 1 3 .
ORI GI N A N D C UR I N G OF H I D ES A N D S KI N S 47

degree whil e five fed with roots and moist food showed it only
,

mildly It is evident therefore that cockl e is much influenced

by the feedi ng a
.
, ,

n d is m u c h increased by the intensive feedin

g
now genera
,

l ly adopted to prepare sheep earlier for the market

'

A fatty scurfy deposit appears on the cockly skin under the

w00 1 At Seymour Jone request the writer made what chemical
‘
s
-
.

examination he coul d of a very small sample unf ortunately

insufficient for any complete an a
,

l ysis The fatty p ortion appears

to consist of a mixture of glyceride fats parti a
.

l ly oxidi sed with ,

some cholesterol fat possibly arising from the sebaceous glands

and u n s a p o n ifia
b l e by caustic potash though it is s a p o n ifie d , ,

or at least emulsified by steapsin one of the pancreatic ferments

, , .

Seymour Jones believes the disease to be connected with the

extra demand for fat made by the rapi d grow
-

t h of the wool during

the wint er season though the exact mechanism of the process is
,

not very clear .

Colt or dead fat in sheep Skin s is another trouble very

- -

possibl y increased b y the present in tensive feedi ng and i s an

accumul a
,

tion of fat in the skins which Seymour Jones attributes,

-

to an adipose degeneration of the fat cells probably leading to -

hydro l y5 1 s of the fat and crystallisation of the fatt y acids set

free.

FI G . 8A .
— H yp o der rn al in ea
ta .
 CHA PTER VI I

S TR UC T UR E A N D GR O WTH OF S KI N

ALTHO U G H at first lsight the skins of di fferent animals appear

to have little in common a closer examination shows that a
, ,

ll
the Mamm a l ia possess skins which have the s ame gene r a
,

l s t ru c
ture and thus a general anatomical description of the skin of an
ox applies a lmost equally to that of a sheep goat or c a
,

l f though
“

, , ,

on account of the di fference in texture and thickness the practical

us es of these various materials may di ffer widely The skins of
lizards alligators fishes and serpents differ fro mthose of the
.

a , ,

higher nimals chiefly in having considerable mo dification s in

the epidermis so that it be comes harder and forms sc a
,

,
l es ,

and the arrangement of the fibres presents considerable differ

ence In man y fish skins for instance the fibres are in su ccessive
layers at right angles to each other a
-
.
, ,

,
nd di agonal to the skin ,

like the threads in a P almer tyre but not interlaced , .

I n its natural condition the skin is not merely a covering for

the anim a l but at the same time an organ of sense secretion
, ,

and excretion and hence its structure is somewhat complicated

, .

It consists of two principal layers the ep ider mi s ( ep ithel iu m

cuticle) and the cer iu m ( dermacu tis) These are total l y distinct
, ,

.
, ,

not onl y in structure and functions but in their origin In the

”

, ,

egg o f a bird and the o vu m of a higher animal the living germ

consists of a single cell which as soon as f ertilis ed begins to
, , ,

multiply by repeated division ( op Chapter III The mass of cells . .

thus formed early di fferentiates into three distinct layers from

the upper of which the ep idermis arises the cor ium together with
,

, ,

the bones muscles and cartilages is derived from the middle one
and the lower furnishes the epithelial lining of the intern a
, , , ,

l organs .

This distinc t ion of origin c o r re sp o n d s t o a wide di fference of both

'

anatomic a l and chemical characteristics Th e upper a n d lower .

layers are formed of cells of which the wall s mostly consist o f,

keratins and which multiply by division while the structures

, ,

derived from the middle layer consist largely of connective tissue ,

and yield gelatine and allied substances by boiling and though ,

produced by cells are not themselves cellular,

.

A diagrammatic section of skin is shown 1 1 1 fig 9 but for the .

,

actual microscopic appearance of its various parts the reader

48
 S TR UC T URE A ND GR OWTH OF S KI N 49

is referred to the very beautiful photomicrographs given b yMr

A Seymour Jone s in his series of articles on the Physiology
of Skin in the journ of the S ociety of L ea ther Tr a
-
.

des C hemis ts
a
.

( begi nning in September 1 9 1 7 and continued at interv l s to the ,

9FI G al ti f a
—V e r t ic
l f ki ma g ifi d a b t 5
se c d ia m ton o c s n, n e ou 0 e er s

a p id m i ; b g a pa
-

p ill a y la la
. . .

e ier s y ; fib r y n f or ki ; d r er 0, ro u s er o s n

ha fat gl a f w a t gl a f w a
, , ,
'

i rs d e, d ; g p ni g f d
s t t s e n s o en n o uc s o s e

gl a O l y am a ll p a
- -

h ha a l y fib pa
.
, ,

d n i ms l r -
t f th u sc e s t n s r o e co rse ro u s r

ad it t d m wh a t fa p wa d t h ai
.
,

of th i m i h w
e e or u s s th
o n, n ex en s so e r er u r s n s

sh w i th d a
o wi g
n n e r n .

present one of which is by his permission used in

illustrating the present chapter .

A s wil l be seen from fig 9 the upper or ep idermis l ayer is

very thin as c o mp a
. .
, ,

r e d wit h the cor iu m beneath it ( the whole of

‘

which is not included) and it is entirely removed in the process ,

of d epilation but it is yet of importance to the t anner since

, ,

the hair and fat and sweat glands although rooted in the
are a
-

co r iu m l l products of the epider mi s and their complet e

remova l depends on its chemic a l and anatomic a
, ,

l character and ,

its difference from that of the c oriu m .

50 P R I N C I P L E S OF L EA TH ER MA N UFA C T UR E

Th e cor iu m
consists mai nl y of a mass of felted fibres of white
1
,

connective tissue consisting of collagen which on boili ng t akes

up water and is converted into gelatine In its low
, ,

,
“

er part con .
,

s t it u t in g the bulk of the hide or skin these fibres are compara ,

t ive l y coarse and are made up of ,

bundles of much finer fib rils bound

together in some way but in the
'

b thin upper layer which the tanner

“

, ,
”
distinguishes as the grain the ,

texture is much finer the b undles c

,

appear to be s plit up into their

'

— E id er m is l ae individu a l fibrils and are to a con

'

FI G p
'
1 0 y r

s id er a
. . .
,

b l e extent mixed with a net

work o i the s o c a l led
”
elastic or yellow fibres which are
insoluble in hot water and quite di fferent chemic a
-

l ly from the
white collagen fibres The ha
,
_

ir b ul bs with their sebaceous

a
-
. u
,

gl nds and sheaths of ep idermis cells mostly pass complet ely

through this grain layer into the coarser t issu e b e n e a
,

t h which
'

'

may be well distinguished as the p a rs f a

-

s cicu li or bundle layer

Th e ep ider m is is shown in fig 9 at a and in fig 1 0 at a
.

and b . .
, ,

more highly magnified It s inner m ucous layer b the r ete

a
-

.
,
'

m lp ighi which rests upon the Corium c is soft and composed

of living nucleated cell s which m
, , ,

ul tiply by division and form , ,

cell walls of keratin These are el ongated in the deeper layers

and gr a du al l y b ec o m e fla a
-
.
,

t t en ed s they approach the surface

where they dry up and form the horny layer a This last is being
,

constantly worn away thrown o ff as dead s ca

.
_

l es of skin scurf,

and as constantly renewed from below by the multip lication of

the cells. It is from this epitheli a l layer that the hair as well ,

as the sweat and fat glands are devel oped The ep ider mis is -

,
.

not supplied with blood or lymph vessels so that its cells -

are nourished entirely from the juices of the coriu m on which

it rests and hence die as they are push ed away from it
by the younger cells The human epidermis especi a
,

l ly on the
soles of the feet and the p a
.
,

l mar surface of the hand is much ,

thicker than that of most domestic animals and much mis ,

-

apprehension has been created by the supposition that draw

ings of these thicker parts represented the usu a l proportions
of anim a l skin I ndeed in one of the older tanning manu a
. ls
1 C o ri u m ( La
t ) or D er m a( G r ) e ah c s ig n if y b o t h h id e ad l a
n th e er , ad n

a ma
.

p r e su m b l y wh e n d f h id u se or e, in c l u d e t h e wh o l e h id e wh ic h is d e

a a a y ym
,

in t o l e t h er nd re s no n ous wit h p e l t ( Fr Cu ir en tr ip e , G e r B l os se)

mi i t h l a aad t h a
.
, . .

Ep i de r y swhi h l i s e er c es u p on t h e d er m n e r e fo r e b o ve the
a
,

gr m .
 52 P RI N C I P L E S OF L EA TH ER MA N UFA C T UR E

and ul timately into the hair—

sheath where it lubricates the
“

ha
,

ir .

The hair is derived from the ep idermis and is contained I n a ,

sheath of nucleated cells which is continuous with the epidermis

a
,

n d completely surrounds its bulb so that it is altogether an ep i ,

dermis product though rooted deeply in the c oriu m

,
Th e hair .

FI G I2 — Se c t io n of go a
t ki s n sh o win ggswe a
t d u c t sia
n d seb a
z c eo us

a
-

ad a Ma
-

. .

gl n s . U n h ir e d .
( X 84 .
) P h o t o gr p h b y R H . . rr io t t .

itself is covered with a layer of overlapping sc a l es like the slates ,

on a roof but of irregular form These give it a serrated outline

at the sides and when strongly developed as in wool a
.
,

, n d so me ,

furs and further raised by chemical treatment c o n fer t he pro

'
‘

Within these sc a les which are c a

, ,
'

p e rt y o f felting . l led the hair ,

cuticle is a fibrous substance which forms the body of the

hair ; and sometimes but not a l ways t here is a
,

,
l so a central ,

and cell ul ar pith which under the microscope frequently appears

black and opaque from the optic a
,

l effect of imprisoned air

, .

On boiling or long soaki ng in water alcohol or turpentine , ,

 S TR UC TUR E A ND G R OWTH OF S KI N 53

the a irl sp a
c e s become filled with the liquid and then appear ,

transparent .

Th e fibrous part of the hair is made up of long spin dl e shaped -

cell s and cont ains the pigment which gives the hair its colour
,
.

FI G 1 3 Ph o t o m ic r o gr a
— ph by Mr A Se y m o u r -
Jo n es of aha
i ha
i r, r

ad t h
. . .

fo l l ic l e p il i m l
'

t n e e r ec o r u sc e

Th h a i ma l a l y t ad d w wa t b lb a
.
,
”
e y b r d t th
e c e r d r dce o n r o e ro o u n su rr o u n

i g t h ha
n i f lli l e Th a tta
r hm t
o f thc e ti g m l (p 5 5 ) i
e c en o e er e c n u sc e s

f t h ha ta ti g a t t h t p ad g a d a
. .

h w
'

s o t h l f t id
n on i f l li l
e e s e o e l ly r o c e, s r n e o n r u

mi a at h f ma p a
,

t ti g t b lb It ti mbl th di g
t it b a I t p w f l h l d i w ll d fi
er n n ne r e ro o u s co n o r o n r e se es e s re n

a a d ad t h a
. ,

o f th kt e o ree s se d s o er u o s e e ne n e re er

w il l a ia f m it a Th m t h d f a tta
.
,

pp t th rec ti e, er e ro hm t t th s c on e e o o c en o e

g a m m b a f t h i m l i im il a t t h a ha
.
,

ri n e r ne o t f th s i f l li l
u sc e s s r o o e r o c e

f a tta
.

B tw e th p i t
een hm
e t th mo n l i s oh w d d i t hi k c en e u sc e s s o n re uce n c

n e ss ,b t t hi d ti
u i t ma s i ta i d b y
re uc d th p i t
on h w
s ino n ne e on e o n s o n n

ga
th fig — t ha t i t h t hi k ma i th t il it a i
e ure s, ghe t c n e ss r e ns even ro u ou un n

m t th
ee s a tta hi g d wh
e it p a
c d n t t en at g en s re s ou o se c u r e s ro n

da
,

f oun ti g ip on r .
54 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

These cells are easily seen under the microscope if h a i r or wool is

broken up by t reatment with moderately strong sul phuric acid
Th e hair of the deer di ffers from that of most other anim a
.

l s in
being almost wholly formed of polygonal cells which in white
hairs are usually fil led with air In a
, ,

, l l dark hairs both the hair .

.

and sheath are strongly pigmented but the hair is much the more
so and hence the bulb has usu a
,

, l ly a distinct dark form Th e .

dark haired portions of a hide -

from which the hair has been

removed by liming still rem a in
coloured by t he pigmented cell s
of the hair sheaths which can -

only be completely removed by

ba ting and scudding .

Just below the grain layer the -

ducts of the sebaceous or fat -

glands pass into the hair sheath

and secrete a
-

n oily m atter to ‘

lub ri cate the hair The glands .

themselves are formed of large

F I G I 4 — as b a c e o u s gl a
'

nd
nuc l eated
e
cells arrang e d some
'
~

b ha
.

what like a bunch of grapes the

.
’ }

,
i ; e ectr m u s cl e 6, r or , .

( x z ) oo .
upper and more central ones
being highly charged with fatty
matter Their appearance is shown in fig 1 4 A good dea l of
the p asty substance worked out in unh a
. . .

i ring ( yellow on a
white hide) consists of these sebaceous glands mo re or less “

broken down by liming but still rec ognisable by the microscope ,

.

Th e base of the hair is a bulb encl osing the hair papill a h ( fig ,

.

which is a proj ecting knob o f the c or iu m and which b y .

,

means of the blood vessels contain ed in it supplies nourishm ent

-

to the hair Th e hair bulb is comp osed of round soft cells

’

- .
.
,

which multiply rapidly by division and pressing upwards through ,

the hair sheath become hardened thu s increasing the length o f

-

the hair .

Th e cells outside the bulb shown at f in fig 1 5 pass upwards ,

.
,

as they grow and form a coating around the hair known as the
, ,

inner root sheath

I n the larger text books of histol ogy a good de a
-
.

-
l more detail is
given of the structure of hair and its sheath which is omitted ,

here as unimportant for the t an ner .

In embryonic development a small knob of cel ls forms on the

under side of the epidermis over a kno t of capillary blood vessels ,
-

in the cor iu m and enlarges and sin ks deeper into the latter while
, ,
 -

S TR U C T UR E A N D GR OWTH OF S KI N 55

the root bu lb of the young hair is formed within it surrounding

-

the capillari es from which it derives nourishment and which ,

form the hair papilla fig 1 5 I n the renewal of hair in t he

-

, . .

adult animal the process is very similar Th e bulb of the old hair .
-

withers and the hair fall s out and in the ,

meantime a thickening t akes place in the

epidermal coating of the lower part of the
sheath and the young hair is formed below
and usu a
, ,

l ly to one side of the old one ,

g rowing into the sheath and taking the ,

place of the old hair This is one cause .

of the difficul ty of remo ving ground hairs -

in t he process of unhairing since t hey are ,

not o nl y short but deeper seated than the ,

old ones .

The process of development of the sudori

ferous or sweat glands is very simil ar to
that of the h a
-

i rs They consist of more

,
.

or less convoluted tubes surrounded with

wa l ls formed of longitu di n a l fibres of con
n e ct ive tissue of the coriu m lined with a ,

single layer of l arge nucleated cells which ,

secrete the perspiration The ducts which

are exceedingly narrow and with wa
.
,

l ls of
nucleated cel ls like t hose of the outer h a
,

ir FI G 3 — ah a i ; b ha i . 1 .
,
r ,
r

sheaths sometimes op en d irectly through c t i l ; i e o o t u c e 0, nn r r

the ep idermis but more frequently int o Sh a

,

t h ? d 0ut 00t e er 1
‘

Sh a
:
,

th ? d m ic
the orific e of a hair s heath j ust at the e 3 er

oa
- ’
,
t c
surface of the skin Each hair is provided
with a slanting muscle c a l led the a
'

f
.

g f e o rl In o 1 nn r

shea
r r ect or

a
t h ; g b u lb ; h

pa p ma
, ,

or er ector p ili ( see fig which is con h .

.

p ,

tracted by cold or fear and causes the ,

hair to bristle or stand on end by forcing up the attached

skin it produces the effect known as goose skin
, Th e muscle -

.
,

which is o f the unstriped or i nvoluntary kind passes from near ,

1

the hair bul b to the ep idermis and just under the sebaceous
-

glands which it compresses when it contracts thus forcing out

, ,

the oily matter

B eside the hair and h a
.

i r sheaths and the sebaceous and

,
-

sudoriferous glands the epidermis layer produces other structures,

1
Th e m u s c l e s wh ic h are u n d er t he c o n t ro l of t h e will , ad n kn o w n as

volun t ay m l r u sc es,
”
a
re c o m p o se d t h in p l t e s , g iv in g t h e m
of a n ely afi
s r t ip d a
e pp aa e r n ce u n d er t he m ic r o sc o p e whi l e t h o s e c o n t r o ll e d b y t h e
ym p a a
p p a im p l y fi b
,

s th ti e c n e r vo u s s y s t e m e r s ro u s . Se e fi g . 21 .
 L EA TH ER MA N UFA C T UR E
”

56 P R I N C I P L ES OF

a ho rny charact er including horns hoofs claws a n d fin ge r

'

of

nails ; which both chemically and anatomically are an a

, , , ,

l ogous
to exaggerated hairs such as the quil ls of t he porcupine Th e
feathers of birds a n d probably the scales of fishes a
.
,

,
n d reptiles

have a similar origin None of .

these epidermal structures are

soluble in hot water or capabl e ,

of producing gelat ine or gl ue .

The whole o f the hair sheath and -

its glands is enclosed i n a coating

of elastic a nd Connective tissue -

fibres which are s upplied with ,

nerves and blood vessel s and form

’

FI G 6 —D e v l o p m n t o f
1 part of the corium
e e

Yo u g ha
. . .

i n The epidermis together with the

r

hairs is separ a
.
,

ted from the coriu m

by an extremely fine membrane or surface called the hy a
,

lin e
( hy a
l ine = glassy) This ha s been the subj ect of
. much mis
conception fo r it is so extremely thin that many histologi sts
have doubted even its existence and have fa
, .

il e d t o demonstrate
a
'

it microscopic a
,

l ly and it h s been erron eously identified with

,

the upper part of the grain layer which when dry and very thin
as i n the fly wing skiver is almost transparent Ka
-

, , ,

-
t hrein er ,
.

believed that he had separated it by accident in th e tannery ,

and the writer had one of his preparations but it was so trans
parent that it could scarcely be actu a
,

l ly seen under the micro

scop e though its existence could be inferred by the specks of dirt
,

and broken down cells which adhered to it That it has how

-
.
,

ever a real existence is proved by its formin g the Very thin bu ff

,

coloured surface of tanned l eather which takes dyes as well as , ,

the colouring matters of the tan differently t o the g rain imm ed i

ately beneath it from which it is evidently di stinct If it gets
,
.

scraped o ff mechanicall y in the beamhouse or destroyed bac

t er ia
,

l l y in the limes the exposed portion of the skin remains nearly

white instead of colouring a l thou gh it has been equ a
,

ll y exposed
,

to the tanning liquors Indeed it is almost impo ssible t o decide .

by examining t h e finished leather whether the damage has been -

done in the beamhouse or after the leather was fully tanned

Seymour Jones believes that the hy a
.

-
lin e is always destroyed by
the use of strong solutions of alkaline sulphides but such solutions
are sometimes used in the u n wo o lin g of cheap gl Ove l e a
,

t her s wher e -

the preservation of the grain surface is very important To avoid

misconception the hy a
-
.

a
lin e if r e ferr e d t o in the following pages
It s quantity is so sm a
, , ,
”
will be called the grain surf ce -
l l that .
 S TR U C T UR E A N D G R OWTH OF S KI N 57
‘

it is impossible to study it chemica lly except upon the skin and ,

it Is not known whether it originates from the corium or the

”
ep ider mis It is possibly identical with t h e
. basal membrane ,

which can be demonstrat ed in the hair bulbs Seymour Jones -

.
-

I 7
— Se c t io n of c a
lf k i s n , s h o win g a t p il i m
rre c or ad d
u sc l e n e ve l o p

g a Mai t t
-

a
.

m en t of h ir s .
( x P ho t o r ph b y R H . . rr o .

suggests that it is a more or less artificial resul t of liming and ,

derived from the bases Of the cell s of the mucous layer It is .

not identical with elastin since it is not digest ed by the trypsin

,

ferments A clear layer of about O OI min in thickness is very

.
'

well shown in the puered skin on fig 42 p 2 2 6 but whether

this is re a
l ly the hya
. .
, ,

lin e is uncertain .

Th e structure of the cor iu m is quite di fferent from that of the

 ”

58 P R I N C I P L ES OF L EA TH E R MA N UFA C T UR E

pidermis
e which has j ust been d escribed as it is principally
, ,

composed of interlacing bun dl es of white fibres of the kind ,

known as connective tissue ( see fig 1 8) these are composed .

of fibrils of extreme fineness supposed to be cemented together ,

'

a
by a substance somewhat more soluble than the fibres them
selves Th e fibres r e not themselves living cells but are appa
sh a
. - ,

r en t l
y produced by narrow spindle p e d c el l s lying against them -

FI G . 1 8 .
— Co n n e c tive -
t issue fib r es .
(Ra
n v ie r ) .

and possibly travelling up a n d down the fibre R ows of some .

what similar cells exist between the fibres o f sinews which are
a
,

l so of connective tissue though much more comp act than that of

,

skin and in parallel bundl es instead o f fel t e d together Inter

,
‘

woven with the white fibres of the grain layer is a network of the
yellow or elastic fibres These are chemic a
-

so called
-
l ly .

very di fferent from the white fibres which consist of collagen , ,

and when boiled take up water and become converted into glue
or gelatines while the elastic fibres are insoluble in boiling water
, ,

and do not appear to combine with tannin They are also .

digested by the trypsin ferments which t he white fibres are not , ,

 L EA TH ER MA N UF A CT UR E
' I

60 P R I N C I P L ES OF

the spac es between them filled b y some l e ss Orga n ise d a n d more

cement substance
,

soluble substance; often called ( Ger

Kittsu bsta nz ) o f whic h the na
-
.

'

, ture is unknown but which seems

,
-

to be removed b y liming R eimer thought he had separated it

“

.
,
”
and call ed it coriin but his product was later shown to be
,

merely due to the solution of t he hide fib r e s themselves Se y -

mour Jones -
1 9 1 8 p 3 6) speaks of the fib r e bun dl es , .
-

as being united by a soft filamentous substance of considerable

tenacity and elasticity kn o w as areolar tissue This is quite
n , .

”
possible but areolar tissue is only a somewhat old name for
the looser and more open s ort of connective tissue such a
,

s is ,

fo im d belo w the skin and surrounds many organs of t he body

, .

I t was originally supposed to be cellular as the name implies , ,

but is now known to b e merely a network of white connective -

tissu e fibres like the corium and only contain s the flattened ,
(

and elongated cells which are also found in the skin and which ,

apparently produce the fibres

The fib r e bun dles In som e co nnective tissues a
.

re encircled and
tied together by rings or spirals of el a
-

s tic fibre ( see fig and .

some histologists have suppos ed that t hese were the contrac ted
remains of very thin sheath s of elastin with which the fib r e
bundles were originally surrounded b ut which have been torn ,

and ruptured by the swelling Of the fibr ils under the influence
of acids or alkalies ; and though such sheaths have not been
demonstrated t he theory is not alt ogether improbable
,
1
They .

seem to be absent In most of t he fib r e—bund les of the skin

A s to the origin o f the fibres themselves they a
. .

r e not living ,

cells with protoplasm and nuclei and therefore cannot grow by ,

division like the cells of the epidermis but lying between and
against the fibres are many flattened and elongated cell s which

a
ap p aren t ly produce the fibres which may therefore b e coh ,

s id er e d as c ell—products rather than actu l ly living tissues

Nothing is known of the origin of the c ell s which a
.

r e possibly ,

modified migratory cells which l atter are probably identical ,

with white blood corpuscles lymph and saliva cells and the
-

,
-

like and are found not only in the liquid ducts but wander
, ,

ing through the t issues which they are able to do from their
amoeboid ch a
,

racter and absence of cell walls They app arently -

play a large and varied part in the animal e conomy devour ing _ ,

i n j urious bacteria and effete substance of all kinds and conveying ,

it to places where it is required fo r buil di ng up new tissues and

“

they are supp osed to adapt themselves to a ll sorts o f special uses

Th e pa rs pa pill a
.

ri s or grain layer receives its name from

,
-

,
.

Se ym o u r J o es h a
1 s sp o ke
-
o f t h e se a
n s fib s ao l e mm a
n re -
rc .
 S TR U C T U R E A N D G R OWTH OF S KI N 61

the small proj ections or pa pill ae with whi ch its outer surface ,

is studded and which form the characteristic grain pattern

,
-

of the various kinds of skin ( see fig

1
and which con .

tain the nervous ganglia which are the organs of the sen se of
touch .

The study of the structure of the grain and especially of

the arrangement of the h a
,

i r—
pores is very imp ortant as it , ,

is usually the readiest means o f identifying the kind of

'

skin of which a leather is made , which in fin ishe d skins with ’

artificially printed grain is often very difficult (Frontispiece )

a
. .

The examination is facilitated by wetting n d stretching the

skin a n d by the use of a good lens
, or a low power of the [

microscope 2
.

I t has been noted abo v e that the sebaceous glands of the hairs
'

are immediately b e low t he grain layer while the hair bulbs -

,
-

and sweat glands are so mewhat deeper and frequently associ

-

ated with large n umbers of fat cells This is specially the case -

in sheep skins where in both cases t he oily matter is so abundant

that these regions h a
-

ve b een described as distinct layers and

sp oken of as sebaceous a
,
”
nd adipose layers Though it .

is con venient to retain these names neither is strictly appropriate

as La t s ebu m is ta
, ,

llow whil e the fatty matter of the glands is

mainly a liquid wax co n t inin g n o glycerine and much un s a a
-

.
h

ni
po

fia
z
,

b l e matter and in a p urifie d form constituting lanoline while

’

the contents of the cells of the hair bulb layer is a soft t a

, ,

a
llow -

glycerides of oleic and stearic cids and the term adip ose
layer is obj ection ble as liable to confusion with the pa
a diposu s u nderlying the c o r i um which a
a
n n icu l u s

l so contains large ,

quantities of similar fat Cells I t may be noted that these cells -

.
,

which are frequent in loose connective tissue thr oughout the

body are really li ving cells with nuclei and proto p lasm and the
, ,

fat cannot be set free and worked out or expressed till the cell
wa ll s are broken down by liming or some other m eans They .

are shown in fig 20 . .

1 I t wi l l b e n ot ed a
t h t t h e wo r d gr in a is u s e d b y t h e t n n e r in t a a
le at t h s re e a
d iffer e nt se n s e s , wh ic h re
'

p r o d u c t iv e o f m u c h c o n fu sio n Th e
t m l y t hi h ya f m aa a l gl az t t h ki ad m igh t w ll
.

ex re li e t n ne or s n ur e o e s n, n e

b p k
e s f a o h ; th f m a
en o d aa g m
s su c t f t h pa p ill a ad hae i or n rr n e en o e e n r

p m igh t b
o res all d t h pa tt e c f th g a i e l a i g th e f th e rn o e r n, e v n e u se o e

w d or g a i g ai la r
y n it lf or t i t d t t h pa pa
r n p ill ai er se res r c e o e rs r s

l igh t d f m a
-
.

U d 2
th mi th ki i f b by o ve
“

n p er e c r o sc o e e s n s o c o u r se e ro

di t l ight f m a
rec wi d w b y t ha
ro t f a lamp n t at e d b y a b ll
o or o co n c en r u s

a l f t h im a a
,

e y e d Th
co n en s er g i t h mi e r e v ers
p ft o e e n e c r o sc o e o en c u se s

ap d p i ff t y p l i g t t h b gi a pp a
.

p mi i g
'

s eu o sc o c e ec ver uz z n o e e n n er , ro n en ce s e r n

ah ll w ad i
s o o at ill t h a
s, n l di ti f t h ligh t i g i
v ce ver s ,
id d e re rec on o e n s co ns er e .
62 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

It has been remarked that both these fatty layers are specially
prominent in sheep skins and e ch when the sebaceous glands
-

,
a ,
“

and hair bulbs have been removed at depilation const itute planes
of weakness in the skins The grain not un fr e que n t ly p eel s a
-

t . __ _

the s ebaceous layer and it is through this t hat the cut is taken
,

in sp l itting fl —wing skive rs while for ordinary skivers it

y
is through or j ust above the region of the h air bulbs ; a
;

,
n d the ,
-

FI G 20 — Fa
t c e ll s in c o n n e c t iv e t is su e af a
t gl o b ul e p p ro t o p l am s

l l wa
- -
.
. . , ,

n , n u cl e u s ; m , ce -
ll .

fatty layer on the surface of the fle sh split is removed by -

skiving before chamoising I n splitting hides in the United .

States the same loose fatty layer is removed from the flesh split -

by a second thin cut the Split being turned flesh side up in the
,

machine so as to make the substance of even thickness from the

, ,

flesh surface which is to be waxed or otherwise finished In

, .

old days before the Splitting machine was invented grains were
, ,

frequently torn from the flesh at this point with a little assistance
of the hand knife -

A s stated above the surface of skin which is next to the flesh

,
 S TR UC TUR E A N D GR OWTH OF S KI N 63

is firmer than that in the centre and contains a good deal of

elastic fibre and as the fibres r un ne a
,

,
r ly parallel with the surface ,

it has a more or less membranous ch aracter The skin is united .

to the bo dy of the animal by a network of areolar connective

tissue (pa n n ic u l u s a
dipo su s) which is frequently full of fat cells
'
-

, ,

and is then called adip o se tissue This constitutes the whitish .

layer which is removed together with portions of actual flesh “

, ,

in the operation of fle shin g If a .

minute p ortion of adipose tissue be

examined microscopically it will appear ,

to consist of a mere mass of fat globul es

’

entangled in connective tissue I f how .

,

ever it be stained with carmine or log

,

wood it may be at once observed that '

each globul e is contained in a cell of ,

which the nucleated protoplasm by which

the fat was s e c re ta
,

ed is p ressed closely ,

against the wall ( fig .

Many animals ( ox horse etc ) possess a , , .

thin layer of volun tary muscle ( red flesh

pa nn ic u l u s c a
,

rn os u s) s pread over the inner

side of t he skin and used for twitching to

,
,

drive o ff flies In rough fle shin g this is .

sometimes left on and may be a cause of ,

dark flesh in sole leather Even in the .

”W M
finished leather its striped structure may
“

be detected microscopical ly ( fig FI G 2 1 — St ip e d o r r

vol unt a y m u s c ul a
. . .
,

B esides the c onnective tissue fibres the r r

a
-

“ ,

fi b ( R vi e
skin contains a varyin g prop ortion of fine re n r

yell ow elastic fibres especiall y in t h e ,

grain layer If a thin section of hide be soaked for a few minutes

-

in a mixture of equal parts of water glycerine and strong acetic

acid and then ex a
, ,

,
mined un der the microscope the white con ,

n ec t ive tissue fibres become swo l len and transparent pp

( o
p
223 227 a
-

. .
,
”
— n d figs 40 and the yellow elastic fibres may
.

be seen as they are scarcely affected by the acid They are

, .
,

however much better seen when stained blue with fuchsin and
,

Weigert s stain The hair—bulbs and sweat and fat glands are
’
.
-

also rendered distinctly visible by treatment with acid glycerine

On the other hand the white gelatinous fibres are most e a
.

, sily
seen by examining the sectio n in a strong solution of common
salt slightly acidified with acetic acid or in one of ammonium
, ,

sul phat e or by staining with some aniline dyes such as safranine .

Sections are most readily cut for these purposes by the use of the
64 P R I N C I P L ES OF L EA THER MA N UFA C T UR E

freezing microtome or after previous h a

, rdening in alcohol For .

further details see p 3 9 1 and the articles o f Seymour

.
,

Jones in t he 1 9 1 7 et seq , .

Ordinarily in the p roduction of leather only the corium o r

“

fibrous part of the skin is used and in order to obtain it in a suit

, ,
‘

able condition for the various tanning processes the hair o r wool“

, ,

together with the epidermis must be completely rem o vedZWit ho ut

,

damaging the sk in itself and especial care must be t aken that

the grain sur face o r portion next to the epidermis do es not suffer
-

any inj ury during the t reatment All the methods employed
depend upon the fact that the epidermis cells especi a
.

l l y the soft ,

growing ones next to the corium and those of the epidermis layer ,

whic h surround the hair roots are more easily destroyed than the
c ori um itself owing to their di fferent chem ical cha
-

racter The .

unhairing pr ocess consists essentially in breaking down these

cells by chemical or putrefactive agents and removing the ha ir ,

to gether wi th the rest of t h e epidermis by mechanical means .

Of the variou s substances which may be used fo r this purp ose

a
lime is one of the most convenient as its solubility in water is ,

so slight that a soluti on of such a strength as r pidly to inj ure

,

the hide cannot be made and lime being divalent causes only
, , ,

half the swelling of mon o valent alkalies Caustic alkalies on the

a
.
,

other hand are much more soluble and unless c re be taken to use
, ,

only the proper quantity a dangerously strong solution may be

,

made with consequent damage to the skin The addi tion of small .

amo unts of sulp hides to the lime solution accelerates the unhairing
owing to t he ir s p e cia
l so lv en t a c t io n on the epider mi s structures
'

and also in the case of alkaline sulphides by the caustic alkali ,

which is produced by their reaction with the lime Even if “

used alone strong solutions of alkaline s ulphides rapidly

,

destroy both hair and epidermis , converting them into a mass

which may be swep t o ff the s kin like wet p ulp and yet they ,

have practicall y no inj urious action on the true skin R ohm .

has p atented the use of the p ancreatic ferments (t rypsin etc ) , .

for unh airing .

I n the sweating p rocess the epidermis cells are bro ken

down by putrefactive organisms and their products e sp e c i ,

ally the tryptic ferments so that the hair becomes loose , ,

and may then be either rubbe d or scraped o ff A mmonia .

,

which is produced during the putrefaction has also an ,

important solvent action and its presence doubtless tends

,

to quicken the processes both of unhairing and of de

struction .

To obtain useful knowledge of t he s t r u c t u re of any particular

'
 S TR U C T U R E A N D GR OWTH OF SKI N

skin it is not necessary to have a very el aborate or expensive

microscope and it is qui te possible to obtain much information
,

merely by the use of a good pocket lens as for instance in the

, ,

examination of various forms of grain and the embossing of

one skin to imitate another
.
 CHAPTER VI I I

WA TE R AS U SED IN TH E TA N N E R Y

OF a
all the materi ls employed in tanning none is of more indis
a
,

pensable importance th n water and its quality has undoubtedly

,

great influence on tanning though it is constantly blamed for

,
.

faults and troubles which are really due to the mistakes of the
tanner
Wa
.

t e r is chiefly used in tanneries for soaking and wash ing

hides and skins for making the limes the bates and the tanning
, , ,

liquors for steam b oilers and in dyeing Fo r all these p urposes

,
-

, .

it should be as free as p ossible from impurities but Since water is ,

“

a
the most universal solvent in Nature it is never found pure but
al ways contains miner l matter derived from the rocks and
, ,

soil through which it h a s flowed as well as organic impurities

,

from decaying animal and vegetabl e matter A sso ciated with

a
“

the latter are usuall y living org nisms of putrefaction ( ba c ter i a

.

) ,

which may affect the quality of the watet for tanning even
'

more seriously than the mineral impur ities The purest natural .

waters are those which have flowed only over hard sandstones
and volcanic rocks while limestone dissolves freely in the carbonic
,

acid of rain water Water sufficiently pure for laboratory use '

ca
-

n only be obtained by disti l lation The steam wat er from .

-

heating p ipes usually contains large quantities of dissolved

iron and often also volatile organic matters from the Oil etc
which finds its way into the boiler I t m a
, ,

y sometimes be made .

fit for use by boiling ( which p recipitates the ferrous carbonate

present ) , and subsequent settling or filtration The us e o f s t e am
’

water containing iron is a frequent source of stai ns and discolora

tions in the tannery which more than counterb a l ances the
advantage of its softness .

Th e hardness of natural waters is mostly due to the sal ts of

lime and magnesi a which they contain which precip itate Soap in ,

the form of insoluble stearates and oleates which are useless for ,

washing I t is commonly estimated by determining the amount

.

of a standard alcoholic soap solution which must be added in

order to produce a permanent froth on shaking Theoretically .

about 1 2 parts of soap ( sodium stearate or oleate) are destroyed

by 1 part of calcium carbonate or an equivalent quantity of
66
 “

68 P R I N C I P LES OF L EA TH ER MA N UF A C T UR E

ing process When an equivalent amount of lime is added

.

to a solution of h ydric calcic carbonate it displaces the water ,

of the half bound carbonic acid forming a second molecule ’

of c a
,

lcium carbonat e which is precipitated together with that ,

originally present as is represented In the following equation

,

C C a
8 3

Hydric magnesium carbonate is also precipitated b ylime b u t

the reaction is somewh a
,

t different the magnesia being removed ,

as hydrate as fol lows .

{ fign
g c no n h ( 4)
It will be noted that 2 equiv a l ents of lime are req uired to
\

precipitat e I of magnesia Two molecules of sodium hydrat e

a
.

( N OH ) or potassium hydrate ( K O H ) may be substituted for

I of Ca ( OH )2 with similar res ul t s and in some cases it is
p rac ,

tically advantageous to use the former as the sodium carbonate ,

formed in precipitating the temporary hardness reacts again

on the permanent t hrowing down the lime and magnesia as
'

carbonates ( Se e p . .

The use of lime for softening temporary hard waters was .

originally p r o p o se d b y Thomas H enry '

of Manchester , ,

but was first applied as a practical process by Clark who after , ,

adding the requisite quantity of lime to the water in a mixing

va t allowed it to stand in a large tank to clear by subsidence
, ,

the precipitated carbonate of lime taking from six to twelve hours

to settle The process in its original form is a perfectly satis
.

factory one except for the capacious settling tanks which are
,

required which in some cases are inconvenient and expensive

, .

Messrs Ar chb u t t and eeley patented a modification of the

D 1 ’

Clark p rocess by which the time of subsidence is much shortened

and a
, ,

ccording to which the precipitated carbonate of lime of

p revious O erations is allowed to remain in the tank
p and the ,

fresh charge of water and lime is mixed up with it by means of

steam inj ectors which blow in a current of air through perforated
pipes at the bottom of the tank and a
-

t the same time very ,

-

Slightly warm the water The action goes on much more rapidly . .

at a Slightly raised temperature t ham in the cold ; and rather

curiously the stirred up precipitate instead of increasing the
, ,

time of clearing settles rapidly and carries down with it that

,

formed in the new Operation The process is particularly suit .

able fo r treating waters containing magnesia from which a ,

1
jo u r n . S o c Che m I n d
. . .
, 1 89 1 , p .
51 1 .
 WA TER AS U S ED I N TH E TA NN ER Y 69

lime and magnesia is apt to be precipitated in

c o m p o un d , o f a
colloid form which chokes fil t er —cloths and will not readily settle
,
.

A ftersoftening the water is usually carbonated by passing

,

the gases produced by burning coke into the floating exit pip e -
7 o P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

through which it falls in order to retain any remaining traces of

,

carbonates of lime and magnesia in a soluble form and prevent ,

their subsequent precipitation in the pipes The apparatus is .

made by Messrs Mather P latt of Manchester and its arrange ,

ment is Shown in figs 2 2 and 23

Several modifications of the Cl a
. .

"
rk process have been intro
d u c e d in which the precipitation is carried on continuously
,

Ge n e r l / a Ar r ag
n en w n i/ 01
'

Ap p aat r us

s of t e n in
g g a
l i/ on s p er ho u r .

Tr a n s ve r s e

it forms saturated lime—water which is passed Slowly up a ,

cylinder where it deposi t s the excess of suspended lime The

, .

clear lime water so produced is mixed with a fresh portion of

-

the water to be softened in a second cylinder also provided with ,

an agitator the proportion of the two liquids being regulated

,

by cocks The carbonate of lime is at once precipitated and is

.

removed by passage through a fil t e r press Thi s process has -

.

long been in successful operation on a considerable scale at

Messrs H odgsons tannery at B everley ’

Sever a
l other forms of fil ter have a
.

l so been employed with

 WA TER AS US E D I N TH E TA NN E R Y 7 1

success and a
,
l so methods in which the treated water traverses
tanks with sloping partitions on which the carbonate of lime is
,

deposited The latter plan was originally patented in France

.

FI G . 24.

by Gaill et Huet and has been introduced into England by

-

Stanhope .

A very good automatic apparatus is now made by Messrs

R o yl e s Lt d of I rlam near Manchester of which a section is shown
.
, ,

in fig 24. .

In this apparatus the bicarbonate of lime is precipitated

by hydrate of lime (lime water) and the sulphate of lime by ,

soda The softened water is then filtered and discharged The

apparatus acts entirely automatically ; a
. .

l l that is necessary is _

to supply the lime and soda daily and follow the very simple ,

and clear directions supplied with each apparatus .

72 P R I N C I P L ES ,
OF L EA TH ER MA N UFA C T UR E

Th e apparatus consists essenti al ly of an automatic lime

saturator and decanter B a soda chamber D a water distributing , ,
-

tank E with a lime slaking division A and soda mi xing divi sion
- -

C a reaction chamber F and an automatic self cleansing filter K

, ,
-
.

Th e lime saturator B requires no stirring contrivance and

lixiviates the lime completely and owing to its upwa
,
'

rd widening
shape it turns the saturated lime water into a clear fluid
,
.

B y a c onstantly uniform water supply thr o ugh the micrometer

valve 3 from the distributing tank E which is conducted down
wards through the centra
,

l pipe 0 the lime paste at the bottom ,

is stirred up and thoroughly impregnated , and rises at first ,

partly with the water until the rapidity of the rising water
,

diminishes SO much , owing to the upward widening shape of the

saturator that the un di ssolved lime particles a
,
r e no longer able

to fol low so that the saturated lime water clarified then leaves
, , ,

t h e saturator B at the top and is carried into the reaction chamber

,

F by way of the mixing pipe E

'
.

Lime dissolves in a definite proportion in water until the l atter

is saturated This property renders it possible to continually
keep a uniform stream of satura
. .

ted lime water supplied as r e

quired for the precipitation of bicarbo nates of lime and magnesia .

This uniform addition o f lime Water is so important that on it

substantially depends the degre e of purification of the water .

Neithe r in the form of powder nor milk of lime can lime be added
in so constantly uniform quantit y .

Th e soda apparatus D acts in an equally Simple and safe manner .

Whereas lime dissolves only in a definite proportion soda is much ,

more soluble A quantity of soda that will su ffice for one or more
.

days is di ssolved in the chamber C and let down into D through

cock Q The action of the soda appa
. ratus is based on the fact -

of the soda solution having a greater Specific gravity than water ,

and thus the water flowing from the distributing tank E through
the sm a l l micrometer va l ve I — which is adj u sted in accordance
with the amount of soda required— into the so dach a
'

m b er D ,

remains always on the surface of the soda solution ( no mixing

occurs) and displaces the same it being carried through the sm a ,
ll
pipe from the bottom upwards and into the mixing pipe E ,
’
,

and finally into the reaction chamber F .

Mr E Munro P ayne has patented the use of sodium phosphate

.

for water softening and it is no doubt an excellent precipitant for

-

lime both as temporary and permanent hardness but its price

, ,

prevents it taking the place of lime and sodium carbonate on any

considerable scale
A comparatively recent process c a
.

l led the P ermutit is of , ,

 WA TER AS U S ED I N TH E TA N N ER Y 73

much greater interest both practically and scientifically Th e

, .

following details have been kindl y furnished by Mr A Glover .

of the R esearch D epartment of the Wholesale Co operative -

Society in Manchester who has practical experience in its

,
,

working
In accord a nce with your request I t ake the liberty to send ,

on a few notes on the P ermutit p r o c ess o f water softening which

I trust wi l l b e of use to you I have arr nged the notes under
. a
the following heads
( )
1 H istory
( 2 ) Composition of Permutit
.

( 3 ) R eactions .

( )
4 A dvantages .

( 5) Disadvantages .

( I ) I n recent time it has been S hown that naturall y so ft waters

of certain districts were origin a l l y hard but after percolation ,

through strata containing minerals known as z eolites gave

soft waters The zeolite is the generic name Of a group of
hydrated double silicates Th e bases found in chemic a
.

. l com
bination with these silicates are principally magnesium sodium
ca
, ,

l cium and al uminium These zeolites exchange bases chemi

cally but su ffer no physic a
.
,

,
l change .

( 2 ) Hence the application of this idea P ermutit is a patent .

name of a synthetic compound whose chemical composition

may be represented as follows
a0
.

2 81 0 11 1 20 3 N , 2 ,
6H20 .

It is a porous materi a l and appears like grou nd quartz

,
.

( )
3 A ssumi ng Permutit to be represented d iir in g the reactions
as Na s and Since P ermutit gives only a base exchange during
,

water softening the following equations will explain the process

,

of water so ftening
Ca H Na m —> CaPm 2 Na HCO3
( CO 3)2 2
P

Mg ( HCO3 ) 2 + Na
2
P m —
>M
n 2N a
HC0 3 .

H ence the temporary hardness is destroyed and sodium bicar ,

bonate is left in solution

a
In time the maximum exchange
has t aken place n d the P ermutit becomes inactive To r e
generate the P ermutit a 1 0 per cent solution of common s a
,
.

l t is .
.

run into the plant R egeneration takes place as follows

.

C Pma 2N a
Cl -
9 N aPm 2
a
C Cl 2

Mn 2N a
Cl —NaPm >
2
MgCl z .
74 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

The plant is now washed out and the hard water supply is turned
,

on as before
P erman en t H a
.

r dn ess — Th e following equations indicate the

.

reaction
a
N 2Pm a a
C SO4 —Ca
Pm9 N 2SO4
Na
.

Na
Mg C1 —Mn
s Cl 2
> 2 .

A fter a time regeneration with common s a l t solution is necessary

( 4) A d ata
.

g v n es

a
.

( ) W ith certain waters it is possible to get zero hard ~

ness using this plant

( b) No chemic a
.

l s to be measured out .

( 6 ) No filtration be cause no precipitate 1 s produced

,
.

dva
( 5 ) Disa n ta
ges
) Production of Na
(a
.

H CO3 for tannery work . This

may be harmful .

( )
b No t applicable for all waters A water that is too
ha
.

r d will necessitate constant regeneration of the

P ermutit A water containing much MgCl 2 and

Ca
.

Cl 2 will be di fficul t to control because ,

Na P m M Cl
g z M n 2 Na Cl

aa
2 ,

N s a C Cl z -
e C Pm 2N a
Cl .

Since common salt is required for regeneration of the P ermutit ,

I think that an equilibrium of the reaction must take place as

N aPm 2 C CIZ a Z Ca
Pm 2N a
Cl .

H ence under ordinary working con di tions I do not think that all
the permanent hardness ( i e Mg Cl 2 and Ca Cl z ) especially if it is
. .
,

high will be removed

,
.

Nevertheless for general com mercial purposes I think that

,

it has many useful applications .

So far as is yet known from the tanner s point of Vi ew it is

’

, ,

hardl y necessary to make any d istinction between lime and

magnesia either or both of which may be considered Simply as
,

hardness A hard water probably softens dried hides m o re

.

Slowly than a purer Water though it is possible that the observed

,

di fference in the time required may b e due in many cases to the '

lower temperature of wells from which hard water is gener a l ly

derived In the actual limes the hardness of the water can
.

have no appreciable influence though if so dium sul phide be used

a
,

l one for unhairing a certain waste occurs from temporary

,

hardness which may render it advisable to add a little lime It .

 76 PR I N C IPLE S OF L EA TH ER MA N UFA C T UR E

but if o ils or fats obtain access to the boiler a soft bulky

,

, , ,

adherent deposit is formed keeping the water from the plates , ,

which may become red hot and lead to collapse or explosion , .

This e ffect is not produced by mineral oils which o n the con -

t ra
, ,

r y tend to prevent adherence of scale to the plates and as

suitable minera
, ,

l oils are not only cheaper but much less inj urious
to t he working part s of steam engines than animal or vegetable
oils or tall ow they sho ul d a l ways be used in preference for
,

cylinder p urp o se s -
.

Water which is temporarily hard owi ng to calcium and

magnesium carbonates is unsuit a ble for dy eing as t he carbonates ,

react with basic dyes precipitating the colour base and so ,

-

rendering a part of the dye useless Further as this precipitate .

,

is deposited on the skins it causes uneven dyeing and gives rise

t o spots and streaks In dyeing with basic dyes therefore it is
.
, ,

advisable to add sufficient acetic acid to the water before u se to

exactly neutr a l ise the carbonates present Of course this treat
ment is quite unnecessary when acid dyes a
.

re e mployed as acid ,

is usually added with the dye and with dyewoods the presence ,

of a little calcium salt is advantageous

of tot a
.

A s each degree
a
l hard ness represents a soap
“

destroying power of t least 2 oz of so ap per 1 0 0 gallons of water .

,

allowance must be made in making up fat liquors with soap

and oil for the loss of soap due to its precipitation by the miner a
-

l
matter in the water The sticky lime soaps are apt to adhere .
-

to the leather and interfere with glazing so that it is much ,

bet ter to employ a soft water

P erm a n en t ha
.

r dn ess of water is generally caused by s ul phates

of lime and magnesia and more rarely by chl orides and nit rates

a
.
,

A s none of these can be precip itated by lime permanent hardness ,

cannot be rem o ved by Clark s p r o c e ss n o r c n it p ro du c e t he ’

, ,

inj urious effect on limed hides which have been attributed to

temporary hardness Neither can the lime a n d magnesia present
.

combine with the tannins if used for leaching since they are ,

already fixed by stronger acids and at most can only act in ,

ju r io u sl
y by slightly lessening the solubility of the tannins .

Even this e ffect cannot b e regarded as proved though it deserves ,

further investigation P ermanent hardness is therefore of little

.
1

1
Th e in v e st ig t io n s a of N ih o u l In fl u en c e d e l aa
t n ure de l
’
e a u su r

l
'
extr at i
c on d es mat ie re s t a at
nn n B e s, u ll de laB w a o se u x c u ir s d e Lieg e
t a i g wa a
.
,

S ep t e m b e r 1 901 ) on t he nn n t er s o f B e l g iu m see m ed to sh o w th t
a a
p e r m n e n t h r d n e s s is m o r e i n j u r io u s i th
n t a
e exti f t a i g ma
t ia
rl c on o nn n er s

a a a
t h n h s g e n e r l l y b e e n su p p o s e d If t h t a i e i t d a di m nn ns ex s e s so u or

t ai m a f m a i a
.

po l t i l iq
ss u s s n u o r s ve r y fr e e ro id it y it i q it
c bl , s u e conce v e
 WA TER AS US ED I N TH E TA N N E R Y 77

moment as regards the ordinary uses of the tannery though it ,

has considerable influence in some of the processes of dyeing and ,

acts very inj uriously where soap is used for scouring as in the ,

washing o f sheep s kins for wool mats since each part of lime
- -

reckoned as carbonate destroys at least twelve parts of pure

soap ( sodium stearate or oleate) producing a sticky and ins oluble ,

lime soap whi ch adh eres to the fibre In sole leather tan ning
'

-
.

permanent hardness is sometimes advantageous especiall y if ,

it be due to calcium and magnesium sulphates and Vignon ,

recommended that sulphuric acid should be added to the water

before use in quantity suffi cient to exactly neutralise the car
bona
a t es which cause temporary hardness as magnesium and
c l cium sul phates are not inj urious but tend to plump the
hides It must be remembered however that the carbonic acid
,
,

liberat ed may still have prejud ici a

.
, ,

l e ffects on limed hides .

P ermanent hardness is most obj ectionable in waters employed

fo r boiler feedi ng and calcium sul phate is especi a
-
l ly so as
, ,

it becomes nearly insoluble in water at 1 50 C or 5 5 lb °

. .

steam pressure and IS deposited on the plates as a hard crystal

line sc a
-

l e which must be chipped o ff with a hammer Wh ere

many boilers have to be worked wi t h a hard wa
.

t e r it is much ,
.

the mo s t satisfactory to soften the water with caustic soda or ,

with lime and soda together before it comes into the boiler , ,
,

but in cases where the plant required would be too costly boiler ,

compositions are sometimes used with good e ffect though con

sid er a
,

b l e caution is advisable since some of them a ffect the ,

plates inj uriously The active constit uent of many boiler .

compositions is soda ash or sodium carbonate which acts by

double decompo sition with the c a
-

l cium sul phate forming sodium

sulphate and precipitating c a
,

l cium carbonate as a sediment

which is easily washed out Most tanning materi a
,

l s and e ven
‘

.
,

spent tan liquors will prevent or lessen incrustation if mixed

“

with the feed water but sometimes corrode the plates if used too
'
,

freely This danger is lessened if they are used in conj unction

H eavy miner a
.

with soda l oils either introduced in small

.
,

quantity with the feed water or painted on the sides of t he boiler ,

when cleaned are useful in preventing the format ion of a coherent

,

scale .

Th e removal of permanent hardness from water is easily

a
t h t t hey m igh t at wit h a l i m l p hat f rm m g i
re cl bl al i m c c u su e, o n so u e c c u

ta ann t Wl
es ad K Th N ta i
i so n E ig m an ern e on -
nn n n

9 8 ) ha t ha
. ,

1 1 h w ve t th ff t f l t l yt
s o nw hi h d t mb i e e ec o e ec ro es c o no co ne

wit h h i d p wd i i
e aia
-
b ly t o ai th ta i
er s ad d im i i h
nv r o r se e non -
n n n s, n so n s

th ae ppa t a m t
re nf ta i o un o nn n .
78 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

effected in most of the forms of apparatus employed for the

softening of water b y lim e by using a c a
.

l culated quantity of
.

sodium carbonate in addi tion The reaction is r epresented in .

the case of calcium sulphate by the following equation

a
C SO4 N aC0 = Ca
z CO + Na80 3 3 2 4 .

The conversion of magnesium s ul p hate into carbonate may be “

similarly effected but as the latter is somewhat soluble an

addition a l equiv a
a
, ,

l ent of lime must be used to precipit ate it as

hydr ate Magnesium s l ts from their solubility do not cau s e
scale on boilers ( though the chloride 1 s a
.
, ,

p t to produce corrosion )
but they are equ a l ly destructive of soap with the c a l cium s a
_ ,

Caustic soda will remove temporary hardness n d after b ecoming

l ts
a .

converted into carb onate will further react on any perm a

,

nent
hardness present and its use is therefore sometimes convenient
in sm a l l softening plants but it is not more effective and c o n
s ide r a
, ,

b l y m ore costly than a suitable mixture o f lime and so dium

, .

carbonate Even with these Ar chb ut t states that the cost of ,

softening permanent hardness IS about ten tim es as great as that

a
of removing temporary hardness with lime onl y

a
.

B eside the method j ust mentioned v rio us others are describ ed ,

for the softening of perm nent hard waters ( see pp 7 1 -

"
.

A s regards the influence of other impurities our knowledge ,

I S far from complete b u t t h e following are the most important

,

matters likely to be present

a
Mn d under n y circumstances is obj ectionable It frequently
contains organic slime and org a
.

nisms which encourage the

putrefaction of hides placed in it to wash or soften It a l so
a
.

l most invariably contains iron as one of its constituents and ,

hence stains leather and gives dark coloured liquors It is not -

.

easily removed by filtration as large fil t e r beds are expensive ,

-

and difficul t t o keep in order and much space is required to

clear water by subsidence Some mechanic a
.

l filter which can

.

be easily cleaned and used under pressure o ffers the best chance
, ,

of success The Pul someter Company make one consisting of

.
,

sponge tightly packe d below a perforated piston To cleanse

the fil ter a stream of wa
.

ter is passed the reverse way and the ,

piston raised and worked up and down either by hand or power , ,

so as to loosen and knead the sponge Filter presses in which .

-

cloths or in some cases sand are used as the filtering medium

, , ,

are also well adapted for the purpose If a water be softened .

1
P r o cee d i ng s of I n st f M ee k
o E n g in eer s 89 8 , p p
1 40 4
—5 4 in wh ic h
a
l a a a
. . .
, ,

m uch v ubl e in f o r m t io n on w t er -
s o ft en in g is give n .
 WA TER AS U S ED I N TH E TA NNE R Y 79

by Clark s or other process the precipitated chalk carries down the

’ ‘

mud with it together with most of the organisms

I ron is a
.
,

l ways an obj ectionable impu rity in the tannery

though it is less injurious t o the qua
,

l ity than the appearance of

the leathe r produced and indeed German sole leather tanners
,

frequently put old iron in the handlers to darken the colour of

the leather and apparently if not re a
,
l ly to qui cken the tannage
, , .

It must not be present i n waters used for dyeing I ron oxide i s .

frequently present as a mud merely and in this case can be ,

removed by fil tration It is rarely in solution in any other form

than that of acid carbonate sin c e sul p ha
.

t e or chloride coul d not

,

exist in presence of bicarbonate of lime In this form iron is .

,

precipitated at once by boiling or on the addition of lime like

the tempora
,

ry hardness due to other bases in the form of ferric ,

hydrate, and more slowly by o x idation on exposure to the air .

The mud produced by softening waters which contain iron must

be completely removed by fil tration or subsidence before the , ,

water is used for leaching or the iron will redissolve in the acids
,
‘

of the liquors Iron is not perceptibly inj urious in the limes

.
,

but in the bates and Wash pits sometimes causes stains which -

are scarcely visible till blackened by the tanning liquors In .

presence of sulphur ( from sulphide of sodium or the decomposi

tion of sul phates by t he sul phur bacteri a
a
nearly always present
in b tes a n d soaks ) the st a

a
-

i ns become bluish or greenish black -

and black deposit is frequently produced on the sides of the

pit in which the threads of sulphur bacteria ( Thiothrix) can
often be recognised by the microscope As ferric s a
-

l ts not onl y .
‘

combine with the tannins but are themselves tanning agents ,

( see p. they are rapidly absorbed by leather and iron is ,

always present in leather ash ( Fo r detection and estimation see .

p 40 ; p
A lu min aexcept as clay is rarely present in waters and
. .

, , ,

probably harmless in any water likely to be used in tanni ng

S oda
,

is sometimes present in considerable amount as sulphate , ,

chloride or carbonate The sul phate slightly increases plumping

in l imes The chloride if present in materi a
.
,

.
,
l quantities as in ,

tidal rivers lessens it and may cause thin and soft leather
, , ,

and in large amounts will greatly impede the proper e xhaustion

of many tanning materi a
a
ls So di um carbonate is someti m es
.

present in considerable qu ntities as in some of the waters of the ,

Leeds district It may coexist with temporary hardness and

.
,

produces similar inj urious effects but waters in which it is present ,

cannot have any real permanent hardness It may be neutralised .

by the very cautious addition of an acid or by admixture of a ,

80 P R I N C I P L ES OF L EA TH ER MA N UFA C TUR E

permanent hard water It tends to increase plumping in the

limes but neutra
-
.

,
l ises the free acids of the tan liquors which are
necessary in sole leather tanning
C opp er l ea
.

d and other metallic bases are not likely to be

, ,

present in any waters used for tanni ng l n quantities sufficient to

be inj urious
S u lphu r i c a
.

c id rarely occurs free in water and then only in

such traces a
,

s wo ul d be harmless for tanning though possibly

’

inj urious to steam boilers A s sulphates it is most common

Alk a
. .

l ine sul phates are not kno wn to have any deleterious action .

Th e sulphates of lime and magnesia are the principal cause o f

permanent hardness I ron s ulphate is sometimes found in ,

colli e ry waters from the oxidation of pyrites

N itr a tes a
.
,

n d n il r it es in water are usuall

y the result of pre
s ewage contamination and are o n l y im p o rt a
.

vio u s nt as an ,

indication of the possible presence of the p utrefactive ferments ,

and are of little moment in waters o nl y used for manufacturing

purposes while th ey seem to be even useful in promoting the
,

”
working of bran drenches by supplyi ng the ni trogen required ,

by the ferment .

C hl orin e is seldom or never p r e s e n t ain water in the free state ,

but only in the form of chlorides most frequently that of ,

sodium ( common salt ) the e ffect of which has been referred to ,

on p 7 9 The action of other chlorides is probably similar

as regards the swelling of hide Ma
. .

gn es iilrn chl ori de is very .

a
obj ectionable as a constituent of b oiler waters as it liberates
hydrochloric cid at high temperatures a
- .

n d corrodes the plates ,

at the surface of the water This inj ury can be prevented by .

addition of soda
Ca r bon ic a
.

cid has been referred to under temporary hardness

“

It s presence in the free state is a matter of some importance to

the tanner ( s ee p
S ili ci c a
.

cid in a soluble form is present in some waters in con

s ider a b l e quantity Such waters are said to harden leather but

of this the writer has no person a
.
,

l experience .

F e w accurate researches have been made on the e ffect of the

impurities of water on tanning and though from what has ,
1
,

already been said it will be seen that they are not without effect , ,

it is probable that in many cases the water is blamed for troubles

which are simply the result of mismanagement and credited with
virtues which are re a
,

l ly due to careful and skilful manufact ure .

1
S e e N ih o u l loc ci t a
l so R ep o rt of A m e r ic aC
n o m m is s io n o n E ff e c t
ad Wa ai ad ad
.
,

of H r t er on T nn ns, 1 9 1 8, p .
40 9 ; n Wil s o n n

Ke r n ,
l oc . cit .
 WATER A S US E D I N TH E TA NN E R Y 81

Th e hardness of water and the dissolved carbonic acid which

it cont a
,

i ns are tog ether with its temperature the principal

“

, , ,

factors which d et er min e whether a hide will plump or fall in it .

Almost the onl y careful investigation of this point has been

made by W Eitner 1
He plac ed pieces of hide unhaired by
sweating and quite flat and f a
.
,
.

,
l len in water for four days at a ,

temperature of 46 F ( 8 C ) with the following results °

.
°
.

1 . In distilled water Scarcely at all plumped .

2 water saturated with COZ Well plumped

with lime b ic a
. .

3 rb o n

ate 2 0 German °

sc a
,

l e o f hardness Tolerably plump .

magnesia bicar
bonate 2o do ,
°
.

lime sulphate ,

2 0 do Well plumped °
. .

magnesia s ul
phate 2 0 do B est plump e d °
'

. .
,

magnesium chlor
ide 20 do No t at all plumped
°
. .
,

common salt ,

2 0 do
°
.

( 20
°
German scale equal 3 6 or parts of Ca CO3 per
°

see p .

The pec uliarities which were shown by the hide pieces on

removal from t h e water were maintained throughout the tanning .
,

which was conducted in imitation of the A ustrian method the

”
,

hide being swollen and coloured through in weak birch bark -

liquors made with distilled water and acidified in each case with
“

equ a l quantities of lactic acid and finally l a

,

i d away till tanned

in a mixture of oak b rk and va a
, , ,

l onia No 6 from magnesium . .

,

sulphate was the best then No 2 No 3 was less good but

'

a
. .
, ,

a
ll the pieces from 1 to 6 were fir m close and of good substance , ,

n d texture No 1 having swel led well in the sour liquor

, . On .

the other hand 7 and 8 scarcely swelle d l n liquor but remained

fla
, ,

t throughout and were looser thinner and of finer fibre

,
From , ,
.

thi s experiment it is clear that while sulphates and carbonates

exert a _f a
vo u r a
bl e i nfluence on plumping chl or ides do the reverse , ,

as they themselves not onl y do not plump but they place the ,

hides in an unfavourable con di tion for the plumping action of

acids in the liquors These experiments are quite borne out by
.

the wr iter s experi ence in practice The water at the Lowlights

’
.

1
G e r b er iii p . . 1 83 ; o
p . a
l so Ch p aX . .
82 P R I N C I P L ES OF L EA TH ER M A N U F A C T UR E

Tannery which in dry weather was mostly obtained from beds

o f what was o rigin a

a
,

l l y sea sand and which consequently contained

a very abnorm a l proportion of chl orides ( up to 68 p rts Na
-

Cl per
required speci a l and very careful management to make
thick leather not withstanding the fact that it contained a con ‘

sid er a
,

a
b l e quantity of calcium and magnesiu m sul phates These
facts l so indicate the importance of the thorough remova l of s a
.

lt
from hides int ended for sole leather Plumping is not a desirable . .

thing in leather i ntended for dressing purposes and it is possible

that the use of a sm a g e of s a
l l p erc en t a
,

l t in the liquors or wash

'

waters might in some cases enable bating to be dispe nsed wi th .

There is no practicable means of r emoving chl orides from water ,

but Eitner suggests the addition o f a small quantity of sul phuric "

acid to water cont aining much temporary hardness ( bicarbonates) ,

in order t o convert it into permanent hardness ( sulphates) which , ,

as stated above plumps better The amount required may be

ca a
.
,

l culated from an acidimetric determination of temporary h rd

ness ( see p 19 ; .p A simple but not very .
,

ac curate guide is to add enough acid to purple but not to redden

litmus paper even after moving t he l a
, ,
.

t t e r abou t in the water for

‘

some minutes In practice the a cid must of course be very

.

thoroughly mixed with the water by stirring and plunging It must .

be borne in mind that Eit n er s experiment was on sweated hides ’

and that with limed hide which is kept plump by the dissolved ,

lime retained in the hide di fferent results as regards carbonic acid

,

and bicarbonates wo ul d be obtained B oth these wo ul d convert

the lime in the hide into ch a l k which is insoluble and inert a
.

, nd ,

the hide would fall at any rate when the lime was completely
,

carbonated whi le hides wo uld remain plumpest in waters most

free from substances capable of neutra
,

l isin g lime From this

“

we might conclude what may be a

.

priori expected that the purer

the water the plumper limed hides rem a
, ,

i n i n it but i n soft but

a
, ,

peat y waters hides fall rapidly from the neutr lisation o f the ,

lime by the weak organic acids of the peat Such waters are .

dangerous for domestic use from their solvent action on lead '

but this danger can be entirely removed by storing the water in

limestone reservoirs or allowing it to flow slowly through a
,

limestone culvert before use In some town s in the north of

England a sm a ll quantity of lime is added so as to neutra
.

l ise the
water as it leaves the reservoir and before it enters the mams .

Wh erever the conditions of putrefaction or decaying organic

matter are present as in a bate hides f a l l rapidl y and i n extreme
cases even the presence of the stronger acids will not maint a
, , ,

in
plumpness Eitner mentions the case of a stream at Viss o ko in
.
 CHA P TER IX

P H Y S I CA L CH E M I S TR Y I N A P P L I CA TI ON TO L EA TH E R
M A N UF A C T UR E

all sciences are rea

'

TH OUG H ll y parts o f one great whole its ,

immense extent makes it necessary to specialise and to separat e ,

by more or less arbitrary divisions On e of the latest of these

“
.

is Ph ysical Chemistry and it is rapi dl y increasi ng l n both

scientific and technic a
,
.

l importance though its limits are not easy

to defin e While the g enera
,

. l chemistry of the past deal t mainl y .

with the properties and reactions o f elements and their com-

pounds and was satisfied to state that under given conditions

such a nd such actions wo ul d take place ph ysic a
-

l chemistry seeks
,

to find the underlying laws of these changes and to e xplain

/

them by mechanic a l and physic a

,

l causes which can be exactly

and mathematic a l ly expressed In gener a
. l chemistry the atomic
theory the theory of val ency and the laws of gas and vapour
pressures r ep r eseii t the beginnings of physic a
, ,

l chemistry but it ,

now embraces large portions of the kindred sciences of electricity

and thermodynamics and some knowledge of physics is necessary

a
,

before they can be understood .

A s it cannot be assumed that all readers of this work r e

familiar with these ideas it is necessary to treat them in an “

elementary and explanatory way before a

,

ttempting to apply
them to the problems of leather manufactu re a large part of
which depend on physic a
,

l chemistry for their elucidation Mathe .

matie s is as far as possible avoided and where used is always of

,

the most elementary sort

C on stitu tion of Ma tter — It is one of the fundament a
.

l ideas of
general chemistry that a
.

l l compounds are built up of atoms ,

but modern chemistry has taken a further step and explains that ,

the atoms themselves are built up of electrons which are c o n ,

c e ive d as particles of e l ec t ric it y it s el f These electrons are both

'

negative and positive and it is usu a

.

,
l ly supposed that one or more
large positive electrons occupy the centre of the system with a ,

number of negative electrons grouped round them This View has .

been greatly strengthened by the fact that elements like radium

give o ff a constant stream of electrons and in doing so undergo ,

change themselves radium itself becoming ultimately converted

,

84
 P H YS I C A L C H EMI S TR Y IN TA NN I N G 85

into a form of lead The electrons themsel ves are minute charges
.

of or electricity and of course exert the usual attractions ,

on those of opposite sign which constitute chemical affinity , .

Electric currents are in all probability streams of free elec , ,

trons
S ta tes of Ma tter — A ccepting the ordinary chemic a
.

. l theo ry we ,

assume that all matter as we know it is built up of mol ecul es

consisting o i groups of atoms held together by their chemic a
-

l
( electrical ) a ffinities and t h at for any individual substance these
molecules are a l l exactly a l ike cont aining the same number of ,
“

the same atoms arranged in the same way We may now try to
,
.

form some mechanical conception of matter as we see and feel it

in its various forms— solid liquid and gaseous In no case are
the molecules at rest but a
.
, ,

l ways in a state of rapid vibratory

motion which we c a
,

l l heat and the higher the temperature the ,

more rapid is the movement of the molecul es and the greater ,

the spaces through which they move They strike each other .
,

and reb ound and tend to separate b u t on the other hand they
, , ,
“

are drawn toget her by an attraction very similar to if not identical

with the attraction of gravitation and very possibly electric a
,

, l in '
,

its origin This attraction is very powerful when the molecules

a
.

re closely approached but like gravitation rapi dl y diminishes

with distance These attractions a
, , ,

. re opposed by the energy of

heat which thus takes the same part in molecular physics which
,

the energy of planetary motion does in the solar system

Ga
.

s es — I n the gaseous or vapour state the spaces between the .

particles are so great that th eir at tractions are inconsiderable ,

and if unco nfine d they woul d fly o ff into space while their blows
.
,

on the walls of any vessel which contains them are the cause of
their pressure The pressure is thus proportionate to the number
.

of blows per second and consequently to the number of gas

molecules in a gi ven space a
,

n d if we double the density of gas , ,

we therefo re double the pressure ( B oyle s law) Temperature is ’

.
,

in fact most accurately measured by the pressure ( or its r e

c ip ro c a
,

a
l the volume ) of a given quantity of gas each degree
, ,

Centigr de corresponding to an increase o f volume or pressure

of that at o C or freezing point ( Gay Lu ss a 0
c s or D alton s
’ ’

law) From this l a

.

. w a remarkable conse q uence follows : at

—2
7 3 C if the law holds a gas wo ul d have neither pressure nor
°

volum e or in other words the molecules wo ul d ha

.
, ,

, ,
ve none of the ,

motion we know as heat and hence — 2 7 3 C is known as the ,

°
.

absolute zero of temperature Temperatures measured from

this point are genera
.

l ly denoted by T and it is found that ,

measured in this way many relations are much simplified It .

 86 P RI N C I P L ES OF L EA TH ER MA N UFA C T U R E

is of cours e impossible to reach absolute zero but in liquid ,

hydrogen it is approached within a few degrees 1

If di fferent gases a a
.

re confined together in t he s me space they

will of course take the same temperature and the m olecules ,

of each will exert their pressure on the walls independently of

“

the others so that the tot a l pressure will be the sum of the
partial pressures of each of the gases It can be shown a
,

l so
t ha
.

t each molecule must on the average acquire the same energy

of motion whatever it s weight so that it follows that the
, ,

heavy molecul es m ust move more slowly than the lighter and
that a ll molecules whatever their weig ht m
,

ust exert the same

, ,

pressure or at constant pressure must occupy the same volume :

,

This is A vogadro s law and the fact that at a given temperature

’

and pressure there must be the sam e number of molecul es of any

gas or vapour in the same space is constantly used to determine
the relative molecular weight of di fferent substances
‘‘

The Li qu id S ta
.

te differs from the gaseous in that though ,

mobile it can b e retained m an open vessel and can o nl y escape

, ,

by t aking the form of vapour or gas We may conceive that the

,

molecul es of liquids though still possessing heat motion are so ,

-

much closer together that their attraction i s sufficient to prevent

their separation though they can still move within a limited ,

distance Their motion can indeed be shown indirectly by the

constant vibration of sm a
.

l l particles such as bacteria ( B rownian ,

motion ) which can be seen in the microscope and which is caused

, ,

by the bombardment of the liquid molecul es

Va
.

ssu r e — Though the average velocity of the molecul es

p o u r p r e -

is a constant at any given temperature individual molecules ,

may have their velocity increased or diminished by collision with

others so that a certain proportion if they reach the surface
may pass through it and take the form of va
, , ,

p o u r o r gas On
‘

1 T h e se l w s a
p e r fe ct g se s of a a
r e m t h e m t ic ll y e x p r e s s e d b y t h e a aa
a
e qu t io n p v = R T wh e r e p i s t h e p r e s su r e 1) t h e v o l u m e T t he b so l u t e a
a a a a aa
, , ,

”
t e mp er t u re n d R t he g s c o n st n t w h ic h is t h e 19 X 1) o f gr m
a a
-

aa a
, ,

m o l e c u l e o f g s t 1 T n d u n it p r e s su r e n d o f c o u r se v r ie s wit h t h e u n it s
a a a
,

m m n d v o l u m e m e s u r e d in c c
2
u sed If p r e s s u r e i s in g r s p e r c

a a a f a t a
l ga
. . .
. . , ,

R =8 4 7 3 6 T h is qu t io n is o n l y
e pp r o x im t ly t e ru e o c u se s ,

a ad ia a
.
,

t h o u gh v e r y th
ne rl y s o o f h y d r o g e n n e d ti
ev i on s on ly i se r o u s s

t h p i t f l iq f a i a pp a a th m l
,

aa
ti h d fi t ly b o e cul e s t he m
‘

e o n o ue c on s ro c e rs ec u se e

ha aa t a ad a th y a
, ,

l
s e ve s l l m
ve dl y
n c u vo u e, n se c o n b ec pp u se e ro ch e ch

ly t ha t th i a tt a a l
, ,

o th erl so c o se ti e r r c ons c n no o n g er be n e gl e c t e d Th e

q a f ad Wa a ad i a
.

e uti on o l i t d v nti er s n ro u c e s c o rr e c ons f o r t h e se , ppn s roxi

ma t ly t
e f t h l i q id t a
ru e t It i
e ve n o e u s e .
_
s =R T ab
b) — , e in g

a t at f a
co n s tt a ti ad b t h at a
n o l l m r c on, n e c u vo u e of t h e m o l e c ul e s .
 -
N

P H YS I C A L C H E MIS TR Y IN TA N N I N G 87

the other hand vapour molecules striking the surface may ,

-

, ,

be entrapped by its attraction and revert to the liquid form .

Of course the denser the vapour the larger the number of

molecul es wil l be entrapped in this way while the hotter the ,

liqui d the more will escape and thus a perfectly definite vapour ,

pressure will be established for a temperature at which these

numbers are equ a
-

l in spite of the fact that it is merely an average

a
, ,

nd that in di vidual particles are constantly passing from one

state to the other Such equilibria are common enough in
daily life a
.

for instance in the comparative steadi ness of t he

a a
s , , ,

birth and death rates in spite o i l l sorts of interfering c uses and _ ,

business depends to a large extent on the steadiness of averages

We sh a
.

ll meet with many similar equilibria in the course of our

chemical study .

- The vapour pressure depends on temperature only and is

-

not affected by the presence of other gases or vapours in the space

each gas or vapour having its own parti a
,

l pressure If water be .

introduced into an exhausted flask the space wil l become fill ed

a
,

with wat er vapour t a pressure solely depending on its tempera

-

ture and at boiling temperature equal to that of the air outside

, .

If the flask were filled with air at atmospheric pressure before the
water was introduced and then se a l ed the pressure would be ,

that of the air in addi tion to that of the water vapour and at
boiling point might be double that of the outside air a
-

nd ,

explosions have been attributed to that cause

Cr itical S ta
.

te —Ii the liquid and its vapour be gradually heated

a
.

in a closed vessel the density of the v pour will increase with ,

its pressure while that of the liquid will diminish with its heat
“

expansion so that apoint will be reached when the two are

,

identic a critic a
,

l the so called l temperature above which there '

“

, ,

is no distinction or separation between liquid and vapour and ,

no liquid surface A bove this temperature liquefacti on is .

,

therefore impossible and it was want of knowledge of this which ,

caused failures of all early attempts to liquefy the more perfect

gases of which the cri tical temperature is very low that of
, ,

hydrogen being — 23 4 5 C That of wat er is + 3 65 C and its °

. .
,

pressure is 200 atmospheres or abo ut 2 9 40 l b per square inch ,

. .

B oiling P o in t The boiling point of a liqui d is reached when

.
-

its vapour pressure exceeds that of the air above it and is able
-

to form bubbles in the interior and it is therefore dependent on

the air pressure Thus in a vacuum pan water m a
,

.
y boil freely
at very low temperatures
H ea t of Eva a
.

i — When a liquid in an open pan over a

p o r t on

gas burner reaches a boil no len gth of time will raise its tem
-

,
88 P R I N C I P L ES OF L EA TH ER MA N UF A C T UR E .

a
p er t u r e any higher the whole heat of the burner being expended ,

on the work of evaporation that is in overco ming the internal , ,

attractions of the liquid and setting the molecules free as vapour ,

.

Th e quantity of heat consumed in this way is very large 1 00

calories ( p 5 1 4) are required to raise a kilogramme of water from

a
.

0 C to but 53 6 calories to convert it into steam at the s me

°
.

'

temperature (A large amount o f heat ( 80 calories) is also

.

consumed in t he melting of ice at freezing point )

I n ter n a
.

l P r essu r e — From the attractions which have j ust been

mentioned the interior of a liquid is subj ect to very heavy ‘

pressures but these are only exerted on things actu a

,

,
l l y forming
part of the liquid that is really dissol ved in it and not on what
, , ,

is merely dipped into it which from this point of View is still

outside it Fo r this reason intern a
,

l pressures cannot be directly

“

measured but they can be calculated with some accuracy from

,

the heat of evaporation since Stefan has shown that to b ring

a particle actually into the surface c on sumes h a
,

l f the work which

is required to set it entirely free in the form of vapour Fo r
b o iling ether the intern a
.

l pressure is 1 2 8 4 atmospheres and for ,

water at freezing point atmospheres or about 7 2 tons per

square inch Though the intern a
,

l pressure cannot be directly

measured its e ffects are visible in severa
.

,
l ways as for instance , , ,

in the large force required to tear liquids apart when free from
gas particles a
-
n d in the violent ,
”
bumping of boiling gas free -

liquids of which the pressure must rise much above that of the
,

atmosphere before it can form a fresh bubble

Su rf a
.

ce t en si on is also a consequence of these forces

-
Although .

they are of such great int ensity the attraction rapidly diminishes ,

with di stance and the surface layer in which they have been
parti a
-

l ly overcome is only of a thickness to be measured in

millionths of a millimeter while throughout the r est of the liquid ,

they are undiminished If th erefore we imagine Stefan 3 ’

particle actu a l ly h a
.
, ,

l f o ut of the surface it remai ns attracted by ,

only those particles beside and below it within this very short
range while above it there are onl y vapour particles beyond its
sphere of attraction By the ordinary mathematic a
,

l device of
the par a a
.

ll elogram of forces we can represent or resolve “

ll .

these attractions into a vertical component pulling directly

downwards and ho rrz o n t a l components of much small er amount
p ulling the surface together equally in a
,

l l directions These
“

sm a l l horizont a
.

l components constitute the force known as

surface tension -
In water in which it is larger than in a
. l most ,

any other liquid it only amounts to about 7 5 milligrams across

,

a surface 1 centimeter wide .

 P H YS I C A L C H EMI S TR Y IN TA NN I N G 89

Though
the force is thus small its effects are visible in many ,

ways Certain insects walk on the surface of water as though

.

it were covered by an elastic rubber sheet and a drop or a bubble ,

will contract and draw back if the pressure within it is lessened

a
.

P erh p s its most import ant e ffect is that of capil larity A liquid
will rise in a wet tube of sm a
.

l l diameter considerably above the

a
level of the surface outside and in the same way oil is sucked up
by a wick or bsorbed by leather or fabric In a wider tube
,

the l iquid is drawn up round the walls so that the surface is

,

a
,

not fl t but takes the well known meniscus shape In a vessel

,
-

which the liquid does not wet on the other hand the edges of the , ,

liquid are depressed and the surface is convex like that of the
mercury in a ba
, ,

rometer .

Surface tension may be measured by the extent to which the

-

given liquid will rise in a small tube but for most purposes the ,

easiest method is t hat of weighing a given number say 1 00 drops

which are a ll owed to f al l slowly from a sm a
, , ,

l l horizontal opening ,

such as the bottom of a burette As it is not easy to measure

‘

exactly the outside diameter of the dropping tube it is simplest ,

to make a preliminary experiment with water of which the

surface tension may be assumed as 7 5 and c a
,

-
l cul ate that of ,

othe r liquids measured with the same tube as proportional to

the weight of drops as compared with those of the water The
dropping end of the tube shoul d be thin smooth a
.

nd quite free
from grease Very sm a
, ,

l l quantities of some impu ri ties especially

.
,

organic greatly affect the tension

Much controversy has arisen as to wh ether the actu a
.
,

l surface
is a region o f increased or diminished pressure and elaborate
-
“

theories of tannin g and of colloids generally have been based

, ,

on the former assumption which in the writer s opinion is , ,

’

entirely unfounded and unsupported by facts It need only be .

said that if the explanation of the causes of surface tension which -

have been given here and which are held by the most eminent
authorities on the subj ect and especi a ll y by v a
,

n der Waal s and ,

his pupils are correct the surface is a region not of increased but
of di minished pressure and density and that the actu a
, ,

l boundary ,

between th e liquid and its vapour is a sort of critical layer where

the liquid escapin g from the internal pressure is of an equal
density with t he vapour condensed by the attraction of the liquid
surface 1

Efi ect of Di ssolved Su bsta n ces on S urf a

.

c e ten si on — Certain sub

stances especi a
-
.

l ly salts increase both the surface tension and the

, ,
-

1
C1) . Pr o ct e r , a
Th e N t u r e o f t he Liqu id Su r f a
ce , 3, 1 9 1 9,
p 48
. .
90 P R I N C I P L ES OF L EA TH ER MAN UFA C T UR E

a
intern l pressure Others o f sm a l l surface tension themsel ves
.
,
-

naturally lower that of Water when dissolved in it and some

.
,

organic matters such as soaps saponins etc reduce it to an

, , ,
.
,

extraordinary degree
S u rf a ce en ergy is equ a
.

-
l to the area of surface x the surface
tension and it is an important law that it tends to reduce
,

itself to a minimum in every possible way either by diminish ,

ing the surface or reducing the surface tension Thus a drop -

.

of water falling fr eely or of melted lead in a shot tower

J
,
-

always takes t he spherical form since this possesses the

sm a
,

ll est surface in proportion to its volum e and fo r the same

reason globul es of one li quid suspended in another are a
.

l ways
spheric a
,

l The same law also demands that if two globules of

.

liquid come in actual co ntact they must coalesce since the

a
,

surface of t he larger volume is less than that of the two sm ller

one s A nother consequence is the law of Willard Gibbs that if
.
,

a solution contains a constituent which lowers surface t ension -

this must accumulate in t he surface and this has been shown

e xperiment a l ly to be the case and is one of the causes of a
,

ds orp ,

ti on under which heading it must be further noticed

,
The same .

fact i ntroduces a difficulty into the measurement of the surface

tension o i impure liquids since the tensio n diminishes if the ,

surface stands long enough for the impurity to accumul ate in

it and lower results are obtained by the ordinary statical
,

methods than by dynamic meth ods in which the surface ,

is constantly renewed Some organic mat t ers especially the .

,

sap oni ns not merely accumul ate in the surface but appear to
, ,

become coagul ated there and form a coherent fil m

w
.

So far we have considered only liquid surfaces 1 n contact ith

their own vapour or with inert gases the influence of which may
,

generally be disregarded but classes of surfaces ( or more strictly , , ,

interfaces) very important for technical purposes are those in

which one liquid is in contact with another immiscible with it ,

or with a solid P etrol or ether upon water or water upon

chloroform are instances of the first c a
.
,

, se whil e any solid immersed ,

in a liquid presents the second I f a little petrol be poured on .

water in a test tube it will be noted that the meniscus betw een
-

them still exists but is flatter than that on the surface of either
in contact with air The reason is th a
,

t a portion of the attraction

.

of one liquid is exerted on the other and thus partially com

p en sa t e d and the surface tension of both is lessened that of
“

, ,

the lesser becoming actually minus and the tension of the ,

interface is merely the difference between them This rule is .

borne out by exp eriment if it is remembered that practical ly all

92 P R I N C I P L ES OF L EA TH ER M A N UFA C T UR E

saponifyi ng the tra ces of free fatty acids which are always present
’

I t is highly probable that these third substances act also b ycoating

the globules when formed as has been expl a i ned in t he preceding
,

paragraph and so preventing their coalescence and rendering

, ,

the emulsion permanent The bearing o i these facts in the .

preparation of fat liquors is obvious Some oils are much more

readily e m ulsifia
-

b l e than others especially if they contain free

fa t ty a c id s or some oxidised fats a
,
'

s is the case with sod oil and ,

degras A ddit io n o f a trace of oleic acid to a neutral oil is often

. x

useful Sul phonated oils are al s o very powerful emulsifying

.
'

agents The author has examined a sampl e of mineral oil con

.

taining at most 20 per cent of sulph onated oil which emulsified .

spontaneously to a milky liquid when poured into water Su l .

phonated and oxidised oils all contain traces of water Soluble . -

substances which probab ly play the part of the intermediate

coating substance
I t must not be forgotten that in a
.

ny emulsion of two liquids

either m a
‘

y form the separate gl o b ul e s o r disp e rse phase

S o l u ti on — Emulsions or susp ensions of solids m a
.

y be so finely
divided as to possess most of the properties of solutions and will ,

be considered later under the head of C oll o ids but true solutions ,

may be regarded as mixtures so intimate that the individual

molecules of the dissolved body come within t he Sphere of
attraction of those of the solvent and take part in its internal ,

a
pressure thus forming a single homogeneous liquid
, .

M ny liquids will mix or dissolve in each o t her in any propor

tions e g water and alcohol ; the attraction of the alcohol for
a
, . .

the water—molecule being as great or greater than th t of alcohol

'

for alcohol or water for wat er In other cases such as water and
, .
,

oil or water and petroleum spirit practically no mixture takes

, ,

p lace ,
their mutual attraction being small ; and each retains a
considerable surface tension at the points of contact though -

less than that of the free surfaces since each exerts an attraction ,

on the other There are also many intermediate cases such as

.
,

water with chloroform carbolic acid or ether in which each , , ,

solvent dissolves a p ortion of the other but the two solutions ,

do not mix but form separate layers In these cases an e quil i

, .

b r iu m is attained in which there is j ust as much tendency for

,

either of the liquid s to pass into as out of the other layer In this .

there is an extraordinary resemblance to what has been said of

vapour pressures and the tendency to pass into solution is often
-

called solution pressure and it may be noted that when e quil i

-

b r ium has been r eached not o n ly is the solution pressure but ,

-

the vapour pressure of each constituent equal in both solutions

-

.
 P H YS I C A L C H EMI S TR Y IN TA N N I N G 93

Like vapour p ressures the solution pressures usually increase

a
- -

with rise of temperature more of each constituent p ssing into ,

the other till at last the composition of the two layers becomes
,

identical their surface —tens1 ons disappear and complete mixture

, ,

takes place With phenol ( carbolic acid) and water this takes
.

place at about 7 0 C The similarity of this to the miscibility

°

of liquid and va
.

a p o ri r at the critical temperature is very striking

n d the point where complete mixture occurs has been called

the critical temperature of the two solutions I n these liquid

,

mixtures either body may be considered as the solvent or the ,

dissolved substance The distinction is quite arbitrary but .

-

usually that present in largest quantity is called the solvent .

Distribution between two S olven ts — If a substance is soluble in

both ot two immiscible solvents it will be distributed between ,

them in a constant ratio according to its solubility in each what

e v er it s q u antity and this ratio is generally c a
, ,
’

, l led the partition

”
constant The point is important in the separation of sub
.

”
stances by shakin g out as for instance the extraction of
tannin from aqueous solution by acetic ether a
, , ,

s it enables ,

us to predict what quantity will be removed by successive

shakings .

If as sometimes happens the

,
molecular complexity is ,

different in the two liquids as i n the case of acetic acid where

the molecules are twice a
, ,

s large in benzene as in water the ,

ratio of concentration instead of being sim p ly Ca /Cb as in the

, ,

/b
first case will be CaC fi in which the fractional
, p ower ,
”
fix
wil l be

a
that of the relation o f the two molecular weights ; thus for the
i
case mentioned it will be CW/C or s /C where w is the w ter B ,

and B the benzene solution This case is p erhaps not of much

a
.

consequence to the t nnery chemist but is mentioned because ,

” 1
of its analogy to what is called the adsorption formula .

A ds orpti o n — I f finely divided charcoal or many other fine ,

powders be shaken u p with dilute solutions they will in many

, ,

cases dependent on the nature of the dissolved su b stance fix a

, ,

portion on their surface much larger than its concentration in

the liquid and larger in proportion in dilute than in more con
c en t r a
,

t e d solutions Thus bone charcoal is constantly used to

.
_
-

decolorise sugar solutions and charcoal wi ll also remove con

si d er a
,

b l e quantities of tannin from aqueous solution The pro

portion remo ved can genera
.

l ly be stated by a formula of the

1
Th e d iv is o r in af at i a
l p
r c on o we r is a ro o t t h u s Ci is t h e s qu a
re

ro o t o f C, or VG .
Ci is t h e —
c u b e ro o t o f C s qu ad ad
re , n so o n .
94 PRI N CI P LES OF L EA TH ER MA N UFA C T UR E
1
— 01 C” 1
,
where x is the Weight of substance absorbed ,
m
777

that of the absorbent ,

aa constant v ar ing with the substance
" y

I
C the concentratio n of the solution and a fractional index
ii
, ,

o f ten about 5 also varying with the dissolved sub stance

,

I t has been shown by Will ard Gibbs , that n y substance which

lowers the surface tension must n ecessarily accumulate in the -
a .

surface ; and experiments with froth and other liquid air or ,

-

l iquid vapour surfaces have c o n firm e d his theoretical conclusion

'
-

.
,

I t has been constantly assumed by coll oid chemists t hat the same
reasoning must apply to the contact of liquids with s olids but
this is b y no means obvio us since in such ca
,
'

s es the liqui d surface ,

has a negative tension and tends to spread on the Solid Fo r , .

a fu ll discussion of the theory o f adsor ptio n see Fr eu n dlic h s ’

Ka pill a
,
-

rchemi e and other books on colloid chemistry .

Most of What has been said about liquid solutio ns is also t rue
of solutions of those solids known as crystalloids .

S ol ution of S o l i ds — Matter exists in two states known as

crystalloid and colloid The c o ll o id st te is amorphous .
'

a ,

and in solution has no defini te point of sat uration and in most ,

( probably in all) cases its particles are larger than single molecules ,

and are often known to be aggregates ; and its solutions are

emulsions or suspensions rather than true solutions I t is
however of such importance in l e a
.
,

, t he r manufacture that it will ,

be dealt with in a separate and later chapter since most of the ,

materials of leather manufacture exi st in t he colloid state .

1
ah a i d t h t i a
T h is f o r m u l sl p l aa ti
re ce ve ad p b a b ly no e o re c ex n on , n ro

ha s none It i a p p li a bl t a sg a t ai t y f h m i a
c l eat i whi h o re v r e o c e c re c ons, c

d a p id l y a t fi t a d g a d a a I t i f q t ly a
.

p ro cee r lly d rs n ll d r u e cr e se s re u en c e

a w hi h it lf i a aa i t h m i
.
,

th e d pti i th m
so r on so mi erm c se s sn o er , s n so er s

a a
-

f q a l t mp a y t m ay p m t t hi k t h a
.
,

t pl t b
“

cu rve o e u e er u re , e n eo e se e o n ec u se

th f a a
e c o u r se o ti ab a ppre im a
c t ly
on c p e t d by t h f m la
n e r ox e re r sen e e or u

it i a sp f t ha t th
ro o at i i p hy i a l a ed tre h mi a l ad m a
c ony b s s c n no c e c n e

la d a a fa p h a l i by m a j t ifi d
,

c s se s msu r ce eno enon , conc us on no e ns us e

it will a im a t ma y w hi h a b i
-

ly h mi a
,

i
s nce pp t ly p ro x e re l r e se n n c re o v ous c e c

It i a ma th ma ti a f t h f m l at h a
.

l f th f m t if
‘
s e q c c o n se uen ce o e or o e or u , ,

i t a a w p l t t h i l ga
1
d f pl t t i g
5 d it h m th l t wil l b
“

ns e o o n n e o e r o r s, e r e su e
7
at a l i d t t h ai a t t h a
s rig h t l i i ne nc ne
gl p t d by
o
i Th i i
e x s e n e re rese n e . s s

r al y t h a i at a
re e c l a
se d pti n p im c u t th li b i g a lm t
so r on ex er en s, e ne e n os

inv aia bly m

r l o re d ( It m t
or t b
ess f g tt i
c u r ve pl t ti g us no e or o en n o n

ga l ga t ha th t a ga
.

ne ti ve it h m o t i
r bl s, ly t h i d i tin wh il e es, on e n ex s ne ve , e

t h mat i a m a
e n i ss ad t g t t h t
re ns ga ti l ga it h m m
n t b o e e ru e n e ve o r us e

su bt a t d f m th i d
r c e ro) e n ex .
 9 6 .
P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

osmotic 1 pressure of dissolved bodies Thus a porous .

earthenware battery—cell may be immersed in a solution of cop per

sulphate and filled with one of potassium ferr o cyanide I n this
,
.

way its pores will be filled with a gelatinous preci p itate of copp er
a
ferrocy nide which is pervious to water but impervious to most
, ,

dissolved substances I f now the cell be filled with a dilute .

soluti on of some cry stalloid say sugar and its top closed by a , ,

perforated cork fitted with a vertical tube and the cell be placed ,

in water the latter will pass into the cell and the dilute solution
, ,

will rise in the tube to a height of many feet abov e the water .

a
outside By substituting a mercury pressure gauge for the
.
-

vertical tube ex ct m easures of the p ressure in the cell can be -

made which is the osmotic pressu re of the dissolved substance

,
.

A t first sight it is paradoxical that water should flow into the

solution ap parently against a heavy pressure but the explana
, ,

tion is simple Mention has alre ady been made of the enormous
.

internal pressures of liquids produced by the attractions of their

molecules In the solution a port ion of this is borne by the
.

osm otic pressure of the dissolved substance and the water flows ,
‘

in from the o utside till an internal mechanical pressure is pro

du c e d equal in am ount to this osm o tic pres sure The resem .

blance of the p henomena of solution to those of vapour pressure -

is very obvious and it is found to be even quantit ative sin ce

'

, ,

the measured osmotic p ressures are exactly equal in amount to

those which the dissolved body would produce if it Were in the
state of vap o ur at the same temperature and occupying the same
volume as the solution I t acts in fact p recisel y as the p artial .
, ,

pressure of a vapour There are several indirect ways of .

measuring the osmotic pressure of dissolved bodies as fo r ln , ,

stance from the lowering of the freezing point or the raising of

the boiling point of the solution a
, .
,

s compared to those of the p ure

_

solvent which are easier of execution and generally more exact

,

than the direct measurements and show that in a given volume ,

at the same temperature the same number of m o lecules will produce

the same osmotic pressure whatever their nature or conversely , ,

that at the same osmotic pressure and temperature equal volumes

of a n y solution must contain the same number of molecules The .

use of these facts in d etermining molecular weight is o b vio us

'

1
So l u t io n p re s s u r e -

adn o s m o t ic p r e s su r e a a
lly
re re t wo n a
m es fo r t h e
s a
m e f o r c e wh e n t h e s o l id is p r e s en t in t h e s o l u t io n ; t h e f o r m e r b e in g
e m p l o ye d to s ign if y t h e t en d en cy of a lid t so o d is so l v e , ad t h l a
n tt e er t h e

p r es s u r e p r o d u c e d b y t h e d is s o l v e d b o d y wh ic h t e n d s t o p r e v e n t f u r t h er
s o l u t io n T hu s , in aa a
s t u r t e d so l ut io n in c o n t c t wit h it s so l id t h e t wo a
aa
l wa q a
.
,

p r e s su r e s re
y l b t s e u , u ex ert ed in o p p o s it e d ir e c t io n s .
 P H YS I C A L C H E MI S TR Y IN TA NN I N G 97

Many liquids do not conduct electricity and

El ectro lys is — ,

pu r e water only does so to a very limited extent but many ,

solutions conduct freely The substances which do so in solution .

are called electrolytes Th e conducti on is of quite a different.

character to that in a metallic wire which undergoes no per ,

manent change in the p rocess while that of the electrolyte is

'

always accompanied by chemical decomposition and the actual ,

transference of matter from one pole or e lectrode to the

other I f for instance the solution is one of sil ver nitrate a
.
, , ,

certain quantity of electricity will be required to deposit a gram

equivalent of silver on the kathode or as it is generally termed ,

the negative pole while an equivalent of nitric acid ( or more ,

strictly of NO3 ) will be liberated at the anode or positive

.
aa
pole I f the s me current passes through a solution of copper
sulphate it will lso liberate an equivalent of copper or a
,

gram atom at the kathode and an equival ent of SO4 at t he

-

anode and through acidified water it will liberate 1 gram

,

atom of hydrogen at the kathode and the equival ent i gram

atom of oxygen at the anode This qu a ntity of electricity .

which is a perfectly definite one is called a Faraday or farad ,

“

1
after the discoverer of the law
I o nisa a
.

tion —
A curious apparent devi tion from the law of
.

osmotic pressure is noticed in solutions of salts acids and alkalies , , ,

and indeed of electrolytes generally thus a dilute solution of

so di um chloride produces an osmotic pressure nearly double that
corresp onding to the number of molecules of Na Cl p resent
and in fact behaves as if it were a solution of Na
,

and Cl existing
separately Such a solution conducts a current of electricity
.
,

very readily while at the same time the chlorine is carried to

,

the anode and t he sodium to the kat hode where they separ ate
as ordinary molecules of Na a
,

and C I2 (
the N decomposing the
water presen t and forming Na
2

OH) I n fact the modern theory .

,

of electrolysis asserts that these dissociated atoms are not sepa

rated from each other by electricity but that they exist already ,

separated in t he solution of the electrolyte and merely act as ,

carriers for the electricity and that the work done by the latter ,

is not that of breaking up the salt —molecule but of giving its ,

dissociated atoms charges of electricity which enable them to

Combine as new molecule sand escape from the electrolyte
.
Com .

1
a id t h t m p it i
I t is b e t t e r t o ad ga
voti ad be er s os ve n ne ve n su

s t it t ua d ad k a
e th d
no at h p l
e e t d wit h t h p it i
n o e, s e o e co nn c e e os ve

o f th batt y i
e all y t h ergati f th ds rem p it i l l ad aw il l
e ne ve o e eco os o n ce n s
-

bab ly a ga
, ,

b b l w th
e s e en l t i e o t i p fl w f ti l t
e e e c r c c u rr e n s ro o o ne ve e e c r o n s

p ai g i t t h k a ad t f t h a d
,

ss n th d n o e o e, n ou o e no e .
98 P R I N C I P LES OF L EATH E R MA N UFA C T U RE

p
a
lex salts do not always break up 1 nto single atoms thus calcium
sulph ate dissociates into Ca and 5 0 4 hydrogen sulph te ( sul ,

p hu r ic acid) into 2 H and 5 0 4 and so on These dissociated atoms , .

and atom groups are called ions and may be monovalent

-

, ,

divalent or polyvalent carrying electrical quantities or charges

, ,

in proportion to their valency Without discussing the ultimate “

natur e of electricity itself the matter is most easily p ictured by ,

assuming that the molecule of t he undissolved salt is made u p of

an ion with a charge kation e g Na ) and an ion with a , . .

”
charge anion e g C1 ) by the electrical attraction of which
'

, . .
,

charges they are held together I n the ionising s olution these . .

attractio ns are balanced by those of other ions and perhaps

a
,
.

by those of the solvent itself so that t hey c n wander freely ,

within the liquid but in order to take the molec u lar form of free
elements and escap e say as Na
, ,

2 and C1 2 the pair of kations must

, ,

go to the pole or kathode and gi ve up one charge and ,

at t he same time a pair of anions must go to the pole or

anode and receive a charg e Thus the N aand all
other kations separate at the kathode and the Cl and a
.

ll other ,

anions at the ano de The more modern view is that the kations
.

a
are positive because they are short of a negative electron ,

and the anions negative b ec use they have one in excess the
galvanic current b eing therefore a stream of
‘

electrons flowing ,

in at the kathode and passing out at the anode to combine with

,

positive ions .

F rom w hat has been said it will be obvious that free ions can
only exi st in solution and c n neither evaporate n or sep a a
,

,
rate as
solids but that in the liquid they act much like other dissolved “

molecules exerting their own osmotic pressure independently of

,

each other or of the dissolved salt but with the limitation that ,

the solution must always contain equal numbers of and ions .

Electrolytes vary much in their t endency to ionise and even the ,

best of them are only completely ionised in i nfinitely dilute Solu

tion s but t he io n is a
,
t io n always increases wit h d il u tio n Just as we .

have sp oken of solution—p ressure we may also speak of ionisation ,

pressure since the ionisation is also an equilibrium d etermined

,

by the point at which as many molecules break up into ions as

those which recombin e and if the ion ic concentratio n exceeds ,

this point ions recombine till the equilibrium is restored This

, .

point has been determined for a large number of substances and ,

is called the ionisation —constant Strong acids and bases .

are those in which it is large weak ones those in which it is ,

very small Thus for acetic acid it is only 0 0 000 1 8 that is

acetic acid is only half ionised a t 0 oooo 3 6 norm a
.
, ,

l while a ‘

,
.
1 00
‘

P R I N C I P L ES OF L EA TH ER MA N UFA CT UR E

weak ens it still further The s a l t say sodiu m acetate ionises

a
.
, ,

much more freely than the aci d yieldi ng sodium ions rid acet -

ions and the latter added to those from the acetic acid increase s
, , ,

the acet ion concent ration beyond the very low ionising pressure
-

of aceti c acid and compels the acet ions to recombine to u nionised

a
'

acid Thus b y adding sodium acetate to acetic a

-

.
“
cid or mmo~ ,

nium Chloride or sulphate to ammonia we can reduce th eir

active acidity or alkalinity to a
,

a
‘

n y desired degree without lessen

ing their power of combining with and neutr lising bases or acids .

This has many uses iri leather manufactur e ; th us in deliming

'

with an acid we can sufficiently r e du c e it s activit y to prevent

swelling ; and in St ia
,
”
sn y s method cf neutralising chrome ’
1

leather the alkalinity of ammonia is so reduced by the presence

of amm oniu m sulphate that it is impossible to carry t h e neutr a
,

li
‘

sation too far The presence of neutr a

,

l salt s of strong acids

a
.

n d bases has howe v er little effect in redu cing the activity of

, ,

1
the stronger acids and bases
strength of an acid or a
.

a As the di fference between the

n d its combining power fo r bases ( or acids )
. which is what IS
determined by titration may still n o t b e qui te clear to t he
l kali
,

reader and a
,
”
s it is one of t hé greatest importance in leather
,

manufacture it may be well to give yet another illustration from

'

pr actice Th e normal soluti on o f a

,

a
n y acid ( 1 e q per liter) will
~
. .

n eut ralise and comb ine with an equal quantity of the norm l
'

s olution of any base but may b e v er y d ifferent in sourness or

appar ent a a
,

l k linity as these properties are due to the free ions of

H+ a a
,

n d OH which are liberated t the same t ime as t h e acid

’
.

or basic ions and it is the H and OH ions whi ch cause the swellin g
of hide Lime and caustic so d a a r e almost equ a
,

l ly stron g al kalies
but we can safely put a b a
. ,

rr o u l of lime into a li me pit while the

same q u a ntity of caustic s o da would dissolve the hides We a

-

ll

a
.

know why this is but little of the lime d ssolves and most
i

remains at the bottom of the pit n d go es gradu a

, ,

l ly into sol u tion ,

to strengthen the liquor as it is taken up by the hides A lmost . .

the same e xplan ation with a difference applies to hydrochloric , ,

and acetic acids though both apparently dissolve at once The ,

. .

hydrochloric acid su ffers almost completely the sort of super .

a a a ta a aad b a t h tw i
'

1
Th e m t h e m t ic l
t m f s e en t is t h t if n re e o ons o

w h i h aa
lt (
c aid b a) i s mp d a
or d k i it ic i a ti — t at
or se c s co o se n s s on s o n co n s n

t ha a f i th f t h t w
, ,

f m wh i h it i b i ro t th i c s o v ous e n cr e se o e er o e o

ions m t in a th us t ati f th
cre i i d
se ak i a t at e c o n c en r on o e u n o n se c, s s co n s n

A im p l il l t a i t ha
t a pa mi g t a
-
.

ti ty f it h gi l m
'

s e us r on s r o e er r s or en co n o

d a wil l i
nce a t h m b f d a i g p l ( m b i d m ol l 1)
n cr e se e nu er o nc n co u es co ne ecu es

by ta ki g p a A id a a
”
t f m thn it t i g t
r n e rs lt f h yd g
ro o se s n ou c s re s s o ro en

wit h aa al ka a y1 ( O H ) wit h aba

.

id i li lt f h yd
'
~
n c -

on e s, s s o ro x se .
 PH YS I C A L C H EM I S TR Y I N TA N N I N G 1 01

solution which we call ionisation a nd exerts its ful l strength,

immedi ately while the acetic acid like the lime remains in the
, , ,

liquor mostly in an inactive unionised state and o n l y i o n ises when

’

the a lre a
,

dy io n is e d part has been consu med by the hide

As the actu a
.

l ionic concentration is the important point in

many technic a l processes and cannot be determined by titration
but on ly by electrometric measurement or the gr a du a l ch a
, ,

n ge ,

of colour o f indicators ( cp p it will be convenient to speak

. .

of it as the true acidit y or alkalinity of a solution as dis

“

tinct from that shown by titration .

A very interesting example of equ ilibria is given by an ordinary

'

method of prepari ng pure common s a lt H ydrochloric acid is

e Ve n more highly ionised than s a
.

l t so that if the concentrated ,

acid i s adde d to a saturated salt solution a part of the salt is pre

c ip it a t ed In a saturated solut ion of sodium chloride with solid
.

salt present we have dissolved salt at the Solution pressure of the

crystallised s a l t and Na
-

and Cl ions at the dissociation pressur e

o f the saturated s a
-

a l t solution and neither a ffect the others

we now dd hydrochloric acid it has no effect directly on the
solubility of the s a
,

l t but as HCl dissociates largely into H and Cl

If .

it increases the pressure of the Cl ions and so compels the s a

, ,

lt ,

t o recombine till the Cl pressure is reduced to its normal amount

This increases the concentration of the undissociated s a
.
.

l t solution
and thus s a l t is precipitated or cryst a
,

l lises out till the solution

is no longer Supersaturated with respect to the s a l t cryst a
Th e neutr a l isation of acids by a l ka
ls
a
-
.

l ies in solution is re l ly the

combination of the H and OH ions to form water and hence the
heat of the reaction is practically the same for a
,

ll acids and
alk a li es The s a
. l t io n s remain ionised and only actu a l ly com ,

bine when the solution is concentrated

Sa
.

lt hydrolysis — Water ionises to a very minute extent into

-
.

H+ and OH only about 0 1 grm per ton being ionised and its
'
.
, ,

ionisation constant is 1 2 x or slightly over one ten millionth

norm a It might be s upposed that so sm a
- -

l l l an ionisation might
be neglected but in the case of s a
.

,
l ts of acids or bases of which
the ionisation constants are so low as to approach this figure
the results are very important Carbonic acid for instance is .
, ,

such an acid and many of the amino acids present in proteins

come into the same category though their s a
-

l ts with strong bases

ionise freely Sodium carbonate thus ionises into Naand CO3
,

+ ”
. .

When the CO3 comes in Contact with the H+ ion of t he water it

at once co mbines with it to form a l most unionised H 2C0 3 and ,

so goes out of the equilibrium and further water is ionised t o ,

restore its H concentration to the old amount , and this process

4r
1 02 P R I N C I P L E S OF L EA TH ER MA N UFA C T UR E

is repe a ted till the acid reaches such a concentration that its
ionisation is equ a l to that of the water During this p rocess
the OH and Na ions accu mulate in electric equilibrium and as
.

al ka
,

l inity is due to the OH ions the solution becomes strongly ,

alkaline A similar resul t occurs with a little ioni sed base such
.
‘

as alumina and a strong acid the H ions accumulate and the ,

a
so l u t io ii becomes strongly acid as in the case of aluminium
sulph te altho ugh in both cases the salts are chemically norm a
,

,
l .

The salts of s trong acids with strong bases are not

perceptibly hydrolysed and so whether methyl orange or phenol
”

phth a l ein be used as indicator the change of colour is practic a

,

l ly
“

simul t aneous and so soon as sufficient aci d is added to neutrali se

the base the solution becomes instantly alk a
,

l ine but with ,

weak acid s or bases t he change of colour i s very gradual

"

and there is a
,

i wid e interval between the two indicators which in

,

former times was supposed to show that the combination was

not chemical and that there was no definite point of saturatio n ;
-
“

or such ideas as that of a series of valencies successively neutralised

a
w s adopted to account for it Th e simple reason is that owing
to s a
.

l t hydrolysis the increase of H+ or OH concentration is

1 ’
-

1
Th e a
m ount of h y d r o l y s is m y b e d e d u c e d f r o m t h e m ss l w n d t h e a a aa
a a
-

a
id ad b a
io n is t io n c o n st n t s o f t h e s u b st n c e s c o n c e r n e d b u t e x c e p t fo r m o n o
a t a
-

f w hi h i w a
,

v l en c ly s n k it b se s , m on y m one o c s e eco es ve r co

p li a t d ad t h a d t t h la p hy i a
,

d i f b k l h mi t y
‘

c e n e re
g er s r e err e o e r er oo s on s c c e s r

b th a id a d ba a w a a
.
,

Wh ere _ o k th
c m t nf hyd l y i i se t re e e o un o ro s s s no

a ff t d b y d il t i
e c e b t i th im p l u a f ly on, w au k m n a l t e s er c se o on one e onov en

aid b a it f l l w t h a
c or m d il t i
se la w ai ni a
o o ti s (p e s wh i h e u on s o s on . c

ma q a
m 2

wh l m
’
y b p e d by thex ti k
r e sse i th e e u on 11 ere v s e vo u e,
m 1

m th p p ti e f hyd l y i t
ro or t h wh l
on w hi h i t a
o k a ad k
ro s s o e o e, c s en s 1 n
’

ahyd l y i ta i a ta t k b t b a
,

ro t d iff t f m th i
s s con s -
ti — n er en i g ro e on s o n con s n u e r n
, ,

la t o it t h a k i t h i ni a ta t f t h wa
5w wh
’
th e re ti t k on ti k , ere s e o s on cons -
n o e e

aid b a ad kw t h a f wa
—
c or t t
se , Xn Th if t h h y d l y i o er, Io 1 4
u s, e ro s s

ta i a ta t ab a la t d f m it ad
.

cons t i k n w th i s ti no n, l e on s o n co n s -
n c n e c cu e ro ,
n

a ( Cp p m ay p a I
:7
i
v ce ver s . F p . t h i
,
m p l f m l or— n ur o se s e s e or u ,
-
,
_
i

h y d l y ed ( t h wh l b i g t a
17
or 1 —m — wh m i th p p ti , er e s k e ro or on ro s e o e e n en
95 3

au it y) , t h hy d i t a ad k it h t h
'

th i i ti
t at am a
s n x e r on or o er o n c co n cen -
r on, n e er e

ion s i a ti t h hyd l y i
on or y b
e q i d i m ro s s co n s n s e re u re s ore co n

ly a th
-

i t ad i m a q a
,

v en e n n f m s f th m ere ti ( C1 A p p B )
no er or o e s e e u on )

ap id l y a t fi t ad g a d a ta
. . . .
,

Th i
e c u r ve r s e s lly b
r m h iz l ly rs n r u es or on on
e co

ah i g t h a it y a t a
, ,

re c n l f t i fi ite v ti
ue o b t if t h h y d l y i
un n n e co ncen r on u e ro s s

t at i k it y a b a la y a im a
,

co ns n w s lno t d n unpp t ly
c ti n e c cu e or ver ro x e es

ma pa ta
, ,

t d b y pl tti g
e p o If t h n t i
ou c ur vet it y i er e co n s n s c o rre c un s

a b ta
.
, ,

th e e
q i l tu v m b i i g w ig h t en f th co n n e o e su s nce .
1 04
“

PRI N C I P L E S OF L EA TH ER MA N UF A C T UR E

which Overcomes the difficulty by a very simple means I nste d . a

of two t ubes four are used in pairs one behind t he o ther in front
( o ft en aWelsbach gas burner ) In the two
,
v

o f a s uitable light

front tubes the l iqu or to b e test ed with its indicator a

-
.

n d the .
, ,

standard colo ur liquid are placed while behind the latter is a tube
of the un a
,

l tered liquor and behind the liquo r t ube with the ,

-

indicator is a tube of p ure water so that the colour of the liquor ,

is exactly b alanced .

With regard t o t he electrometric meth o d only the principle

can b e explained here a
c
,

nd for Working details the reader is referred ,

to other books
a
1
“

If we imagine two g lvani c cells b o t h ali ke say co nsisting of

a
, ,

copper in satu rated copper sulphat e n d zinc i n Z 1 n c sulphate

solution s of equ a
,

l concentration with their p ositive poles o p p o se d

‘

to each other and their negative a

,

l so connected there will be

, ,

obviously no current produced b ut if the zinc sul phate solutions ,

are of unequal concentration a current will be set up in such ,

a sense than zinc will be dissolved in the weaker solutio n till its ’

osmotic pressure and concentration beco mes equ a l to the ot her ,

that is a positive current Will pass from the anode of the weaker
,

a
to that of the stronger cell until e quihb r iu m is restored It is ,

obvious th t the energy which pro duces this current is the

di fference of ionic osmotic pressures a nd as the relation ,

between these two forms of energy is known the electric pressure

/

,
”
or potential can b e calculated from the ionic concentration
or vice ver s a
,

In our particular case it is the 1 0nic concentration of t he H +

ion which we have to determi n e and clearl y if We could use a ,

plate of met allic H in place of the Z n we c o ul d acco mplish it by

a similar a rr a
,

n ge m e n t This cannot of course literally be d one

but it is found that if we b ubble hydrogen gas over a pl a
i
,

te of _

platinum co ated with platinum b lack enough gas is absorbed ,

1
B o o ks of f
re er e n c e at s o e l ec tr o m e tr i c m e tho d s O st w l d aL u t her fo r
at i a
-

l d ta d Sa
a m
.

pr c ilc f m e t s o 3 9 p 3 W e d
su r e en 0, 1 1 1 oo n

ad La f a y m wh a
.
.
, , , ,

n w d ib t h e e sc r i t b t
e t p
u se i o v er c o n ve n e n u so e ex e n s ve

a ppa a d ig d b y D Sa mi a f H t a
t r us d f th d t
es ne ti rti n or e e er n on o + co n c en r on

i p
n ad t a l iq
u er s Th
n a m a pp a a
nt i fig d ad d
uors ib ed i e s e r us s ur e n e scr n

i g Ea ti g ad D
.

W d b k oo
’
Ps oo on hi g f Ski u er n ( Sp n n r en c n o ns o n s,

O t wa i a t l a
, ,

Th im p l
e sb id g w i m th d de ib d i
r e ld L th re t e o e sc r e n s u er s e s

e q a lly a a
u t b t t b i g
ccur lf taie, d i t q it
u no i t e n se con ne s no u e so co n ven en

h ad l w ag d ad h a p a ppa a
,

t B f th C ld b g t f
'

o n e e ore t e r oo n c e r us ou e o o

L ip z ig Sad a pp a a i ma
.

K hl b y G iffi
’
o er, e t d n A ll
s t r us s e r ns n ex ce en

t a d ma y a l a p a ti a l w k ad
. .

di si
sc u f th s on o bj b l hi t
e su ec n n v u e n s on r c c or n

a f i di a ma
, ,

l th y b f d i So C mp t
’
so on t e u se o n c d o rs, e o un n r en se n s o e s r en us

da
-

La b a t i d Ca or l b g 8 9 9 (Ha
o re g p C p
e ha r s
g ) er , ,
1 0 eru , o en en .
 PH YSI CA L C HE M IS TR Y IN T A NN I N G 1 05

to make it behave like one I n place of the copper and copper .

sul phate we use mercury and a solution of potassium chloride

mixed with powdered HgCl ( c a l omel ) which is very diffic ul t l y ,

soluble and keeps the solution saturated as it is found that this

, ,

arrangement gives a still more constant electromotive force than

the cop per If w e imagine a pair of such g a
. l vanic elements
opposed to each other each composed of a similar mercury ,

electrode and a hydrogenised platinu m plate immersed in an

acidified solution we can see that these two solutions must be of
,

exactly equal acidity ( hydr ogen ion concentration ) if no current is - -

to be produced If instead of adj usting the solutions we measure

the potenti a
.
_

l ( or elect ric pressure ) between the two cells which

tends to produce a current employing a known hydrion solution,

in one cell we can calculate the concentration in the other

a
.
,

A still simpler W y is to measure the potential produced by a

single element consisting of a c a l omel electrode and a hydro
g e n ise d platinum plat e in the acid sol u tion having previously
determined the potential produced with a norm a
,

l acid solution ,

and this is the method now generally used s orensen has found
'

a
.

that the potential of such an elem ent with decinormal pot ssium
chloride solution and c a l omel in the negative and acid normal , ,

with regard to the ionised hydrogen in the positive cell ( corre

s p o n din g to P = O on the Sorensen scale ) is o 3 3 7 7 volt and as
’

the potenti a
H , ,

l rises with the dil utio n of the hydrion solution the

potenti a l for a
,

n y given dilution is P ot = o
‘

— P “
or conversely 1 9
at 1 8 c
°

a
J
, , .

0 0 57
-

7
The Log r ithmi c the expression
Exp r ession N m —4 P M
f
o u bers

of ordinary numbers such as we use in everyday life the ordinary

, ,

A rabic notatio n is sufficiently convenient but when we co me to ,

deal with very large or very small numbers as is frequently ,

necessary in science it becomes very cumbrous It is much

a
.
,

shorter to wri te 1 0
9
than n d it means

quite the same thing and if we are to accumul ate debt at our
,
'

present rate we may have to adopt it Th e explanation of the

expression is quite simple— I o mul tiplied once by itself ( its z u d
power) is 1 00 I O multiplied six times by itself is a mil lion and ,

so on and the exponent 9 used in the illustration means that

,

nine o s have to be affixed to I to express it in the ordinary way

’
.

Wh at is rather more puzzling to the non mathematical is the -

—9
expression I o but it is really equally simple A minus ex
,
.
'

I OOOOOOOOO
I o6 P R I N C IP LE S OF LEA TH E R MA N UF A C T URE

that is the I ( or the first significant figure whatever it may be) is

,

in the 9 t h place of decimals .

In Sorensen s exponential or l ogarithmic notation P 3 means

’

, H

that the divisor of a solution normal as regards hydrogen ions -

a
.

= m
i

or c o n t i n in g I e
q I g r of ionised hydrogen per liter
. is 1 0
3
.
,

or I OOO or that the solution is N/I o o o and so on A s however

, , .
, ,

it is in convenient to have to prefix a multiplier say I 5 X 1 0 to 3

signify a N I 500 solution the fraction a

, ,

l power of I O which equals

‘

, ,

I 5
-
or in other words the B riggsian or common logarithm is
, , , ,

used and we wr ite P 3 1 8 0 1 8 being the log of I 5 Thus the : 4 -

‘

exponent of the 1 0 is simply the index of the log and the decim a
, H ,
. .

ls .
,

are the mantissa .

Th e following short table giving the number from I to 1 0 and

the m a aof the corresponding loga
n t is s a rithms w ill be sufficient
for the conversion of the Sorensen exponenti a l scale into the
divisors of normality :
Numbe r I 2 3 4 5 6 7 8 9 IO

Logarithm 0 3 0 0 48 0 6 0 0 7 0 0 7 8 0 90 0 95 1 0 0 - - - -

a
Hydr ion concentrations of both hydr io n s
-

con cen t m tion s .

—
Th e
and hydroxyl ions in pure water is bout I I x at and on
the exponenti a each equ a
-

l scale P and P l 7 0 7 and this is

t he point of t r u e n e u t r a
-

H ,

l it y and s olutions o i a greater I? are

'

alkaline Th e ionis a tion const ant of water la

H
.

w is the p r o du c t of
or on the exponenti a l s ca
-
.

—1 4
these and about I 2 X I 0
,
l e 1 41 4
-

, ,
,

since the addition of exponents or logarithms 1 s equivalent to the

multiplication of their ~numbers ; and this product is constant
in water and a ll dilute solutions Consequently if we raise the
concentration of hydrio n s to norm a
.

l ity by the addition of acid

that of hydroxyl ions wil l fall to zero and vice versaif we add
,

a l ka
-

li Since the determination of h ydrio n s is much easier and

.

more exact t han that of hydroxyl i 0ns it is customary to express

both acidity and alkalinity as hydrion concentrat ion but the va
-

l ue -

of P c a
,

rt always be found by subtracting P from 1 4 1 4 ( or for

ordinary purposes from I 4) The convenience of the exponenti a
H

l .

scale is obvio u s in practice since when we come to very great , ,

dilutions it is rare that we can attain to much greater accuracy

than to say whether we are de a
,

l ing with millionth or 1 0 millionth

dilution .
1 08 PR I N C IPLE S l
OF L EA TH E R MA N UEA CT UR E

caused by the collisions of the molecules of the solvent in their

1
heat vibrations: -

Th e suspended particles though in constant moti on are pre , ,

vented from actual contact by electric charges which being of , ,

the same sign cause them to repel each other and prevent their
a
,

coalescence but the additi on of an electrolyte such s common

salt to the solution causes their discharge and the sol coagul ates ,

and precipitates This is probably du e to the electric adsorption .

of t he ion o f o pp o sit e charge to that of the particle and as a rule

‘

, ,

the higher the valen cy o f this ion the greater the precipitating
effect A dd itions of very sm ll quant ities of certain colloids
. a ,

mostly proteins greatly lessen or even p revent this precipitation , , ,

and are hence called protective colloids Of t hese gelatin .

is perhaps the most powerful I mgr protecting a liter of gold , .

sol from the precipitating effect of a large quantity of salt ,

probably by coat ing the particles The precipitates from sols are .

often called gels but t he term must not in any way be c on ,

founded with jell i es which have quite different properties The , .

addition of small quantities of protective colloids greatly favo urs

the formation of colloid sols and the presence of gelatin has this ,

effect in the preparation of photographic emulsio ns .

While electrolytes in quantity rapidly precipitate sols the ,

presence of traces seems essential to their fo rmation probably ,

because ions are necessary to give the electri c charge A colloid .

solution of ir o n o x id e in water is obtained by dialysing ferric '

chloride through a parchment —paper membrane through which ,

the iron oxide will not pass while t he hydrochloric acid produced ,

by the hydrolysis readily doe s so but however long the process ,

is continued a trace of C1 is always found in the colloid solution

, .

This s olution has been used as a tonic under the name of Fe r

B rav ais and is quite clear and of a dark brown colour but
, , ,

1
ami
Th e p i it
ult r ig i a
-
l ad t il l m t p f t f m
c r o sc o e n s or n n s os er ec or co n

i t d f a gl a i d d ta
, ,

s s e o ll th ss s
g f t h mi
-
e
p t h l iq id i wh i h
ce on e s e o e cr o sc o e, e u n c

wab il l ia s t l y i ll m i a
r t d by a
n t hi fla t h iz
u ta l b a n m e t at d n, or on e co ncen r e

it b y a p w f l ad a a t ly a
,

on o dj t d
er u d A t h t hi k
n c cur e us e co n e n s er s e c n e ss

f th b a m wa a it w ap t th pa i a
.

o e e tly k w ib l t
s ex c ti l no n, s o ss e o coun e r c es n

k no w l m n f l iq id
vo u A m h im p l
e o b t l q a u t it ati m th d uc s er , u e ss u n ve e o

t a a gl a a di ay
.

i t
s t t h l i g h t i t h l iq i d
o co n cen r d
e e n e u un er c o ver ss o n n or n r

by a b ta t ha
-

s l id e g d su f e y wid agl
s e con t t h b il l iat l y
en s er o v r e n e, so e r n

ill m i a
u t d pa n ti l ae ap f t l y d ak g
r c es d i th
re se en t on er ec r roun s nce e cen re

i da d ad t h l igh t i p j t df m a a
,

o f th d e con k e n s er s r ll id
en e t n e s ro ec e ro s es

h aagl t h a a t p a t h gh t h gl a a t f
,

su c n t it n e c nno ss ro u e c o ver= ss o n cco un o

t tao l fl ti re P ba ecb ly th b ton f th i th Z iro ad i id e es o e se s e e ss c r o con

m ay p p ag d p aa aw w ll ad
.

d e n s er ,b t f u or b l id n ur o se s oo r o o ns er s e n

m wh a ai t m aip l a Th il l m i a di a y da
,

is so t e t e s er ti f
o n k u e . e u n on o or n r r

g r o u n d c o n d e n se r s is in su f fi c ie n t .
C O LL OI D SO L U TIO N S A ND C O LL OI D S TA T E 1 09

is extremely unstable being precipitated immediately on heating

, ,

or even on dilution I t is highly probable that colloid solutions

of alumina a
.

n d chrome oxide might be produced by similar means ,

and the subj ect will be again al luded to in dealing with chrome
and with the theory of tannage
Ma tual P r ecipit a t io n of oppo sit ely c ha
.

r ged C o ll o ids — I t has

been stated that the colloid particles have electric charges prob ,
;

a
ably from attached ions and that th e repulsion of these similar
'

a
charges prevents their cont ct If however a colloid sol of .
, ,

ch rge be mixed with one of charge the particles attract each ,

other and produce mutual precipitation and if the quantities ,

are electrically equivalent t he p recipitation may be quite com

,

p l e t e but if one or other is in excess neither is usually completely

, ,

separated I t is probable that t he precipitation of gelatin by

.

tannin is an instance and in this case if the gelatin be in excess

, ,
“

a p ortion of the tannin remains dissolved Many dyestuff s are .

a
coll oidal and we know that basic dyes are constantly precipitated
,

b y acid ones . I t is hard to make ny distinctio n between such

reaction s and those which are strictly chemical since both are ,

due to the combination of and ions but t h e colloidal charges ,

vary with the size of the particles and thus are less definite than ,

those of single ions

Ka ta a —I f a
.

ph or e s i s n d E l ec tr i c Os mos e n electric current be .

passed through a colloid sol t he charged particles will move

,

towards the pole or anode and the charged towards the

,

pole or k athode that is to say towards a region of higher electric

‘

, ,

charge of the sign opposite to their own A rrived at the pole they
usu a
.

llv b ecome discharged and often form a clot of precipitate

, ,
,

but cases are known where they take fresh charges of the opposite
sign and return t owards the other pole sometimes meeting a nd ,

precipitating oppositely charged particles midway The particles .

thus behave precisely like the ions in electrolysis and of course ,

like them possess an electrolytic conductivity though a small one , .

Electric osmose is the converse of kataphoresis If a cel l is .

divided into two compartments by a porous partition with an

electricall y charged surface ( as for instance earthenware , , ,

powdered glass bladder or parchment paper) and a current be

passed through the liquid will flow through t he p a
, ,

,
r t it io n in the

opp osite direction to that in which the material of the partition

would have moved if it were in the form of suspended particles ,

and if it cannot escape will rise considerably above the level of

,

the side from which it flows This effect explains the theory of .
‘

electric tanning so far as it has one If an alternating current .

is used there will be no steady flow but merely a vibration ; ,

I I o PR IN C IP LE S OF L EA TH ER MA N UF A C T URE

and if a continuous the process is complicated b y electrolytic

'

decomposition and indirect destruction of tannin

, .

Kataphoresis is important as being the simplest mode of

determining the sign of the charge on suspended particles The .

experiment is usually mad e in a U tube If the particles are not -

visible to the eye their concentration in the two limbs of the tube
,

is determined by analysis The following table gives the sign

i
.

of the charge on a few of the commoner colloids The charge .

is often reversed in ac id and alkaline solutions and with ampho ,

teri o bodies changes at the iso e l e c t r ic point ( see p I I I )

'

. .

P ositive Solutions Negative Solutions

( to kathode ) .
( to anode ) .

H ydroxides Met a
( of l s ( Au A g Pt P d I r Cd )
Fe ,
Cr ,
Al , , , , , , .

Cu Metallic sulphi d es
S ome met a Silver h a
.
,

l s Pb Bi F e ,
l ides
, , .

( prob ably hydroxides in water ) P roteins in alkaline solution . .

P roteins in acid solution Silicic acid in alkaline solution . .

Silicic acid in acid solution Starch mastic caramel resm .

, , , ,

shellac .

I odine sulphur s e l e n 1 u m tel , ,

_
,

l u riif m .

Oil emulsions .

N a l O ga
t a i
ur C o ll oids — These proteins gums a
r n c nd the like
are now frequently styled emulsion colloids on the a
, , ,

ss u m p -

,
:

tion by no means proved that their apparent solutions are fine

, ,

emulsions o f one liquid in an other They have many analogies .

with the suspension colloids but also marked differences and it

is not unlikely that their colloid chara
-

, ,

c t er arises from quite

different causes They all have large molecular weights and
.
,

a
mostly a tendency to polymerisation ( the grouping of several
or m ny molecules together) a n d their solutio ns have large

a
,

viscosity and not unfrequently t ke the form of c onsistent j ellies

a
,

( not gels ) T heir solutions are not precipitated by small

.

quantities of electrolytes n d the salting out which occurs ,

when some salts are added in large quantities is probably quite a '

different phenomenon Their solutions generally show at least ‘

traces of reflected light ( Tyndall effect ) when a powerful be am is

passed through t hem but it is only rarely that separate particles ,

can be detected by the ultra microscope and these are possibly -

accidental impurities Many of them especially the proteids .

, ,

are amphoteric or capable of ac ting both as acids and bases as

, ,

will be readily understood from their chemical constitution

( see Cha p ter X L) T heir molecules or particles .possess electric
I I z PR IN C IPLE S OF LEA TH ER MA N UF A C T URE ‘

solution ,
'

as to allow some colloid particles to pass while retain

so

ing others Fo r details the original paper must be consulted

Fra c ti o n a
l pr ec ipit a
. .

ti o n is another means which can sometimes

be employed with success for the separation and purification of
colloid solutions Sulphates of ammonia o r soda are frequently
.
'

employed for this purpos e If added in sufficient quantity the

whole of the really colloidal constituents may be flo c c u l a t ed
a
-

n d se p arated generally carrying down with them some non

,

colloidal matter wh ich may be removed by r e solution and r e

,
-

precipitation I f the quantity of the precipitant added be in

.

s uffic ie n t to precipitate the whole of the c olloids the first “

a
precipitate will be mainly of t hos e most easily dehydrated ,

while those with a greater ttraction for water can be brought

down by a further additi on of the salt Oi course neither of .
_

t hese fractions is a pure individual proteid but this may be ,

app roached by repeating the operation perhaps with a less or ,

different addition of the salt The p recipitation seems t ob e .

one of simple dehydration and the salt retained in the precipitat e

,

may be removed by dialysis The theory of this salting out .

is somewhat uncertain I t is possible that it is due to the hydra

.

tion of ions withdrawing the water from its function as a s olvent ,

or that the j ellies though p ermeable to th e ions are not so to

, ,

the unionised salts t h e osmotic pressure of which t herefore

,

express es the water from them j ust as in the case of dehydration ,

by alcohol which does not i onise t o any extent P roteins are

,
.

usually in solubl e in water at the isoelectric point .

— Many o rganic colloids re m ain in more or less viscous

J el l i e s

solution even at low temperatures b u t others i ncl uding gelatin , , ,

set to a more or less coherent j elly on cooling Much discussion

has taken place as to t he p hysic a
.

'

l structure of these j ell ies the

a
,

earlier school of colloid chemists holding with B ut s chl i and v n

B e m m e l e n that they had a sponge like structure with open pores -

which might even be made visible under the microscope while ,

the adherents of the e m ul sio n t he o ry of organic colloids have ~

held that they consisted of globules containing water ( or some '

other solvent) separated b y a liquid consisting of a weaker colloid

solution I t has however become evident especially since the
.
, , ,

work of the writer on the gelatin equilibrium with acids that ,

neither of these th eories can be maintained at least in their ,

original form and that the net like structure if it exists cannot
,
-

, ,

be of more than molecular dimensions since the whole mass is in ,

chemical equilibrium with the surrounding solution and must ,

therefore be within the sphere of molecular attractions The .

prevailing idea at p resent seems to be that of a network of mol e

C O LL OI D SO L U TIO N S A ND C O LL OI D S TA TE I I 3

cules possibly crystalline From Chapter X I it will be seen that

, . .

these molecules are probably long chains of amino acids which -

would lend themsel ves to such a structure Jellies also present .

striking analogies in their behavi o ur with external solution to

that of two immiscible solvents with a third substance soluble .

in both and p robably the safest position is to regard them as

,

solid or semi —solid solutions without theo rising too much at

,

1
present as to their ultimate structure .

I n the following p ages attention will be particularly directed to

the gelatine j elly not only because it specially interests us by its
,

close relation to skin but b e cause it is typical of mo st other ,

gelatinising colloids A solution of gelatine heated above 7 0 C .

°
.

undergoes chemical changes which gradually diminish its setting

p ower which after continued boiling entirely disappears but

a
, ,

below 7 0 the change from solid to liquid seems quite rever

°

sible A solution of good gel tine at 70 shows few or no ultra

.
,
°

microscopic particles and only a very slight Tyndall effect , ,

and may well be an actual solutio n of large m ole cules A s it .

co ols both the Tyndall effect and the viscosity increase but only
, ,

slowly owing to the sluggish motion of the particles and it is

, ,

often some days before the full effect of a given t e mperature is

a
reached A s the temperature nears the setting point the rise
.

of viscosity is much greater though even fter complete setting ,

the firmness of the j elly continue s to increase for many hours or

even days The viscosity near n d below the setting temperature
. a
seems to be of a different type to the ordinary frictional viscosity
of h igher temperatures and is apparently due to some sort of
a
,

structure s it is diminished by vigorous stirring or even by

, ,

passing through an ordinary capillary viscosimeter 2

Solutions .

so dilute as to be ap p arently quite liquid below the settin g point

still show these effects and a
i

d is c suspended in the liquid by a ,

torsion wire will only move a short distance and take up a per
manent position at a slight torsion Such liquids also s how the
dip o l a
.

r isin g effects of strain in the polariscope if examined in the

annular s p a c e b e t we e n a fixed and an interior rotating cylinder

1
a gai b t a whi h l t im a
Ce r t in or n c t ly f m ma
su s n cesf dl c u e or ss e s o n ee e

y ta l ta k a t fi t a ad ma
.

l ik j l l y l ik d it i f
a id a
e cr s s e rs e y e co n on, n even ss e s o cr s

ta a ha
-

lli nelt ft
s s bl
ve o m b l a t j ll i
en G la
co ns ti er e r e se n ce o e es e n

a b y ta a p a ad m b ha
.

c n e lli d b ycr y l ws se ti v er s o ev or on , n so e o se r v e r s ve

no t d e mb la t t h a
re se d lik y ta
n ce l i tho lt a mi
re p S a p e cr s s n e u r c r o sc o e o s

l ka a f fatty a id a
-
-

b t aa
.

f m
or y d id d j ll i
ve r ec eli e lt e s, ud d id d l yre ne s s o c s, n ec e

cr y ta ll i
s ne

g a b t a
.

2
Op A i K ll id h B i h ft 7
r sz o 9 5 l
o c e in t i e e e, I 1 1 on s r c n

h a t i g ad
.
, .
, , ,

A i r sz d ib m i
e sc r lt i
es so e cur o u sli g l id j llir e su s n e n n coo n so e es ,

b ut at h s ta
i d gl y i
e se co n it i d iffi ne lt t d a w l i
cer ne , s cu o r c o n c us o n s .

8
 P R I N CI P L E S OF LEA THER M A N UF A C T URE
“

I I 4

( Kund t ; Wi ecl Ann which is quite

88 1absent “

.
p .
,
1 ,
I 3 , 1

in much more viscous li quids such as glycerine and sugar

syrup th ough it is sh owri by fatty oils
a
.
,

I f we place a sheet of dry gelatine 1 n water it swells b sorb ,

ing perhaps seven or eight times its weight of water but does ,

not appreciably dissolve A condition o f equilibrium is reached .

when t he osmotic pressure within t h e j elly is equal to the s um of

the c ohesive attraction of the gelat ine for it self and the osmotic
pressure of the water outside An incre a se of the cohesion of the
gelatine wo uld tend to ma
.

a
ke it contract and expel part of the
‘
“

water n d this co ntraction w ould tend further to increase the

,

cohesion of the gelatine The equilibrium is therefo re a very

'

unstable one and slight causes might be expected t o produce great

,

changes i n the degree of swelling which 1 5 indeed the case I f we , .

increase the temperature we diminish the cohesion o f t he gelatine

a
,

till at a point it become s les s th n its attraction for the water -

,

and the j elly suddenly l o se s it s solid conditi o n and dissolves “

'

Th e mel ting point of good g e latine v a

-

ries somewhat but 1 s usually ,

between 2 5 and 3 0 C With glu e s and inferior gelatines it is

° °

often much lower owing to th e pres ence of g e l a

.

t o s e s and forms a ,

useful t est of commercial quality

The absorpt ion of w
.

ater by dry colloids ( inclu ding gelatine) is _

.

'

accompanied by contraction o f volume ( compression o i the '

wa ter absorbed or of the colloid itself) and by evolution of heat .

,

and as has been pointed out by Korner it is opposed by increase

,
1
,

of temperature but at the same time the cohesion of the j elly is

,

decrease d whi ch favours swelling Solution on the other hand

a
a
, .
, ,

absorbs he t and is therefore favoured by rise of temperature

, .

Th e problem is therefore very complex n d the actual result ,

probably varies with the degree of hydration of the j elly

I f we place the swollen j elly in alcohol it parts with w a
.

ter
a
,

n d c ontracts Th e gelatine and alcohol are not mutually

soluble ; the sum of the attraction of water for alcohol a
.

n d the

cohesive attraction of the gelatine is greater than the attraction

'

of the l a t t e r fo r water and as the alcohol cannot pass into the

'

a
,

gelatine the water passes out and the j elly contracts The
, , . .

greater the concentr tion of the alcohol; the more completely

is the j elly dehydrated and in strong alcohol it may become
'

quite hard and solid This method of dehydration was adapted

by St ia
.

s n y for estimating the water content of pelt I f we like to .

express the same facts in language more familiar to the modern

chemist but perhaps less clear to the non—chemical reader we may
, ,

say that the alcohol exerts an osmoti c p ressure outside the

1
a
B e i tr g e z ur wiss e n s c h a
f tl i c hen a
Gr u n d l g e d er Ger bere i , F r e ib e r g ,
1 89 9 .
1 1 6 P R I N CI P L E S OF L EA THER MA N UFA C T URE

detailed chemical constitution of gelatin e is as yet uncertain

a
“

but it is known ( see Chapter X I ) to consist of chains of mino .

acids linked by the carboxyl of one to an amino group of the -

next l e a
,

vm g an ami no group NH 2 at one end of the chain and a

,
-

carboxyl ( COOH) at the other H ence hide fibre absorb s both .

acids and bases with great avidity so much so that the sulphuric
a
,

acid of de cinormal solution may be c ompletely removed by hide

leaving only wa
,

ter without a trac e of acid recognisable by litmus .

a
A lkalies are absorbe d in a similar way and in both cases the ,

gel tine or gelati nous fibre acquir e s a greatly increased power

of ab sorbing water and consequently of swelling Familiar ’

cases of this are the swelling of hide b y acid a

.
,

n d by lime and in

a
,

n either c ase c n the added substance be removed in any reason

“

a bl e t im e by mere washing with water

_ H ence to free hides from
l ime or acids it is necessary to n eutralise the alk li with acids
'

a
.

a
( see p 2 0 3 ) or the acid with chalk or lkalies ( p
.

If hide or skin previo usly swollen with acid be placed m ,

strong sol uti o n of co mmon s alt it is dehydrate d and the swelling

"
.

,
a
co mpletely reduced and as in Knapp s experiment with a
,
'

l cohol
’

it is converted into asort of white l eather which however

, , ,

swells again strongly if plac ed in wat er This is the caus e of .

pickling which is describe d in Chapter X V: A similar acti 0n

a
,

takes place with acid gelatine which becom es quite hard n d'

horny .

When dry gelatine is plac ed in water it absorbs it with great ,

avidity at fi rst but afterwards m Ore slowly forming a j elly

, , .

Dr y hide behaves in the sam e way ( though the j elly is one of

collagen and not strictly of gelatine) so that the fibres of wet
, ,

hide are threads of colloid j elly Water i s also absorbed by the

a
.

a
hide between the fibres by capillarity .

It may be taken s fully proved that gelatine acts as b ase

with dilute acids form
.

ing a coll oid salt which ionises into a

,

colloid kation and the anion of the acid and which hydrol yses
with excess of water back to gelatin e and the origin a
,

l acid so ,

that the base can only be ful ly sat urated in presence of excess of
acid and an equilibrium is formed dependent on the Ht con
,

centration of the acid which determines t h e p r o p o r t io n of u h '

combined gelatine and of free acid to that of s a t ur a

t e d g el a
,

t in e
'

salt A s the latter ri ses gradu a

'

. l l y with the concentration of the

acid there is no point of neutrality to indicators a fact which led
,
-

earlier chemists to deny the existence of a definite compound .

1

1 T a
B r il s fo r d R o b e r t s o n in h is b o o k on t he a
P hy s i c l C he m i s try o f
a ad N a a
.

Co l l o i d s ( L o n gm ns, Lo n d o n n ew Y o rk, 1 9 1 8) d m it s t he lt f s o r m in g

a a
-

ch aat r c er o f p r o t e in s , b u t b e l ie v e s t h t i t i s not t h e t e rmi n l ami no ad

n
 C OLL OI D S OL U TI ON S AN D C OL L OI D S TA TE 1 1 7

The point of saturation can however be determined by calculating

the in fin it y va
, ,

l ue of a plotted curve
-
.

If we place gelatine in dilute acid ( say N[ 1 00 HCl ) it swells much

-

more than in pure water under favourable circumstances to fifty ,

times its original weight thou gh as the acid concentration is

increased beyond certain Op timu m point the swelling steadily
diminishes in a sort of hyperbolic curve the greatest swelling
a ,

,
.

being obtained with acid of H+ concentration about P

'

With pure water it only swells to seven or eight times its origin a
H

l
weight .

It must be understood that every mass of gelatine j elly or every

gelatinous hide fib r e in an acid solution of any definite strength
-

is in equilibrium with the surrounding solution that is that it , ,

c ontains water gelatin salt free gelatin and free acid in such
,
-

, ,

proportions that there is no tendency for either acid or water

from the surrounding solutions to pass int o or out of the j ell y ,

though both can pass freely through its surface .

In applying these facts to the p roblem of swelli ng we may

.

simplify the t ask by neglecting the un ionised substances which ‘

-

in this case passing freely in or out of the j elly affect it only ,

indirectly and by confining our attention to the ions t hemselves

,

which are proved to be the real active agents .

.

Admitting the existence of gelatin salts we have to consider ,

t he e ffect of their ionisation on the swelling Th e gelatin ion

'

-
.

remains colloid that is it tends to agglomerate into masses or

, ,

large particles which do not di ffuse and consequently exert no ,

appreciable osmotic pressure so that the ionised salt still remains

a
,

a j elly or colloidal solution Th e anion in this case the Cl ion

on the other ha
.
, ,

nd tends to di ffuse and exerts osmotic p ressure

, ,

but cannot leave the j elly on account of the electro chemical

'

attraction of the gel ion It therefore swell s the j ell y thus draw -
.
,

ing into it the outside acid s olution This however contains t he .

, ,

hydrogen and chlorine ions of the ionised acid in equal quantity '
,

and while the former can en t e r t he j elly without hindrance the ,

latter are opposed by the osmotic pre ssure of the ionised Cl ’

already inside The results are that the acid which enters is less
.

c abr o x yl g r o u p s w h ic h a ti b t t h N H ad CO g
e n t er pin t o c o m b in on, u e n ro u s

a t th li k a
e g n f t h de ff o t a m i —a id w h i h f m t h p
e i t i
er en ad no c s c or e ro e n, n

t hat c o n se
q t ly t h u en l l id a lt i i i t tw e co l l id i ad d t
o s s o n se n o o co o o n s, n o no

h yd l yro It i p
se ib l t h a t t hi m a
s y b o sst f m th
e p t i s e ru e o so e o er ro e n s,

f a f g la t a t d a
.

o r e ve n o lt s ti s w it h m o e id th n g h it i t o re c o n cen r e c s, ou s no

i a
u n ver sll y a d m it t d b t i t i tai ly e t th a wit h t h m aid
u s c er n no e c se e on c

salt f g la
s o ti w it h w h i h w a
e n d at h hl id c f i ta e re c o n c ern e s e c or e, or ns n ce,

ta ad d h y d l y Th i i a
,

cer i ly d n i i Cl i
o es o n se -
l
o n s, fim d n o es ro se . s s so co n r e

b y t h e wo r k of J . Lo e b .
 1 1 8 P R I N C I P L ES OF L EA TH ER MA N U F A C T U R E
*

a
concentr ted than that outside that the total concentration of ,

Cl is greater and that of H f less in the j elly than in the outer

'
,

solut ion and as the acid H cannot enter without it s associated

,

Cl a layer of positive H forms outside the j elly surface opposed

,
' t
r
,

and balanced by a similar layer of negative Cl within Thus ’

.

the t w0 sides of the surface are in di fferent electrical condition

or in electrical language there is a potenti a
_ ,

,
l between them ,

( D onnan s M embrane P otential ’

and the surface layer
outside the j elly has a sm a
-

ll electric c harge If instead of

being acid the j elly a n d o u t e r solution were alk a
.
,

l ine say with

“

, ,

soda the gelatin being amphoteric woul d form a sodium

“

a a a
, , ,

l t i t i place of a gelatin hl id
‘

d the charge w uld be ’

g e n e n c o r e n o ,

negative instead of positive It i s obvious that between these . .

conditions there must be an isoelectric point of neutrality at

“

which there is no potential charge This does not necessarily . .

o ccur at the exact acid and alkaline n eutrality of water but is

dependent on the rel ative acid and alk a

,

l ine affi nities of the

in di vidual proteid In gela tin and hide fib r e it is slightly on
t h e acid side of neutra of actu a
-
,

lity PH = 4 7 or N l hydr ion

“

concentration and this is the point of minimum swelling and

greatest flaccidity of the skin and the gelatin is insoluble a
,

nd
'

neutral and on the acid side of t he isoel ectric point acts onl y as
,

a base and on the alkaline only as an acid With regard to the

actu a
,

a
l t nning process these charges are also of the highest
importance as negatively charged tannins can only combine with “
,
.

positively charged hide .

Th e osmotic pressure tending to swell the j elly is therefore a . .

balance of two opposin g forces that of H+ pressing in and of , ,

Cl ( or some other acid ion ) pressing out D onnan has shown

'
-

that when t he jell y and its outer solution are in electric a

.

l and
‘

chemical equilibrium the proportions of the two are connecte d

by the law that the product H+ multiplied by the Cl within
,

the j elly must equal that of the Cl of the outer acid No w ’

.

the H and C1 of the outer acid are equal while in the j elly C1 is in
excess and the sum of equal s is a l ways less than that of unequ a
,

, ls
which give the same p ro du ct Thus the sum of is 8 t hat of .
,

is 1 0 yet both give the p r o du ct 1 6 Since the osmotic

pressure is proportion a l to the s u m of the ions there is thu s a
, .

l ways ,

a slight osmotic force tending to swell the j elly greater as the two ,

factors are more di fferent The greatest difference occurs when .

the quantity of free acid is very small and the chlorine in the j elly
is a l most entirely due to t h e ionisation of the gelatine s a l t and it ,

n a
Do n n a n d Ha
rr is Do n n a
1
n Z e i ts E l ec tr o
.
, 99 , 1 9 1 1 , 1 554 .
, .

f .

c he m .
, 1 7 , 1 9 1 1 , 57 2 . A b st . 1 00 , 1 9 1 1 , 8 48 .
1 20 P R I N C I P LE S OF L EA TH E R M A N UFA C T UR E

a
of so simple a character that it may be gi ven l n detail To avoid .
,
-

complications c used by the liqui d capillarily retained bet ween

the fibres o f actual hide thin sheet s of the best French bone
gelatine were mostly employed but the same met hods c a
,

n be ,

applied to skin itself wit h very approximate results and as it is ,

desirable that these should be extended the writer woul d welcome

any c o operati ve work of a n accurate char a
,

-
cter The earlier
_
‘

experim ents were only i ntended as preliminary and Coignet s ' ’

a
,

gelatine was used without further purific tion b ut in the later

work it was carefully puri fied so as to be a
,

l most ash free by ,

-

slightly acidifying with 8 0 2 to remove calcium sulphite and

pho sphate and then Washing fo r some d ays on nets with many
,

changes of distilled water This gelatine however must have

retained sm a
.
, ,

l l quantities of alkali since its P in aqueous solution , H

was 5 5 instead of 4 6 whi ch corresponds to isoe lectric gelatin

, .

It was not found however that this had m uch influence on t he , ,

determinations sm c e any traces of salts we r e p r e t t y thoroughl y

,
‘
‘

re moved by the considerable volu mes of dilute acid e mployed in

the experi ments A s gel t in cannot be dried at a high tempera
“

. a
ture withou t materially affecting its solubilit y air dry gelatin
“
‘

wa
- -

s p reserved in a stoppe red bottle and moisture was deter

mine d by drying a po rtion at I OO C in va
,

cu o and this together

°
.
,

with the traces of ash were allowed for i n the wei ghings P ortions

a
.

of 1 grm were weighed into wide mouthed stoppered bottles

.
-

and 1 00 c c of acid of accur tely determ ined concentration

. . .

was added and allowed to stand with occasional gentle shaking

a
,

for forty eight hours which w s foun d to be sufficient to obtain

'

practical equilibrium The contents of the bottle were then .

a
poured into a funnel fitted with a finely perforated porcelain
pl te covered with a clock glass and a l lowed to drain for two
a
"

, ,

hours into graduated cylinder The volume subtracted fro m

. .

1 00 c c gave that absorbed b y the gelatin any traces of moisture

. .
,

which the air dried gelatin contain ed being negligible against-

unavoidable losses by evaporation and liquid retained on the

surfaces of vessels The quanti t y was a l so d e t e r m in a
b l e as a
'

check by weighing t he swo l l en j elly The co ncentration of acid

’
'

in the cylinder with which the j elly was in equilibrium was , , ,

determined by titration with sodium hydrate and phenolphthalein

a
,

and that absorbed b y t h e gelatin w s calculate d We thus

'
“

ascertain the total acid absorbed by t h e gel a

.

t in and the volume

‘

of the swelling p roduced The absorbed acid is not however

entirely combined chemically with the gel a
.
, ,

tin but a considerable ,

portion exists as free acid imbibed m the swelling and the pro ,

portion of this to the acid actually combined was still to be deter

COLL OI D S OL U TI ON S A N D C OLL OI D S TA TE 1 21

mined To accomplish this advantage was taken of the fact

.
,
-

that the addition of neutral salt while it reduces the swelling , ,

and expels the merely absorbed acid does not affect that actually ,

combine d with the g elatin The swollen j elly was returned to

the wide mouthed bottle and co mmo n s a
.
,

-
l t was added so long ,

as it wo uld di ssolve A fter standing at least twenty four hours .

-

with repeated sh aking equilibrium was again established and the ,

j elly was reduced to a horny mass retaining only about 1 5

of the solution The acid present in the expelled s a l t solution
.

was again det ermined by titration and calculated to the whole ,

volume of the solution originally absorbed remembering that

of a saturated s a
,

1 00 c c l t solution only contain 88 6

. of -

water No appreciable error can arise from the assumption t hat

.

the small remaining quantity of acid solution remaining in the

j elly is of the same acid concentration as that expelled }
'
l

We have thus the means of determining ( I ) the free acid unab

sorbed which forms the extern a l solution with which the
j elly is in equilibriu m ( 2 ) the fre e acid absorbed by the j elly
and ( 3 ) t he chlorine ionised and non ionised combined with the ,
-

j elly base The sum of ( 2 ) and ( 3 ) can be further controlled by

the titration of the dehydrated j elly with alk a
.

l i hydroxide which
with phenolphth a
, ,

l ein as indicator completely decomposes the

gelatine s a
,

lt The t abl e in A p p B p 5 9 1 gives a series of

. .
,
.
,

such determinations with varying quantities of acid and includes ,

the whole of the results in the series of experiments to which

they refer which are more concordant than wo ul d be e xpect ed
,

from the comparative roughness o f the method ‘

In the di lute solutions used the ionisation of the gelatin chloride

was found to be complete or at least equal to that of the hydro ,

chloric acid which to simplify calculations was assumed to be

, , ,

wholly ionised and we were thus enabled to give numerical ,

values to the chlorion and hydrion concentrations both of the

j elly and of the extern a
,

l acid solution and it was found that ,

these so obtained by calcul ation agreed within experimental

, ,

error with those obtained by the direct titration of the total

hydrochl oric acid in each ( see p .

It is obvi ous that from the results of these experiments two

distinct series of c urves can be c a l culated : those of relative con

1
A s a
t a
t d ur e s o l u t io n of aslt at 5 C tai 6 4 g m
1 f a
°
lt p con ns 2 r o s er

ad h aap g f
. .

1 00 gr m or 3 1 9 gr m p er I OO c c n 4 A wi g s s r o 1 2 0 s, o n

a t b f ll y a a
. . . . . . .
, ,

to t h e p r e se n c e o f H Cl th e l ti so u on t t d w it h c nno e u s ur e

a
l t it i p b a tly a a a la
,

s b ly s ro fi
su f c ie n t f th p
ccur p f t hi
e l ti or e ur o se s o s c cu on

a m t ha ta ig i a
,

t o ts su e 1 00 cc . co n i 88 6ns f th -
l l ti o e or n so u on, or 1 00

gr m 73 6
-
.
,
1 22 P RI N C I P L ES OF L EA TH ER MA N UFA C T UR E

c en t r a
of the different constituents of the j elly and it s
ti ons

e quilibrium acid solution which have been discussed a nd a

, ,

second series dealing with the actual quantities of each associated

with I grm or 1 mol of gelatine from which the composition of
. .
,

the gelatine salt and the co mbining equivalent of gelatine can

be determined Wh en a strong acid combines with a strong
base t he p o in t of exact n eutr a
.

l isation is easily determined by

titration with a suitable indicator ; such as phenolphth a
, _

l ein ; but .

where either the acid or the base is very weak the salt hydrolyses
again to free acid a
,

n d ba se and c omplete saturation of t he one ,

can only take place in presenc e of an excess of the other Thus .

,

in t itrating gelatin with an acid there is no point at which the ,

indicator changes sharply and the whole of the gelatin is only

converted into chloride in presence of a large ( and theoretic a
,

l ly
an infinite) excess of acid a fact which led earlier chemists to ,

suppose that no definite c o mpound was formed From t he .

curves of concentration however we can determine the pro , ,

a
p ortion of gelatin chl oride forme d as the acid is gradually ih
cre sed in strength and watch its rise very rapid at first but
gradually becoming slower till it pproaches a horizont a a
, , ,
.

l line at
the point of compl ete saturation To thi s point we cannot push .

it since long before the acid has r eached the requisite strength
,

it begins to break up and diss olve the gelatin b ut if we can find

a mathematical expression which exactly reproduces th e part of
the curve which we can observe we can calculate the point at
which the horizont a
,

l would be reached A s the case is one of .

ordinary hydrolysis it is probable that it will be covered by

,
_

Ostwald s hydrolysis formula which for the purpose in View is

’

conveniently stated as i where x is the concentrat ion of the

x 13

external acid and h an or dinary hydrolysis constant In ad di tion

to k we have a
.
,

l so the molecular weight as a second unknown

“

by which the weight of 1 0 0 0 mgr actu a

, ,

l l y taken for the e x p e r i .

mental curve must be divided to bring it to mole cul ar proportions

a
.

B oth these might be found by simult neous equations from di ffer

ent points in the curve or by the approximation method described
in the original paper ( Tr a
,

ns Chem S oc ; 1 0 5 1 9 1 4 p The . . .
, , .

actual curve was ve r Y a a

t l Y re P
c c ur e r o du c e d bY y
x
x

x
x
1 000

83 9
Wt h represents gelat i ne as a d1 ad base W t h
c1 I
x +1 '
05

a second very weak affinity and a mol ecular or at least , ,

e
qu iv a
1 24 P RI N C I P L E S OF L E A TH E R M A N U F A C T U RE
'

isoel ectric point the gelatin combines direct with their anions ,

and on the alkali ne side with their kations but to the writer
it seems more probable that what takes place is me rely a double
decomposition a n d sub stitution of an element the salt for one
a
,

l ready in combination with the gelatin such as has j ust been

,

described.
 CHA PTER XI

TH E CH E M I S TR Y OF H I D E

C HEMICAL C ONSTITU TI ON
I n tro du ctory — A part from sm al l quantities of inorganic matter
and of pigment the chemic a
.

l constituents of hide belong to

,

that class of nitrogenous organic compounds called proteins

or proteids compounds of quite exceptional interest since they
a
, ,

form part often the maj or part of ll living structures and are
involved in a
, , ,

ll life processes Many proteins are familiar to .

everybody The white of eggs for instance consists of water and

protein largely egg a
.
, ,

a
l bumin a pro t ein easily coagulated by heat
a
-

Milk contains c o a
, ,

s is evi dent whenever an egg is boiled g ul

able a
.

l bumin and casein another protein ,

Th e former largely , .

sep arates as a solid s urface fil m when milk is heated whilst ,

casein is separated by the addition of small quantities of acid

such as vinegar or by a clotting ferment like that cont a i ned in
rennet All anim a
,

. l tissues are mainly protein Skin hair .

, ,

nails and h orns muscle e t c are composed of solid proteins whilst

, , .
, ,

blood contains in addition to the suspended corpuscles and the

,

fibrin at least two other proteins in solution In spite of the

,
.

fact that chemists have been interested in proteins for over a

century we are still much in the dark in regard to their chemic a
,
l
constitution A great deal has been accomplished especially in
the last twenty five years and we are now well a c qu a
.
,

in t e d wit h
'

the simple chemical units of which proteins are composed We

know a
.

l so the principal mode Of linkage between these units .

What we do not know is first the order or pattern in which the

units are arranged— a
, ,

matter of great consequ ence ; and second ,

the number of simple units needed to form the protein unit or

molecul e The chemical investigation of proteins has be e n found
.

very difficult since many methods widely applicable in other fields

,

of chemist ry ha v e proved almost useless When it is realised .

that proteins crystallise only in a few instances and then with ,

difficul ty that they have no definite melt ing points or solubilities

, ,

and that they are all very similar in chemical composition it ,

becomes obvious that ordinary methods of purification etc are ,

quite inadequate and that a new technique is required On this,

.
1 26 P RI N C I P L E S OF L EA TH ER MA N UFA C T UR E “

account progress was for a long time very slow but the interest ,

of the subj ect has attracted many workers in recent years with ,

the resul t stated above .

Lie b ig s view was that one protein existed and only one and
’

, ,

that the various substances which appeared to differ Were simply

more or less pure varieties of the one protein I t was by Liebig
that a reliable method of ultimate org nic analysis was elaborated
which when applied to proteins showed that a very great simi
a .

la ri t y in chemical composition existed amongst them Th e

amounts of carbon nitrogen a n d hydrogen do indeed fall w
.

, ,
ithin
ver y narrow limits as the following table of composition shows :
,

Carbon 51 5 per cent .

H ydrogen 7
Nitrogen 1 5—1 9

Sulphur o 4 —
2 5

a
- ~

P roteins are known now whose composition f lls outside the above
figures e g the protamines but they are not commonly met with
, .
, ,

and di ffer considerably in o t her respects from the general run of .

their class I t is then not surprising that Liebi g thought of the

.
, ,

proteins as one substance difficult to obtain pure Methods of

, .

arriving at chemical constitution were few in his day and ,

‘

empirical composition was almos t the only sure and definite

knowledge obtainable Mulder held a mo dified view He. .

regarded protein as one parent substance which combined in

various ways with other things e g sulphur and phosphorus to , .
,

give the different substances occurring in Nature This view like .

,

that o f Liebig though reasonable enough in its day has had to

, ,

be abandoned by reason of the cumulativ e evidence o i subsequent -

work Very many different proteins are now believed to exist

. .

The question may be asked What are proteins 9 A lthough ,

the chemical ( ultimate ) composition of most of them is charact e r

is t ic o f their c l a
ss ye t that particular composition is not invariable

a
-

, ,

nor confined to proteins The same empiric l formula may

“

belong to substances showing the widest differences in nature

and behaviour a n d which could not r e a
,
‘

so n ab l y b e classed together .

P roteins may be suitably described as nitrogenous organic sub

stances always found in the colloid state and which are broken
, ,

up into amino acids by boiling with acids or alkalies or by the

-

,
“

action of certain ferments or enzymes e g trypsin This breaking , . . .

up is known as hydrolysis and is of great importance I t forms

,
.

part of the digestive processes occurs in the liming and bating of ,

hides in the manufacture of glues and gelatines and also in all

, ,
,

putrefactions On this account some explanation must be given

.
,

and first something must be said about acids and amino acids -

.
1 28 P R I N C I P L ES OF LE A TH ER J MA N UF A CT UR E

In all amino acids derived from proteins one amino group is ,

-

attached to the carbon atom nearest to a carboxyl group This

applies to glut a
m i c acid which ha
.

s two carboxyl groups as well , ,

as to lysine w ith two amino groups

, .

A mino acids di ffer in one very important respect from other

-

acids the difference being d ue to the nature of the amino—group

,
.

This gro up is basic A s a consequence amino acids can form

‘
-

.
,

salts not only with bases but wi th acids .

Eg . .

Cp . C6 H 5 NH 2 + HCl -
> C6 H 5 NH3 C1 aniline hydrochloride
, .

H NH 2 + H Cl
. ammonium chloride .

In the presence of bases therefore amino acids act as acids and , ,

-

a
form metallic salts in the presenc e of acids however they act , ,

s bases and form hydrochlorides etc Tyrosine for instance is , .

, ,

only soluble to a very slight extent in water but dissolves readily

in hydrochloric acid as hydrochloride and in alkali as t yr o sin a
,

te .

This behaviour l s expressed in the word amphoteric a word ‘‘

implying the capacity of a substance to act as either acid or base

accordin g to circumstances P roteins a r e also amphoteric by .

reason of the way in which they are built up of amino —acids

‘

Gelatin for instance can form either hydrochloride or gelatinate

, , .

Hydro lys is — The term hydrolysis used in our definition of pro

. .

teins still requires explanation From the point of view of organic

chemistry we m a
.

y look upon hydrolysis as the breaking up of a

,

compo und by the addition of the elements of water Ex p eri .

m entally this 1 5 only occasionally accomplished by simple treat

ment with water I n nearly every case it is nece ssary to heat the
.

substance with more or less dilute acid or alkali An example .

or two will help here Take the case of ethyl acetate If this
. .

substance be boiled with water the reaction ,

CH3 COOC2H5 + HO H— > CH

3 c o o n + C 2H5 OH

will at first proceed in the direction indicated but aft er a time ,

an equilibrium is reached I f the complete hydrolysis of ethyl .

acetate is to be accomplished acid or alkali must be used A cid , .

in sufficient strength although it does not appear in the equation

, ,

will enable the reaction t o be completed in a great number of

cases and all the acid originally used can be recovered t the end
,
a
of the experiment A lkali when used aids the hydrolysis by
.

neutralising the acid product ( forming sodium acetate in the

example ) until no more acid can be formed Compounds which .

are hydrolysable in this way are those which we can imagine to

have been formed by loss of water between two molecules The .
 TH E C H EMI S TR Y OF HI DE 1 29

formation of ethyl acetate from acetic acid and ethyl alcohol is

such a case Hydrolysis in the case of proteins is very often
.

carried out by long boiling ( six to twenty four hours) with fairly -

strong acid ( 20 per cent H Cl or 3 0 per cent H Z SO4) More wil l . . .

be said on t he experimental features in later sections of this

chapter F o r the present it must be understood that amino
acids form by far the greater p art often a
.

l most all of the products , ,

of hydrolysis It is therefore reasonable to assume that some

.

mode of combination b etween amino acids a combination or -

condensation involving loss of Water is responsible for the ,

typical prot ein m olecul e .

C on s titu tion —It is generally believed that the union of amino

.

acids to form peptides is the princip al mode o i combination in

a
'

rotein formation T here are indeed sev eral w ys in which the

“

p
a
.
, ,

m ino —acids could combine with loss of water but since Hofmeister ,

in 1 9 02 surveye d the evidence there has been little doubt that loss
of water between the amino group of one acid and the carboxyl -

group in t he other is the principal mode of union 1 n building u p

a protein .

NH 2 R . COlOH + H ] NH . R 1 c0 0 H
co . NH R 1 00 0 H + H 20

The body re p resented on the right hand side of t he eq u ation is

called a dipeptide Tr ip e p t ides t e t r a
-

p e p t id e s etc contain the

.
, , .
,

appropriate number of amino acid radicals F o r it wi l l be -

realised at once that theoretically there is no limit to the number

“

of amino acids that can be combined t ogether to give one poly

-

peptide Experimentally the synthesis is diffi cul t but an

d e ka
o kt a
.
,

t ide containing eighteen radical s has been prepared

p p
e ,

which proved to be remarkably like a natural protein A ssuming .

the polypeptide structure for proteins hydrolysis is easily under ,

stood Every —CO NH group is by the addition of HO H

. , ,

converted into an acid —COOH ) and an amino group — NH 2) -

NH , R co NH R I c o NH R 2 c 00 H + z H, o
—
. . . . .
. . .

> N H R COOH + NH R COOH

2 2 1 + NH 2R 2COOH .

I t is easy to see that the polypeptide structure gives t he possi

biht y of great variety and complexity in proteins Plimmer .

states that there are 2 7 6 possible dipeptides P ossible tri and

t e t ra
.

p e p t id e s are far more numerous as with increasing com ,

p l e x it y the variations in arrangement of acid ra di cals which may

occur increase out of all pro p ortion to the number of radi cals
involved according to the laws of permutations If we consider
three acid radicals ab and c and consider pentapeptides which
.
,

, , , ,

9
1 30 P R I N C I P L ES OF L EA TH E R MA N UFA C T UR E

they co ul d form we soon find that we could write down new ones
,

apparently indefinitely
aaaaa aaaa
c

a a a a
- - - -
- - - -

c~ ~

aa aaand so on
- -

7
- -
c - -

,
.

Of course a polypeptide a b c is This quite distinct from b a

—
a
c - - -

complexity is made greater still by the formation of br nched

chains and ring struc tures possibility of anhydride formation etc
, , .

and the presence in many proteins of other groups not of a peptide

character Mucins for example contain carbohydrate
.
, , .

CH 2 CHNH CO CHR 2 NH CO '

ex a
m ple is a hypothetical pentapeptide having a ring
'

The
structure The broken lines show where hydrolysis will take
.

place When it is remembered that eighteen o r m o re amino

.
‘

acids may be involved in a protein molecule it is easy to see that ,

only by the merest chance can a natural protein be synthesised ,

even if we assume that we know all about the type of structure .

A s a matter of fact this assumption would be far from j ustifiable

, ,

for in any case the analysis of a protein does not show the order
in which the amino acids hav e been linked A s it is here that
a
-

the greatest causes of variety lie it wo uld appear that wh t is ,

needed most is some method of experiment allowing amino

acids to be split o ff one by one or in small groups so that the order
obtaining in the protein c a
,

n be wo r ke d o u t l
.

I t is possibl e for amino acids to unite in other ways without -

loss of water between the molecules A s the amino acids are .

-

both acids and bases it is at least possible for them to combine

,

with each other

NR 2 R COOH + H2N R I
. COOH3 N R 1 c 00 H .

Cp . CH3 COOH + H 2N H—
> CH
3 COOHg NH ,

ammonium acetate .

An d as polypeptides always contain both free amino groups -

1 32 P R I N C I P L ES OF L EA TH ER MA N UFA C TU R E “

H Y D R OLY SI S or PR OTEIN S

course o i hydrolysis whether effected by acids alkalies

Th e ,
, , ,

or enzymes may be ro ughly re presented by the following

,

scheme :
P rotein ( c o l l g e n casein alb umin
e , , ,

Metap rotein (Li b e e r ku hn s

’
j elly)
t
P roteoses (g l a
e t o se s , albumoses)
t
P epton es
t
Simple P olypeptides ( kyrin s )
t
A mino -
acids .

The prote in is broken up into s impler bodies and these again -

into others until amino acids are produced which of course cannot
,
-

a
b e further hy d rolysed Thus metaprotein is only a little less
"

complex than the origin l protein and retains many of its pro ,

p e r t ie s Proteoses are formed by the hydrolysis of metaprotein

.
,

and so on I t must no t be ass umed that the whole of the original

.

protein is converted into p roteose before any peptone or amino “

acid is formed In some cases ( e g hydrolysis of cas ein by

. . .

tryp sin ) even amino acid the last product is present from the -

, , .

very beginning of hydrolysis Further it must be understood

that there is no sharp distinction between s a
.
, ,

y ; albumoses and ,

peptones and that on the other hand differen t albumoses or

a
, , ,

different peptones may be present together mongst the pro

ducts of hydrolysis of a single protein The usual test s and .

methods of s epara tion for the products of hydrolysis will now

be given
Meta o t ein s —These are only f a
.

pr miliar in the hydrolysis of

albumins a
.

n d globulins and are prepared by the action of dilute

( 0 4 to 1 0 per cent ) acids and a

,

-
l kalies at moderate temperatures
A s they a
. .

re insoluble in water they are precipitated on neutralisa

tion Metaproteins are rendered insoluble in acid or alkali by

.

boiling with water They are distinguished from globul ins by .

their insolubility in dilute solutions of neutral salts .

P rot eo ses are soluble in water but completely precipitated by ,

saturation With ammonium sulphate They are in fact divided .

, ,

into two classes primary and secondary the former being com
, ,

l e t e l y precipitated by half saturation, the latter only by complete

p
 TH E CH EMI S TR Y OF HI D E 1 33

sat uration wi th ammonium sulphate . There are also other

distinctions .

Nitricacid
Potassium ferrocyanide
and acetic acid
Copper sulphate

A lth o ugh secon dary proteoses app ear to approach the peptones
in pro perties they are not as a rule regarded as formed from
,

primary proteose s by further hydrolysis B oth kinds of proteose .

are formed at the same time roughly s p eaking from the protein
, ,

molecule
P ept on es a
.

re not precipitated by saturated am m oni um sul

.
,

a
phate They retain however sufficient of the protein character
to give precipitates with g l lotannin and phosphotungstic acid
P eptones are very soluble in wa t er a
,

n d give evidence of lower

'
.

a
,

molecul r weight as they diffuse though only slowly through

, , , ,

parchment paper An important reaction for the purification

.

of peptones is due to Siegfried A fter secondary proteoses have .

been remo ved by saturation with ammonium sulphate ( pre

fer a b l y in t h e presence of sul phuric acid ) iron ammonium alum ,

in saturated ammonium sulphate solution is added U nder .

these conditions peptones only and no amino acids are pre

c ip it a
-

, ,

t ed .P ure peptone can be recovered from this precipitate ,

and is colourless and ash free in contrast t o t h e discouraging

-

brown masses obtained by the earl ier workers Siegfried takes .

the view that p eptones are not so simple in constitution ( mol .

wt 40 0—600 ) as is often supposed and regards the evidence from

.
,

freezing point determinations as unsound Instead of peptones

-
.

being fairly simple polypeptides corresponding to the above

molecular weights they are he considers feebly bound com
, , ,

pounds of such polypeptides largely dissociated in water , ,

especially in dilute solution This would partly explain ( I ) the

’

higher molecular weights found by freezing point determinations -

when the peptone is dissolved in phenol ( 2 ) the very great in

a
,

crease in molecular weight with incre se in concentration .

Siegfried has prepared bodies which he calls kyrin s by fu i t her

hydrolysis of peptones Fo r exam p le t he peptone formed by the
.
,

action of trypsin on gelatin was heated with 1 2 5 per cent hydro '
.

chloric acid at 3 8 C until the specific rotation of the solution

°
.

assumed a constant value The kyr in in solution proved to .

be decidedly basic in p roperties yielded arginine lysine and , , ,

1 34 P R I N C I P L ES OF L EAT H ER MA N UF A C T U R E “

glutam i c acid in equimolecul a r proportions when ful ly hydro

lysed and in fact was shown by further work to be a tripeptide
,
.

P olypept ides — I t is probably safe to assume that some simple

polypeptides are formed in the ordinary course of hydrolysis and ,

th at the more complex peptones are not split up directly into

amino acids The work of Siegfried on the kyrin s supports this
-

View There is however an important point to be mentioned

.
, , ,

namely ; that acids and enzymes are to some extent able to for m
a
peptides and other nhydrides from amino acids I n the course
of protein hydrolysis therefore wh ere the various stages are not
-

a
, ,

sh rply defined it is always possible that peptides present may

,
.

have been formed from amino acids resulting from the hydrolysi s
~ -
.

The presence of peptides wo ul d then indicate a step back

a
.

A min o cids have been previously described and are t he end

-

products in complete hy drolysis It has already been stated .

,

however that amino acids may be present in certain cases from

,
-

the very commencement of the process

Gen er a
.

l A large amount of the work done o h products of

— .

partial hydrolysis has be en with fibrin albumin or gelat in as

origi nal material and it is doubtful whether the above cl a ssific a
, ,

tion 00ul d be easily or usefully applied in the case of every protein

In t he c a
_ .

s e of keratin for instance hydrolysis has to be carried

, ,

further than with gelatin bef ore soluble products are obtained .

Gelatin dissolves in cold lime water in a day or two and the solu ,

tion gi ves no precipitate on neutralisation Keratin is acted upon .

much more slowly and the solution obtained ( e g a used lime

liquor) invariably gives a precipitate when neutra
, .

l ised
“

Obviously in the latter case it is impossible to te st the behaviour \

with ammonium sulphate solutions I n this connection it is

“

interesting to notice the co mplexity of used tannery lime liquors .

We have present proteoses peptones amino acids etc derived

from at least four diffe r e n t p r o t e ins These substances a
-

, , , .
,

r e in .

the form of calcium salts Further since certain bacteria present

.
,

have the power of acting upon and deaminising amino acids

we have in lime li quors free ammonia and a
-

l so acids ( as calcium
salts) derived from amino —acids by loss o f a m m o n ia
,
‘

. .

A c id Hydr olys i s — Prot ein is heated with fiv e or six times its

weight of concentrated hydrochloric acid or 2 5 to 30 per cent .

sulphuric acid Until the protein is quite dissol ved the heating
.
,

sho ul d be carried out on the water bath The solution is after -

wards boiled under a reflux condenser until hydrolysis is com

p l e t e i e until the biuret test ( p 1 40 ) fails
,
. . This often takes . .

about six to twelve hours with hydrochloric and twelve to .

twenty four hours with sulphuric acid but may require two or
-

,
1 36 P R I N C I P L ES OF L EA THER MA N UFA C T UR E

make very great improvements in the estimation and separation

of monoamino acids He extracts the aqueous solution with a
non miscible solvent butyl a
-
. .

-
l cohol in which indeed the amino
, ,

acids are only very slightly soluble Bu t a continuous extraction .

process is used similar to the extraction of tannin solutions by

amyl acetate in qualitative an a
,

l ysis Some of the amino acids .

-

crystallise out from the alcohol during the extraction others are
“

not extracted This method has been applied to the quantitative

.

hydrolysis of gelatin with the very interesting result that over

,

9 1 per cent of the protei n i s now accounted for D akin s figures

‘ ’
. .

are given below and should be compared with those of t h e older

,

anal ysis ( p 1 3 5) which stood for many years as the best

.

available :

Glycine Proline
’

A lanine Oxyproline
Leucine A spartic acid
Serine Glutamic acid
Phenylalanine Histidine Total 91 3
-

Tyrosine

a
A l k lin e Hy dr oly sis —Thisis of v ery great interest in leathen
.

manufacture but has received much less attention than acid

,

hydrolysis R esults so far obtained go to show that the products

.
,

by the two methods do not differ ve ry much Alkali seems to have .

the more powerful action It has been stated t hat gelatin soon .

dissolves in cold lime water In N/z o acid however hydrolysis

,
.
, ,

is very slow at ordinary temperatures In some cases resistant .

bodies formed in acid hydrolysis are mu ch more quickly broken

up b y alk a li A bderhalden found that a r esistant body obtained
from silk could onl y be hydroly sed further by the use of a
.

a
l kali .

Two other important points are : ( I ) cystine n d arginine ar e

'

decomposed by a l ka
l i and ( 2 ) optic a
.

l ly active amin o acids are

,
-

rendered completel yinactive

A study of slow a
.

l kali hydrolysis at or di nary temperatures

would be of very great interest to leather trades chemists ’

especi a
,

ll y with regard to the nature of the liming process ; Th e

great difficulties presented have no doubt deterred workers from
taking up this subj ec t .

En zyme Hy dr olys is — This subj ect is of paramount importance

to physiologists and biochemists and has been the subj ect of much ,

investigation In leather manufacture enzyme hydr olysis occurs

.

in both liming and b ating and must therefore receive some con ,
 TH E C H EMI S TR Y OF HI DE 1 37

sideration Severa . l enzymes are capable of breaking up proteins ,

and amongst the most important are pepsin and tryp sin Such .

hydrolysis however is never complete A resistant body named

, , .

antipeptone is formed which is never completely broken up

,

even by the combined or rather successive action of different

enzymes though a
, ,

,
l most complete h ydrolysis can be obtained in
some cases if a sufficiently long time is all owed Fischer and .

A bderhal den found that antipeptone contains all the phenyl

al anine and proline of the origin a l pr otein Of the two enzymes .

mentioned trypsin effects the more complete hydrolysis pro

d u c in g as a rule considerable quantities of amino a cid s wh e r e a
, ,

'

s -

pepsin rarely carries hydrolysis past the peptone stage Th e .

course of action of pepsin on fibrin is according to Cole as

follows
Fibrin
t .

Soluble globu lin

Metaprotein

t t
Pri mary albumoses Secondary albumoses

Kuhn e scheme tryptic digestion is

’
s fo r

Secondary albumoses

A nti peptone

A mino -
acids .

With regard to this latter scheme it must be stated that the

“

hemipeptone is a hypothetic a
,

l substance and has never been

isol ated and that some observe rs have found that nearly all
,

the tyrosine is separated from casein in t he first hour of tryptic

digestion .

Enzyme hydrolysis is much affected by conditions of tempera

ture reaction dil ution etc Pepsin requires an acid medium
, , , .
,

and is most e ffective in 0 2 per cent hydrochloric acid or at .

,
1 38 P R I N CI P L E S OF L EA TH ER MA N UF A C T UR E

PH = I 4 about Weaker acids must b e used in appropriately

higher concentrations In a l ka
°
. .

l ine solutions pepsin _ is very.

rapi dl y destroyed especially on warming It has be en stated

, .

that peptic digestion pro duces nothing simpler than peptones and
polypeptides Indeed it would app ear accordi ng to Cole that
pepsin c a
.
, ,

nnot break any peptide linkage since it does not hydro

lyse any Synthetic polyp eptide Tryp sin acts best in alkaline .

solution at P about 8 1 It is n o t however destroyed by

H
-
.
, ,

acids but accordi ng t o some observers is in the absence of

protein even more stable in acid than in a
, , , ,

,
l kali In carr yi ng .

a
out hydrolyses by means of trypsin care should be taken to
h ve t h e reaction mixt ure a l ka
,

l ine to cresol red and acid to

phenolphth a l ein Trypsin acts on a l l soluble proteins but not
on a
.
,

l l insoluble ones collagen) It is s o m et im es necessary .

v

to gi ve insoluble proteins a preliminary treatment with dil ute

acid or a l kal i or with pepsin Hydrolysis will then in a n
y
“

case be more complete It would appear that certain linkages .

in the protein molecule are opened up by pepsin but not by

trypsin The products of t ryptic digestion a
,

. r e simple poly
'

peptides and amino acids the hydrolysis never being complete -

even aft e r prolonged action Trypsin is of great interest in .

leather manufacture owing to its capacity for unhairing and , .

bating skins Probably the unhairing action depends on the

di gestion of the softer keratin of the epidermis since the outer ,

horny layer can often be removed bo i ly with the hair The use
d
of trypsin i n bating will be di scussed m a later chapter All that
.

need be said here I S that it appears to di gest rapi dl y the elastin

,

of the elastic fibres whilst having only a very slow action upon
the collagen fibre

G ENERAL CHA RA CTER S or TH E P R OTEI NS

S olu bility ,
e tc .
— Some
important proteins belonging to the
~
"

class of scleroproteins appear to b e quite insoluble in the un

changed condition notably collagen elastin and the keratins
A cids and alk alies effect solution especi a
, , , .

l l y with the aid of heat ,

a
but hydrolysis has first taken place Gelatin is insolubl e in cold
water but l ways swells t o severa l times its o rigin a
.

, l vo l u m e c

The swollen j elly on warming easily melts ( at about 2 5

°

giving a solution of gelat in V ery concentrated solutions can be .

prepared with hot water but it should here be remarked that in ,

no case shoul d a gelatin solution be heated above 7 0 C unless °

.

the hydrolysis which then begins is of no moment Casein is

insoluble in water a
.

l though particles suspended in water are able

,
I 4o P R I N C I P L ES OF L EA TH ER MA N UFA C T URE
tannin The protei n solution should be slightly acid before the
.

reagent is added .

( 3 ) The salts of heavy metals most often used are lead acetat e
zinc a
,
.

n d copper s ul phates and ferric chl oride The protein

’

solution should be faintly a l ka

.
,

l ine The precipitates formed are

'

often soluble i n acid or i n excess of reagent

Th e reactions under ( 2 ) require the protein to be l n the acid or
positively charged condition as the reagents have a compl ex ,
.

negative ion which is believed to be the effective agent in the

reaction The behaviour of tannin is explicable on similar
.

grounds as it is a negatively charged colloid in acid solution In

, .

the reactions under ( 3 ) the p r o t ein jis negative and the positive '

kation of the reagent is effective A consideration of these

a
.

re ctions shows that substances such as copper sulphate and

mercuric chloride can onl y b e used under special conditions for
the steril isation of hides since chemic a l combination may occur
,

and unfavourably influence the subsequent processes of leather

manufacture
C ol o m R ea
.

'
c ti ons — Xanthoproteic R eaction
.
—This is carried :

out by the addi tion of strong nitric acid to the protein or its
S olut ion and then boiling A yell ow precipitate or solution is
obtained whi ch becomes orange on the a ddit io n o f alk a
.

li
‘

.
,

Millon s R eaction —Mill on s reagent is prepared b y di ssolving

’
.
’

one part by weight of mercury in two parts of nitric acid (Sp gr . .

I warming if necessary towards the end of the reaction .

The solution is then diluted with two volumes of water allowed

a
,

to settle and filtered When the reagent is added to protein

, .

solution a whitish precipitate is formed which becomes brick red

on c a
,

reful warming or else dissolves giving a red solution This

, , .

test only gives a positive r esul t wit h proteins cont aining tyrosine
The xanthoproteic reaction is positive with proteins cont a
.

ining ,

tyrosine tryptophane or phenylalani ne i e the aromatic amin o

, ,
. .

acids .

B iuret Test — A ccording to Cole 3 c c of protein solution ( about , . .

I to 2 per cent ) is heated with I c c

. of 40 per cent sodium . . .

hydroxide and one drop of I p er cent copper sul phate solution . .

A pink or violet colour is given not only with pr o teins but with
proteoses and peptones .

Glyoxylic R eaction ( Hopkins and Cole) — Protein solution is

mixed with glyoxylic reagent and an equ a l volume of conc o n ~

t ra
,

t e d s ul phuric acid is poured down the side of the tube A .

purple colour is seen at the surface of separation of the fluids ,

and with gentle Shaking this colour Spreads throughout the

contents of the tube The glyoxylic reagent is prepared by
.
 TH E C H EMI S TR Y b E H I D E 1 41

reducing ox a l ic acid with sodium am a l ga

m or magnesium powder .

The reaction is shown only by those proteins which contain t he

amino acid tryptophane I ndeed the di scovery of this substance
-
.

by Hopkins and Cole was du e to the study of the glyoxylic test .

Sul phur R eactio n — P rotein is boiled with 40 per cent caustic .

soda for a minute or two and then a little lead acetate is added , .

A blackening resul ts by the formation of lead sulphide from the

sulphur of the protein .

Molisch 5 R eaction —Protein solution 1 5 treate d with a few

’

drops of I per cent solution of anaphthol or of thymol i n alcohol

.

-
. .

A fter mixing concentrated sul phuric acid is poured down the

,

side of t he t e st tube A violet colour appears at the surface of

~

separation This reaction is positive wit h p r o t e iris ( a

-
.

.
g mucins) .

which contain carbohydrat e

Cry sta llis ati on of P r otein s — Although cryst a
.

ll ine bodies of a
“

protein nature have been known for many years it is onl y

recently that the cryst a
,

ll isation of proteins has become at all

generally practised Aleurone gr ins were first n o t ic e d in 1 8 50 a
in gluten and occur in the seeds of many plants ( a
.

g hemp seed)
Although they look like cryst a
. .
,

l s y e t they behave di fferently from ,

ordinary crystals They swell f0r instance in water In recent

‘

. .
, ,

years however many proteins have been artificially crystallised

such as edestin egg albumin gelatin and h a
, , ,

emoglobin Th e
typic al method is that of Hopkins and Pinkus for the c r yst a
-

llis a
.
, , ,

tio n of egg a l bumin A solut ion of this protein h a

-
l f saturated .

with ammonium sul phate is prepared and cautiously treated ,

with I O per cent acetic acid until a permanent precipitate

appears A Specified addition a
.

_
. l amou nt of acid is then added ,

which produces a heavier precipitate The mixture is allowed

to stand overnight when the precipitate becomes cryst a
-

, l line .

The protein can be recrystall ised as often as desired Other

proteins are sometimes cryst a
.

We im a rn ,

gelatin until a Slight perman ent precipitate is formed

a
l lised by means of alcohol
for inst nce adds alcohol to an aqueous solution of
Vo n

Th e
,
.

mixture is then left in a desiccator containing strong sulphuric

acid by which means water i s more rapi dl y removed than the
a
,

l cohol Crystallisation begins as the solution becomes richer in

a
.

l cohol and the insolubility of the gelatin increases

, On the .

whole however it cannot be claimed that the crystallisation of

, , ‘

proteins has at present any outstan di ng importance Crystals

obtained from ammonium sulphat e solutions are a
.

l ways largely
contaminated with the sal t and must be further purified by
solution and di a
,

l ysis In any case there is some doubt as to the .

,

identity of crystallised products and the original proteins It .

-

I 42
~
P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

S houl d be mentioned that as a rule the cryst a l s obtained are only

recogn isable as such under t he microscope
C oa a a i aa
.

l t i b H e t — Some proteins l bumins and

g u on y
globul ins , are coagul ated by heat Egg a
. .
,

l bumin coagulates .
-

when its solution is heated to ab out 55 to 60 C This is of course 9

.

a familiar occurrence seen every time an egg is cooked but the ,

nature of the change involved is quite obscure There are how

ever severa
.
,

l points worthy of notice In the first place the

coagul ation di ffers from that produced by a
.
, ,

a
mmo n ium su lphate ,

etc in being irreversible Heat coagul ated egg white c nnot be

.
,
.
- - -

brought back into solution In the second place the presence

of al k al i acid or of neutr a l sal ts ( even in small qu a
-

.
,

n tities ) is of

great influence Di a
, ,

owing to the presence of sm a

l ysed solutions often l ose their c o agul ability
l l quantities of l k a
.

long continued di al ysis will effect a recovery of this property

l i or acid but a ,

In the case of a di a
-
.

l ysed solution no longer coagul able small

quantit ies of neutr a l sa l t will like further dial ysis render
coagulation possible The mounts requi red are much small er a , ,

in the case of c a l cium and magn esium s a l ts than with a l ka

.

li
sa I ncrease in the amount of s a l t ra
.

l ts i ses at fir st the coagula

a
.

tion temperature someti mes by as much s 1 5 to 1 8 C but may °

later cause a f a
.
,

ll I t is therefore obvious that the coagulation

.

temperature can only be characteristic of a protein under exactly

defined circumstances A non coagul a ble protein may be freed
say from a
-
.
,

l bumin by heating the solution and fil tering but as

in di cated above such a process does not pro duce pure a
, , ,

l bumin
Phosp horu s a
, .

n d S u lp hu r C on t en t — A lmost all proteins contain

sulphur The amount present is usually quite sm a

.

l l and varies
P eptones are a
.
,

very much in different proteins s a rule .

, ,

free from sulphur On e class of proteins the keratins is d is .

, ,

t in guish e d by comparatively high sul phur content ( 2 to 5 per

a
cen t ) few others containing so much as 2 per cent On ly one
amino acid cystine cont a
.
,

-
i ns sulphur and the m ount of this
, , ,

element is often taken as a measure of the cystine content of a

protein This procedure IS perhaps not free from obj ection
. .

A few proteins contain considerable amounts of phosphorus .

Of these the best known is casein which contains 0 85 per cent

'

a
-

, .

Dis tr i bu ti on of N itrogen in P ro tein s It has lready been -

pointed out that the am

.

ount of nitrogen contained in a protein

rarely varies very much Nevertheless the dist r ibution of
the nitrogen i athe amounts combined in cert a
.

,
. . i n groups
of amino acids shows considerable variation and is often
-

,
‘
,

useful in characterising proteins A rapid method for the .

determi n ation of t he distribution was first worked out by

1 44
'

P R I N C I P L ES OF .
L EA TH ER MA N UFA C T UR E

1 and much work has been done since by B rown a

87 5 ,
n d Mil lar ,

van Slyke Fischer and Ko el ke r and others and the estimation

, , ,

of nitrogen liberated by the action of nitrous acid on proteins

is now a regular laboratory process described in text books of -

physiological chemistry etc With a pure amino acid the reaction

is usu a
-
.
,

l ly simple as in the case of aspartic acid ,

Ho o c CH . . No
> H OOC CH -
. . CH ( OH) C0 0H + N2 + H O

H alf the nitrogen evolve d c o mes from the amino a ci d A nomalies -

.

occur however even with simple acids B oth glycine and cystine
, , .

give a larger volume of gas than the Simpl e equation accounts for
a
.

Fischer and Ko elker found the re ction between polypeptides and

nitrous acid to be somewhat indefinite and irregular and that the ,

nitrous acid reacts to some extent with the peptide — CO NH

linkages Nevertheless the interesting conclusion has been drawn
.
,

that in the case of proteins t he nitrogen formed with nitrous acid

comes entirely from one of t he t wo amino groups of lysine A -

prot ein containing no lysine should therefore yi eld no nitrogen .

This has been Shown to be true in the case of zein a protein ,

obtained from maize With other proteins it has been shown

that the nitrogen obtained corresponds to h a
.

l f the lysine in the .

molecule This work has received much support from the

form a
.

l dehyde reaction which is described below It is clear that .

during the hydrolysis of a protein the number of free amino

groups increases and that an increasing proportion of t he t o t a l
a
~

nitrogen becomes reactive with nitrous cid Edestin for .

,

instance contains 1 8 per cent of its total nitrogen in free

,
.

amino groups but when fully hydrolysed no less than 7 9 per cent
'

, .

of the nitrogen is in that form Clearly the nitrous acid reaction

gives va
-
.

l uable information as to the progress of hydrolysis

A ction of Form a ldehy de on A min o a
ci ds a
.

n d P r o t ein s —A mino -
.

acids are very weak acids and it is not easy to tit rate them with
alk a
,

l i in the ordinary way owing to the hydrolysis of their

sodium s a If however they are a
,

l ts . l l owed to react with

, ,

formaldehyde the basic character of the amino group is destroyed

,
-

and very much stronger acids are produced which can be easily ,

NH C N CH
R/
.

+H
\ C0 0 H \G
OOH

titrated with alkali The form a l dehyde used shoul d be neutr a

l .

to phenolphthalein the indicator used The acidity d e veloped

by the ad di tion of form a
.
,

l dehyde is thus a measure of free amino

 TH E C H EMI S TR Y OF HI D E 1 45

a
nd carboxyl groups though in most cases no exact cal cul ation
,

can be made Since the various amino acids are present in unknown
,
-

proportions Clearl y during the course of hydrolysis of a protein

the form a
.
,

l dehyde titration will very markedl y increase just as ,

the volume of nitrogen liberated by nitrous acid increases we

shoul d therefore ha ve a means of foll owing the course of hydrolysis
and verifying the information given by the van Slyke nitrous ,

acid method In practice the two methods do as a rule give

parallel results but there are one or two points about the form a
.

, l
d ehyd e titration which are causing it to lose favour In the first .

place formaldehyde does not react with some anhydrides of amino

,

a
acids These bodies are certainl y formed in hydrolysis especially
.
,

when prolong e d as has been shown by Fischer and A bderh l den

On this account a
.
,

l one therefore the formaldehyde titration will

, ,

fail to give a correct indication of the course of hydrolysis If .

amino acids were being produced j ust as quickly as amino acids

- -

already formed were condensing into anhydrides then the titra ,

tion wo ul d Show no Change A s econd obj ecti o n is that t he

reaction between histidi ne ( an amino acid) and form a
.

l dehyde is -

abnormal and irregular Finally the reaction in the case of any .

,

amino acid is reversible and hence in the titration an excess of

-

al kali must be used e g by titrating to a decided red colour with

phenolphth a In spite of a
. .
,

l ein . l l this however it must be con , ,

ceded that the method is certainly useful one great advantage ,

lying in the ease with which it can be carried out

Th e action of form ldehyde on hide appears to be an aa
.

l ogous
to the action on amino acids A certain amount of acidity is
a
-
.

l ways developed due no doubt to the change in the amino

,

groups described above The reversibility of the action on amino

acids except in the presence of excess of a
.

,
l kali is indicated in ,

the case of proteins by two facts : ( 1 ) the formaldehyde can be

easily Spl it o ff quantitatively by distilling the compound in
steam or by boiling with di lute ( N/I o) acid a nd ( 2 ) f orm a l dehyde
tannage is usually carried out in the presence of a l ka li Q ualita .

t ivel y proteins show considerable changes on treatment with

form a
,

l dehyde They are rendered resistant to pepsin and prob

.
,

ably to other enzymes though a digestible protein is easily ,

recovered by treatment with steam Egg white appears to lose .

-

its property of coagul ating on heating Soluble proteins often .

become insoluble Gelatin for instance becomes a hard in

.
, ,

soluble substance and the setting point of gelatin j ell ies rises
per cent ) form a
.
,

I f very dilute l dehyde solutions are used the .

,

reaction appears to require two or three weeks for completion .

The time is much shorter when strong solutions are used The .

1 0
1 46 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

amount o f form a ldehyde which combines with a given weight of

protein has been investigate d by B enedicenti who added 4 c c
of 2 per cent form a
. .
,

l dehyde s o lution to I O c c of protein solution

. . . .

His r e sul t s given by Schryver are as foll ows

, .
,

1 grm gelatin combines with 0 0 1 3 5 grm formald ehyde

I O c c fresh egg —
. . .

. white
. 0 37 5 -

2 grm l powdered 0 03 6 -

1 0 c c blood serum
. . 0 31 5 -

3 grm fib ri n . 0 0 3 45

5 grm casein 0 0294 -

.

Thes e quantities wil l probably be only correct under cert a in

“

experiment a l conditions and too much importance should not be ,

attached to them
A ction of H a l ogen s etc on P rotein s — The action of h a
.

l ogens .

on proteins is complex involving both oxidation and sub ,

stitution In Spite of the very considerable amount of work

.

wh ich has been done on the subj ect we have little or no clear ,

understanding of the react ions involved Al l proteins react .

dir e c t l v with halogens sometimes forming derivatives containing

,

as much as 1 5 per cent of halogen as in some bromine ‘

compounds of egg a
.
,

l bumin serum glob ul in proto and deutero

albumose These derivativeS are readily soluble in a
- -

, ,
-

l kal ine
“

solutions from which they can be r ep re cip it a

. .
V

t e d by acids Some
bromine deriva tives are soluble in a
.
,

l cohol but not in the fat

solvents They can be s a l ted out from a l ka
l ine solution by means
of ammonium sulphate but are not precipitated by the a l ka l oid a
.

l
reagents ; they gi ve the biuret reaction but not the Millon a
,

nd ,

glyoxylic tests A t the same time as the hal o gen derivatives are
formed certain groups appe a
,
r to be eliminated f rom the protein
molecul e In the reaction products with iodine ammonium
.
,

iodide and iodate iodoform carbonic formic and acetic acids

'

have been found and it is supposed that these subst a

, , , ,

,
nces
result from the scission of particular groups .

COLLA GEN
Hide or skin consists of severa l proteins namely collagen , ,

forming the white fibres of the corium keratins formin g the

epidermis and hair or wool mucins and a l bu mins in sm a
,
-

,
ll quan ,

tities in the corium partly arising from blood and lymph and
a
, ,

l so the elastin of the yellow elastic fibres In the fresh hide .

collagen occurs in the swollen hydrated condition and al though , ,

it is the only important hide constituent very little is known of its ,

 1 4 8 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

collagen is converted into gelatin and lastly by the fact that ,

gelatin when heated to temperatures above 1 00 C is gradually °

.

converted into an insoluble substance which apart from lack of ,

fibrous structure closely resembles collagen The molecul ar .

weight of collagen is unknown but certainly very high ; the ,

combining weight of gelatin has been determined by Procter and

a
,

that of collagen may easily be the same ( see Ch pter No

boiling point or osmotic —pressure determinations of the usu a
-
l kind
are possible since Collagen appears to be completely insol uble l n
,

water Indeed unless hydr olysis or other decomposition takes ‘

place col lagen will not dissolve 1 n any reagent Acids and a l ka
.
,

l ies

a
.
,

s well collagen as they do gelatin but no solution takes place unl ess

the cid or a i rly strong or assisted by heat or bacteri a

-

l ka
l i is f a
,

l
action The view commonly held that hide substance dissolves
.
-

in 1 0 per cent solutions of sodium chloride i s probably erroneous

. .

Many of the experiments quoted in its favour have been per

formed on hide incompletel y purified and in no case do the ,

controls appear to have been sufficiently rigi d In o t her resp ects

a
.

collagen behaves similarly to other proteins so far s its in s o l u

’

b il it y allo ws It is acted up0n by form a l dehyde a nd the h a

.

l ogens
'

.
,

dehydrated or hardened by al cohol strong solutions of ammonium ,

'

sulphate etc The usual protein precipit ants behave as tanning

agents partly by chemica
.
,

l and partly by physical means Hide

gives a
.

l l the colour reaction s which can be carried out with s olid

protein including the xan thoproteic and Mill on t ests The first
,
.

product of hydrolysis of collagen i s gelatin which 1 5 made by long ,

a
boiling ( many hours or even days) of purified hide etc Com , .

p l et e hydr olysis gives the ami no cids obtained fro m gelatin

-

enumerated in an earlier section of this chapter The slow action

o r hydrolysis with cold di lute a
.

l kali or acid has not been studied

'

from the chemic a l point of view What is known with regar d to .

gelatin will be described shortly when it wil l be seen that one ,

cannot t ake the identity of fresh and delimed hide for granted .

The di fference may be merely one of space arrangement of atoms

within the molecule ( i e stereo chemic a l ) but i s probably re a l
The salt formation between c o llagen and acids or a l ka
-
. . .
,

l ies probably
fol lows closely the behaviour of gelatin and 1 5 largely a matter of
physic a T hat re a
,

l chemistry ( see Chapter l combination

a
takes place is proved by the impossibility of freeing limed hide
from lime by washing with water The mount present c a n be .

reduced from 4 or 5 per cent to 1 5 per cent but no further .

°
.
, .
 THE C H EMI S TR Y OF H I D E 1 49

GELATI N
Gelatin does not occur in hi de but is the first hydrolyt ic pro
duct of collagen It s interest for l e a t he r t r a
,

de s chemists is very
' ’
.

great since it has many points of resembl ance with collagen and
, ,

has been the subj ect of much chemical investigation The purest .

varieties occurring commercially are colourless and transparent ,

of horny toughness , and of Specific gravity about 1 3 Gelatin .

has no definite melting point but begins to soften with d e c o m

In cold water a
,

position at about 1 40 C l cohol ether or

°
.
, , ,

hydrocarbons gel atin is insoluble but swell s to a transparent

, ,

j ell y in the first named This swelli ng is one of the most im .

portant properties of gelatin and is especiall y marked in dilute

acids and alk a
,

l ies A full di scussion of the subj ect will b e found in

.
-

Chapter X Wh en the j elly is warmed it melts at temperatures

.

from 3 0 to 40 C and a solution of gelatin is obtained which sets

°
.
,

again to a j elly on cooling if the concentration is above 1 per

cent Gelatin solutions Shoul d a
(

. l ways be prepared b y first -

swelling the gelatin then pouring o ff the remaini ng water addi ng

further water as required and finally melting by wa
, ,

rming to a
,

temperature not above 50 C The last precaution is of im °

.

portance if it is desired to dissolve the gelatin unchanged and

avoid any further hydrolysis since a solution heated to above ,

7 0 C will never return to its original state The setting

°
. .

and melting temperatures of the j elly will be found to be

permanently lowered owing to the increased peptone content

in the Speci a
. l text books
,

Methods for the examination of glues n d gelatines will be found

The determination of the melting
-
.
a .

point of the jelly may be mentioned here as it is of particul ar ,

importance An angul ar fragment of j ell y shoul d be put into a

.

narrow glass tube attached to a thermometer the whole in a ,

beaker of water which is slowly heated until the j elly melts Or the .

j elly may be al lowed to set in an open capill ary tube which is

then treated as above the temperature being noted when the ,

water rises in the tube Th e melting point varies very con

sid e r ab l y with the qu a
.

l ity of the gelatine but is little a ffected by ,

variations in concentration between 5 and 1 0 per cent A 1 0 per

'

cent j ell y of best hard gelatine melts at about 3 8 C glue may

.
°
.

melt at a temperature as low as 1 5 C °

P urifica tion — In much chemic a l work the best commerci a

.

l
gelatines have been used without any further pu rification and
with no regard to the origin of the materi a
,

l i e whether , . .

from hide or bones It is obviously too much to e xpect

.

that commercial gelatine can be a pure substance nor can it be ,

1 50 P R I N C I P L ES OF L EA TH ER MA N UFA CT UR E

taken for granted that bone gelatine and skin gelatine are identic a l .

The method of preparation by long boiling of hide makes puri ty

in the chemic a l sense impossible since gelatine formed at an ,

early stage of the process will be subj ected to the prolonged

action of boiling water and therefore notably hydrolysed A ctu a l
examinati on proves that a l l commerci a
l gelatines cont a
i n gel a
, .

t o se s
and peptones often in considerable quantities B ogue has
carried out an a
, .

l yses of some glues and gelatines with the foll owing

results

R ussian isinglass
Edible gelatine
Hide glue

B one gl iie
P epto n e

Even the best French gelatin e contains peptone It is doubt

ful too whether the protein in commerci a
.

l gelatine is a singl e ‘

indi vidual The presence of chondrin has often b een susp ected
.
,

but no strict examination has been made The usual way of

purifying gelatin has been to wash it for severa
.

l days in running
water preferably after treatment with dilute acid Inorganic im
purities are thus largely removed by di a
.
,

l ysis some peptone will

also dis a pp ear at the same time Miss D J Lloyd has lately purified
. . .

gelatin by soaking it in successive changes of acid of concentrations

so chosen that the final product is at its isoelectric point ( i e
-

. .

P =4H So treated the gelatin is milk white and not trans -

parent and the ash content is very low ( 0 1 per cent ) This -

method however does not appear fin a

.
,

, ,
l ly to solve the problem .

D akin in the paper quoted above refers to t he u nsatisfactory

nature of the present methods of purifying gelatin
a
C o gu l ati on by R ea a a
.

d O ti l A i i — Gelatin is
g en ts n p c c t v ty
completely precipitated from solution by h a
,

l f saturation with -

ammonium sul phate ; indeed from a preliminary experiment by

,

the writer it appears to come down in slightly acid solution

between 0 2 5 and 0 4 of complete saturation It is also p re
t e d by magnesium sulphate ; and a
- -

c ip it a
.

l so in the presence of
a little acid by sodium chloride The coagul um is of course
, .

heavily contaminated with the salt used which can be removed

only by di a
,

l ysis A lcohol acts in the same way and the

.
,

amount precipitated is often determined as an index to the ' '

1 52 P R I N C I P L ES OF L EA TH E R MA N UFA C T UR E

stances su ch as alum basic chrome liquor and metaphosphoric, ,

a
acid intensify t he reaction others positi vel y charged colloids , , ,

retard it In any case the reaction will o nl y t ke place in an

a
.

acid solution If a seri es of trials with gallotann in and gelatin

.

be made beginning with acid solutions n d adding small increasing

quantities of a l ka
,

l i the reacti o n will ultimately fail with rather

,

surpri si ng suddenness There has been much debate as to the.

natur e o f the precipitate Di fferent workers have obtained the

“

a
most widely varying resul ts for its composition and it was left to ,

J T Wood to Show that precipitate of constant composition

. .

co ul d only be obtained in the presence of a sufficient excess of

t annin If this excess were provided ( 6 parts tannin to 1 part
“
“

gelatin ) then 1 grm of gelatin combined with 2 4 grm of

,
.
-
.

tannin and variation in the concentration of the soluti ons was

,

found to have very little effect This result is su fficient to dis

a
.

prove any hypothesis based o n so c l led adsorption in which -

conc entrations are the dominant factor and absolute amounts of

no importance The most p robable e x p l a nat io n is that we have
the mutual neutra
.

l isation of oppositely charged colloids since ,

when the reaction takes place in acid solution only we have the , ,

gelatin positively and the tannin negatively charged This is

followed by precipitation In a
.

l kaline soluti o n when both

“

colloids bear a negative charge and n o neutr a

.
,

l isation is possible ,

there is no precipitation I t will be noticed that this is strictly

an a Instead of the mutu a
.

l ogous to an ionic reaction l neutral isa .

tion of oppositely charged ions the reaction is between large

“

coll oid al particles bearing charges probably derived fr o m a tta

, _

che d '

i ons .

V arious salts diminish the solubility of gelatin in water and

raise the melting point of j ellies Such are a l u m chrome a l um
and basic chrome salts P otassium dichroma
.
, ,

t e behaves similarly -

when aided by the action of light Th e dichromate is reduced

.

and tan s the gelatin This behaviour is utili sed in making

'

cements Formal dehyde a Other s a

.

l so insolubilises gelatin l ts
either ra
. .

i se or lower the melting point of gelatin j ellies but their

effect is physical rather than chemic a
,

l
Hydr oly sis — Th e complete hydrolysis of gelatin has a
.

. lready
been referred to and a list given of the products obtained We .

ought to add a little about the phenom ena of partial hydrolysi s ,

though the work in this field has been very scanty Well de fin e d .
-

peptones have however been isolated by Siegfried by his iron

, ,

alum method after the action of pepsin or trypsin These .

peptones have been subj ected to further h ydrolysis with interest

ing resul ts Fo r instance the peptone obtained by the action of
.
,
 TH E C H EMI S TR Y OF H I D E 1 53

trypsin was heated with 1 2 5 per cent hydrochloric acid at 3 8 C

'
.
°
.

A fter 1 1 3 hours the optical rotation had fallen from — 8 4 to

°
-

and r e m a
in e d c o n st a
n t for 2 1 4 h o urs From this solution
’

a body was obtaine d which Siegfried calls a kyrin and which , ,

on hydrolysis yielded only arginine lysine and glutamic acid

, , , .

Further work on this body proved beyond reasonable doubt that

it was an actual tripeptide the elementary analysis giving figures
a
,

l most e xactly corresponding to theory This resul t is an

a
.

important contribution to knowledge of the structure of gel tin ,

seeing that it is less likely under the circumstances of the e x p eri

ment that the trip eptide was formed from amino acids previously -

split o ff .

ELA STI N ,
E TC .

El ati
s n .
— This
protein constitutes the yellow elastic fibres of
the corium and is of a stable character It is scarcely possible
,
.

to isolate it from hide and our knowledge of elastin is mainly ,

derived from that of the tendons and ligam ents particularly

lig amen tu m n u chw the very strong a
,

n d thick ligament in the

,

neck of cattle etc This elastin is assumed without proof to

be identic a
.
,

l with that of the elastic fibres In chemical .

properties elastin shows considerable similarity to keratin being ,

very resistant to boiling water and only slowly attacked by h ot

acids and alka
_

l ies The products of complete hydrolysis have

.

b een given and in this respect elastin does not resemble the
,

keratins The elastic fibres are apparently unable to combine

It has been stated recently by sever a
.

with tannin . l writ ers that

the elastic fibres tend to disappear in the bating process being
acted upon b y the trypsin or other enzymes This is avery
,

attractive view of the bating process and has been strongly ,

supported by published photomicro graphs On the other hand

it has been obj ect ed that elastin from liga men tu in n u cha
.
,

e is

resistant to trypsin These facts are not inconsistent since

the identity of the two elastins is not certain and a
.
,

l so the elastic ,

fibres before being bated are limed which may make a very great ,

difference
Ker a
.

tin s —The proteins of the hair and epidermis belong to

.

the class of keratins These substances are quite insoluble in

.

water though somewhat softened by it and are very resistant

, ,

to boiling water except under pressure If heated with water .

at 1 60 C for a long period the keratin is broken up di ssolving

°
.
,

for the most part and evolving sulphuretted hydrogen The

softer keratins are hydrolysed fairly easily by caustic a
.

l kali ,

but hair and horn require strong hot sol utions The action .
1 54 P R I N C I P L ES OF L EA THER MA N UFA C T UR E

of sodium sulphide is rem a rkable ; harder and softer keratin s

'

a l ike are easily attacked A s is well known quite sm a ll .

,

quantities materially assist the unhairing action of lime liquors

Keratins give a
-
.

l l the protein reactions except when insolubili ty

is an obstacle Since a ll the amino acids giving the reactions are
,
-

present e g tyrosine etc The most striking feature in the

, .

'
.
,
.

c h e m ist r y o f keratins is the high content of sul phur due to the ,

presence of large quantities of the amino acid cystine This

“

amino acid is decomposed by a l ka

-
.

-
l ies producing sul phide whi ch ,

in the case of lime liquors soon oxi di ses to sulphate and thio “

sul phate A solution of keratin in a

-

. l kali gi ves a precipitate

( pro bably of proteoses) on acidi fication This pre cipitate whi ch
“

usu a ll y app e a rs when a lime liquor is neutra

.
,

l ised has been pro -

posed as a fill ing material for leather b ut without any very ,

gen eral success .

Mu cin s The mucins are conj ugated proteins termed gluco j

- -

a
.

proteins since the protein is united with a carb ohydrate group

H ence on hydrolysis with c ids the solution obtained cont a
, .

ins
suga r and is able to redu ce Fehling s solution Mucins are easil y ’

soluble in dilute a l ka
.

l i and are consequently removed from hide ,

by the l iming process They can be precipitated by acetic acid

from a l ka
.

l ine solution ( provided t hat no hydrolysis has taken

place) since they are insoluble in excess of acetic acid The
, .

protein comes down as a st ri ngy mass All the characteristic .

protein reactions are given by mucins On e of t h e most character .

ist ic features of mucins is the great viscosity of their solutions

Ca
.

sein — This protein is never found in hi de but is int erest ,

ing in leather manufacture since it is a constit uent of various

finishes and cements It is t he princip a
,

l protein of milk belongs

.
,

to t he phosph oprotein class is of a more pronounced acidic ,

nature than most proteins forming fairly well d e fin e d caseinates

In milk it probably exists as c a
-
.

l cium caseinate and is usuall y ,

prepared from separated milk by aci di fication or treatment with

rennet when it precipitates at once Casein di ssolves in alka
, l is .

and less easily in acids Fe w proteins have been so t horoughly .

investigated as casein but the minor importance of the protein ,

to t he leather industry does not j ustify any di scussion of the

results here
The a l bumins are soluble in water dilute Sa
.

A l bumin s lt
solutions acids and a l ka
l ies and are the typic a
-

.
,

l coagulating
proteins In neutra
, , ,

l solution they are not precipitated by

saturation with magnesium sul phate or h a
.

l f saturation with -

amm onium sul phate but in acid solution some precipitation ,

occurs Ful l saturation with ammo nium sul phate causes com
.
 CHA PTER X II

SOA RI N C A ND S OF TE N I N G OF H I D E S A N D S KI N S

AS has been explaine d in the last chapter hides and skins come
into the h a
,

nds of the tanner either uncured green as they

are taken o ff the anim a
a l preserved with salt or some other
ntiseptic dried o r dry salted in Which both meth ods are
, , _

combined His obj ect in each case is to remove blood and dirt
.
,

and to restore the hide to its soft and natural condition b ut the
a
tr e tment required varies much with the state of the hides .

Fresh hides merely require cleansing from blood and dirt . .

This is necessary because the blood causes bad colour from the
iron contained in its h a emoglobin and both blood lymph and , , ,

adhering dung are sources of putrefaction which ultimately ,

attacks the grain and fibrous structure of the hide Hence .

washed hides keep better than unwashe d Cold water is most .

desirable as checking putrefaction I f the water is much over

,
.

C or if it is charged with organ i c matt er and ferment germs

°
1 0 .
,
-

or if as is too generally the case the hides are in a partially

, ,

putrid state when received the time of soaking must be reduced

as much as possible and it may be n e c e ss a
,

r y t o sterilise the
,

water with carbolic acid or creolin ( pp 21 In such cases the .

,

use of a wash wheel or tumbler is very desirable rapidly cleansing

-

, , ,

the hides and removing adhering dung which interferes W ith the
liming and is a serious cause of damaged gr a
,

,
in f Th e A merican
pattern of wash wheel shown in fig 2 5 is very suitable for t he
purpose In no case is it desirable to a
-
.

. l low green hides to lie

for more than a few hours in water and unwise treatment at
this time is the cause of many troubles which are only detected ,

at later stages and which are very difficult to trace to their

,

source Weak grain in which the grain surface ( p 5 6) is

destroyed and which tans a whitish colour ; pricking o r p e r fo r a
-
.
, .

, ,

tion of the grain with small p in ho l e s which may go on to pittin g ,

with larger holes and a general weakening of fibre with softening

, ,

and nee dl ess loss of weight are among these results A n ,

,
.

instructive instance may be quoted A large tanner found that

his curried lea
.

ther was affected with small [ spots and rings of

darker colour which rendered it quite unfit fo r staining and Which
, ,

reappeared even when the leather was bu ffed When finished as .

1 56
 S OF TEN I N G OF H I D ES A N D S KI N S 1 57

black grain these Spots had a tendency to spue or r ise as little ,

pimples of resinous matter B efore the leather was stuffed no .

defect was noticeable to the eye but either then o r on stripping , ,

the grease by a solvent they coul d be seen under the micro ,

scope as lighter patches of open and porous grain which absorbed

more than their Share of fat During the tanning process they .

coul d hardl y be detected but in the first colouring they appeared

for a few hours as blackish specks a
,

l most exactly like those

caused by particles of iron or iron rust B y careful observation -
.

they were traced back to the limes Specimens of the limed hide
were submitted to Director Eitner who identified the defect as ,
”
Stippen caused by a species of bacteria which cannot subsist
, ,

in limes and which therefore must have been in the soaks

,
.

These which had been somewhat negl ected from pressure of

,

work were cleaned out and sterilised with creolin solution and
, ,

t he mischief ceased It is worth noting that the tanner d ated

.

the beginning of the trouble from the soaking of some Spanish

horse hides which may have introduced the infe ction Sever a
-

,
l .

very simil ar cases have come under the writer s notice ’

.

It is not absolutely necessary to soak fresh hides or Skins at all

before liming and where the water is scarce or unfavourable or
the Skins t a
, ,

i nted or slipping hair it is best to pass straight ,

into a weak lime In this case the limes must b e worked in.

shifts ( see p 1 7 9 ) and the whole of the oldest liquor run away and
the hides rapidly Changed into afresh lime or the limes will
.

become so charged with organic matter and bacteria that the

hides Will cease to plump and may even putrefy
Sa lted hides a
.
,

n d s kin s require more soaking and more thorough

washing than fr sh ones as it is not only advisabl e to remove the

e

sa
,

l t but to soften and plump the fibre which has been deh ydrated
and contracted by s a
,

l ting If goods with salt in them are taken .

into limes they will not plump properly and creases and wrin kles ,

1
( drawn grain) are formed which no after treatment Will remove
This is especi a
-
.

ll y important in sole leather In deciding on a

method we must bear in mind that s a
.

,
l t is easily soluble and ,

di ffuses rapi dl y into water or weaker solutions; but slowly into

strong and not at all into saturated ones It may a l so be noted
sa
.
,

that though salt is not a true di sinfectant ( p l ted hides .

1
T his o p in io n a
is g e n e r l l y h e l d b y t n n e r s , a a
n d t h e r e is n o d o u b t t h t a
s a
lt d o e s o p p o se a
t h e p l u m p in g o f hid e in c u s t ic s o d s o l u t io n s , t h o u gh a
al y a aid ( ai a l iq
'

no t ne r So p o we r f u ll y s in c s s n t he t n uors ) I t is not

ba a a a f d t am at
.

im p r o bl e t h t t h e wr in kl e s n d cre s es r e erre o re ore du e t o w n

of su ffi c ie n t ad ft s w e l lin g n so e ni n g in t h e wa
t p it t h at
er n o t he p r e sen c e
lt m a a
-

of t he s a
lt Sa .
y i n c re s e s we l l in g in un s ha p d l im r en e es .
 P R I N C I P L ES OF L EA TH ER MA N UFA C T URE
are much l ess prone to putrefaction than fresh ones and therefore ,

a longer soaking may be safely given .

These conditions point to the desirability of free exposure to

water attained by suspending handling frequently or tumbling
, , , ,

and repeated changes to remove the salt The degree of removal

of s a
l t is easily determined by the estimation of C1 in the last
wash water (L I L B p
-
. A merican tanners universa
. . . . ll y soak

FI G . 25 .
— A m e r ic aW ah —wh
n s e el .

wet sa
-
l ted hides three or four days with as many changes of water ,

and frequently finish b y a few minutes in a wash wheel A n y -

.

a
washing tumbler may be used but the cheap and simple con
struction of the A merican w sh wheel Will be easily understood -

a
from fig 2 5 The sides are open so that hides can be put in or
. .
,

removed between the spokes The rim of the Wheel i s gener l ly

perforated for the escape of water W
.

hich is supplied by a pi pe ,

passi ng throu gh the axis ; and the wheel is often driven by a

chain or rope round its circumference No s evere mechanical .

”
treatment such as stocking is necessary or desirable for green
or s a
, ,

l ted hides .
1 60 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

warm weather there would be little danger of putrefaction With

harder drying longer time is required a
.
,

n d more vigorous measures ,

may be necessary A well known tanner recommended a brine

.
-

of 3 0 to 3 5 barkometer ( sp gr 1 0 3 5 or about 5 per cent of

° °

Na This has a
. . .
,
'

Cl ) . do u bl e action not only preserving from putre ,

fact ion but dissolving a portion of the hide substance which is

,
-

undoubtedly a loss to the tanner though it is questi onable if there ,

is any process which wi ll soften overdried hides without loss of

weight since even prolonged soaking in cold water at a tempera
ture which is too low t o allow of putrefaction taking place will
dissolve a serious amount of the hide constituents Chlorides -
.
,

however do not seem well adapted for the purpose in view

, ,

from their weak antiseptic power and t endency to prevent

swel ling Jackson Schulz advised the use of water at 80 F °

for soaking during the winter months Water cont ining a sm a a

. .

a
qu ntity ( 0 1 per cent ) of carbolic acid has been recommended
for the purpose and will prevent putrefaction whil e it ha
-

s no
ll
.
.

, , .

solvent p ower on the hide but o n the contrary ten ds to coagulate

and render insoluble a
, , ,
’

l buminous matters B orax has been pro .

posed for the same purpose and in 1 per cent solution certainl y , , .
,

prevents putrefaction and has considerable softening power but

is far too costly Other m ethods of chemic a
, ,

.l softening are
described on p 1 6 1
Fo r some descriptions of hides a
. .

nd notably for India kips , ,

putrid soaks were formerly much employed the putrefactive ,

action softening and rendering soluble the hardened tissue In .

I ndia the native tanners soften their hides in very few hours by
plunging them in put rid pools into which every description of
tannery refuse is a
,

l lowed to r u n P utrefactive processe s how

ever are a
.
,

,
l ways dangerous as the action through changes of , ,

temperature or variation in the previous state of the liquor is

, , ,

apt to be irregular and either to attack one portion of the hide

,

before another or to proceed faster than was exp ected Hides

, .

are also frequently more or less damaged by putrefaction and

heating during the process of cure n d these damages are
’
,
a '

accentuated in a putrid soak Hence hides in the soaks Te qu ir e .

-

constant and careful watching and the goods must be withdrawn ,

as soon as they are thoroughly softened for the putrefac tion ,

is constantly destro yi ng as well as softening the hides It is

a
.

possible that putref ctive softening is less inj urious to kips and ,

such goods as are intended for upper leather than to those for
sole p urposes as it is genera
,

l ly considered ne c essary in the

former case that a good de a l of the albumin and in t er fib rill a
,

ry

matter be removed and that the fibre be well divided into its ,
 S OF TEN I N G OF H I D E S A N D S KI N S 1 61

constituent fibrils for the sake of softn ess and pliability ; and
thus the putrid soak if acting rightly ccomplishes part of the , ,
a
work which would afterwards have to be done by the lime and
the bate as the actual fibre of the hide seems less readily p a
a
,

cible th n the softer cementing substance

P utrefaction is caused as we have seen by a great variety of
tres
.

living organisms each of which has its own speci a

, ,

,
l products and
modes of action It is quite possible that if we knew what precise
.
,

form of putrefaction was most advantageous we might by appro

p ria
,

t e conditions be able to encourage it to the exclusion of ,

others and obtain better resul ts than at present Putrid soaks

( in the old sense ) are however disused in the present day by a
.
,

,
ll ,

enlightened tanners as it is recognised that the risks outbalan ce

,

the ad vantages and when dry salted hid es are worked the soluble
,
-

salts of the cure accumulate in the soaks to an inj urious extent .

Th e modern method where no chemicals are used is to give one

, , ,

fresh water at least to each pack of hides or skins Even in this .

case considerable putrefaction takes place where the soaking

occupies seven t o fourteen days as is the Case with kips a n d hides , ,

and there is no doubt that the use of chemical and antiseptic

m ethods of soaking will ultimately be generally adopted both on ,

technical and sanitary grounds .

The use of dilute acids for softening has much to recommend

it their power of causing the fibre to swell and absorb water
being at least equ a l to that of the a
,

l kalies while few if any , , ,

putrefactive bacteria can thrive in an acid liquid Very dilute .

sulphuric acid has be en used with success to dissolve the alkaline

“
plaster Of East India kips ( p I t has considerable dis .

infectant power ( p but its action on the hide fib r e is

.
-

undesirably strong .

Sulphurous acid is much more suitable It s use for this pur

pose was patented by Maynard along with anumber of other
.

possible uses but the patent has long lapsed and he did not
, ,

seem to have succ eeded in introducing it into practice Ex p e ri .

ments at the Y orkshire College ( now Leeds University) and also

at a tannery on amanufacturing scale have shown that the
,

method is capable of excellent results The hides are soaked for .

twenty four to forty eight hours in a solution of sulphurous acid

- -

containing about 2 per cent of 5 0 2 ( for manufacture compare

and a
.
,

p 2 4 ; for test i ng
. pp 1 6 ,
r e then transferred .
,

to water where they swell freely to their full thickness They

,
.

may be either limed at once or first neutralised with dilute caustic ,

soda ammonia or sulphide of sodium which for dressing leather

, , , , ,

is perhaps desirable No putrefaction takes place even if they are

.
,

1 1
1 62 P RI N C I P L ES OF L EA TH ER MA N U FA C TUR E .

retained for a considerable time in water a n d the acid has little ,

or no solvent effect on the hide fib r e the strength of which is -

, .

well preserved The liming however must either be conducted

.
, ,

with the aid of sodium sulphide or in old limes since the sterile ,

condition of the hides renders liming in fresh lime very slow

( cp p Fo r experimental purposes a per cent solution
"

of B o a
. . .

ke s metabisulphite of soda may be used to which

’”

I per cent of concentrated sulphuric acid previously diluted

with water is gradu a
.

l ly added during t he soaking t he hides being

first withdraw n Fo r regul a
,

r work it will be found much cheaper

.

to manufacture the acid on the spot by burning sul p hur . .

The use of solutions of caustic soda ( 1 to 2 parts per or

of sodium sulphide ( 1 % to 5 parts per 1 000 ) as suggested by
Eitner Seems at present likely to supersede a
,
l l other meth o ds of
soft ening from their simplicity and safety Twenty— four to forty .

eight hours in either of these solutions which may if necessary ,

be followed by a short soak in plain water seem su fficient to ,

soften either kips or hides Experiments at Leeds University .

have shown that solutions of this strength have little or no solvent

action on th e hide — fib r e but promote its swelling in wat er so
e ffectively t h at n o mechanic a
,

l softening is needed ( though a slight

drumming is advantageous) while putrefaction is almost ent irely ,

prevented so that the solution may be repeatedly used if kept up -

to its original strength which is easily determined wit h s t a n da

,

,
rd

acid and phenolphthalein ( see p Neither caustic .

soda nor so dium sulphide have any inj urious e ffect on liming
“

though it may p rove somewhat slower than with t h e older

methods where the epi dermis Wa
,
s partially destroyed by the

action of putrid ferments The dilute solutions used are not .

only less inj urious to the hide than those of greater stren gth but ,

they are also more effective in softening Eitner ( Ger ber 1 89 9 .

,
‘

p 5 84) states that whe n using a solution of caustic soda of 1 p art

.

in 1 000 strength the time required to soften some hides was

only t wo d a
,

s as against three days for a sodium sulphide liquor

y .
, _

and four days for pure water and that with the soda solution ,

only about 0 6 per cent Of the hide substance of t he skin was

-
.
-

dissolved out whilst when sodium sulphide was used it was 0 7

,
-

per cent and with pure water alone no l e SS than 1 9 per cent
.
-
.

was lost by solution .

Th e use of moderately warm water ( 40 C ) in a drum is quite

°
.

successful in rapidly softening sound hides after they have

previously been soaked for some days in cold water but if they
are tainted in the cure it is very apt to intensify the mischief ,
.

Hides which have partially p u t r e fie d i nternally or which have ,

1 64 P R I N C I P L E S OF L EA TH ER MA N UFAC T UR E
soaked again for a ShO r t time and then be brought into an old
li me A small quantity of sodium sulphide adde d t o the soaks
,

or in the stocks has been recommended as of great value in soften

.

FI G . 26 . a
— F ll er St o c k S ..

FI G . 27 .
— A m e r ic a
n H i d e m ill
-
.

ing obstinate hides a n d probably with j ustice

,
from its well ,

known softening action upon cell ular and horny tissues

Tumbler drums of various forms ma
.

y also be used with good

e ffect for softening purposes especially for skins and are much
, ,

less detrimental than stocking both as regards the weight and ,

quality of the goods ,

 S OF TENI N G OF -

H I D ES A ND S KI N S 1 65

Fo r sole leather and even for kips the use o f stocks has in
, ,

recent years been entirely discarded by many of the more

a
advanced t nners If mechanical work is required at a
. ll t h e
dru m is preferred and is sometimes empl o yed after a few days
,
’

liming the goods bein g first merely softened in fresh water The
,
.

FI G . 28 .
— Dr u m fo r Wa
sh in g or T ai nn ng .

use of caustic soda sodium sulphide or sulphurous acid usually

renders mechanic a
, ,

l softening unnecessary .

The drums employed are in principle like a barrel churn and -

are large cylindrical wooden chambers 6 to 1 2 feet in diameter

'

and fitted inside either with Shelves like the floats of a water
wheel or with rounded pegs on which the hides fall
, The .

A merican wash wheel fig ured on p 1 5 8 is a machine of this kind

-
.
,

and one of a more elaborate description is shown in fig 2 8 , . .

Drums are not only used for softening but for tanning dyeing
' ‘

and many other purposes in leather manufacture It is a dva

, , ,

ta
.

g eo u s to be able to reverse the direction of their rotation to

prevent the rolling up of the hides .
 CHA PTER X II I
D E P I LA TI ON

A FTE R the softening and cleansing of the hide or skin is com

p l e t e d and before proceeding to tan it it is usu a
,
l ly necessary to ,

remove the hair or wool The earliest method o f accomplishing

this was by me a
.

ns of incipi ent putrefaction , which attacks in the

first instance the soft mucous matter of the epidermis and thus

a
,

loosens the hair without materially inj uring the true Skin This .

loosening of the hair often takes pl ce accidental ly in hides

which have been kept too long without salting and is known ,

as slipping and is apt to be accompanied by some degree of

,
“

inj ury to the grain The o l d m e t h o d of loosening the hair by

sweating wa
. .

putrefaction or as it is generally cal led s to

lay the hi des in piles usually in some warm a n d da

, , , ,

mp place
'

Occasion a ll y a slight preli m inary s a

.
,

l ting was given to prevent

too much putrefaction of t he hide The action in this ca se
“

-
.
,

however was very irregul ar and it has been quite abandoned

, ,

in all civilised countries .

A method which is stil l used to some extent in A merica pri nci

pa
,
v

l ly on dry hides i s to hang t he hid es in a closed chamber

‘

generally c a
_ ,

l led a sweat pit fig 2 9 but usually constructed

above the ground level a
-
.
, ,

n d p r o t e c t e d from sudden changes of

'

-
e

temperature by double wall s or by mounds of earth The , .

hides are hung in the sweat pit in small chambers each capable -

a
of holding 50 or 1 0 0 hides The temperature is kept at about .

1 5 to 2 0 C the ir being warmed if necessary by the admission

° °
.
, , ,

of steam below a perforated floor or cooled by a shower of water

from sprinklers SO arranged a
,

s not to play di rectly on the skins

and is thus always kep t saturated with moisture Little if a

, ,

ny

ventilation is a l lowed and a l a

.

r ge quantity of ammonia is i ven

, g
o ff from the decomposition O f the organic matter and no doubt ,

cont ributes to the solution of the epidermis and the loosening of

the hair as the writer has found that ammoniac a
, l vapours a l one
very speedily produce this e ffect It may here be suggested
that the u s e of ammoniacal gas for sheep skins deserves practica
.

l -

trial as the loosening of the wool is very rapid and no injury

,

a
,

is done either to it or to the pelt The ammonia could be r e

covered by passing the air o f the chamber through n a
.

cid
1 66
1 68 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

itself c a usm g
,
weak grain It s most advantageous use is for .

sole leather as although the solution of the hide substance may

, ,
-

not be very much less than i n the case of liming the di ssolved
matter rem a
,

ins in the hide instead of being washed out and ,

being fixed by the tannin contributes to the solidity of the ,

"

leather
I n England lime is the agent almost univers a
.

ll y employed for
unhairing ( now a l most invariably with the addition of a
,
'

l kaline
sulphi des) though every tanner admits its deficiencies and dis
,

advantages It is hard hOwe ver to recommend a substitute

which is free from the same or greater evils a nd lime ha
.
, ,

s one

or two valuable qu a l ities which will make i t very di fficul t to

supersede On e of these is that though it inevitably causes loss
of substance and weight it is a
.
,

l so impossible with any reasonable

, ,

care totall y t o destroy a pack of hides by its use which is by

no means the case with some of its riva
,

ls A nother a d vantage . .

is that owing to the very limited solubility of lime in water it is

of comparatively sm a
, ,

l l consequence whether much or little is

used and even if the hides are left in a few days longer than
necessary the mischief though certain is onl y t o be detected by
careful and accurate observation With a
, , ,

l l other methods exact

time and quantity are of pri mry importance a a
.
,

n d it is not easy ,

to get ordinary workmen to pay the necessary attention to such

details A gain the qualities of li me its virtues and failings
'

have been matter of experience for hundreds of years a

.
, , ,

nd S o ,

far as such experience can teach we know exactly how to deal ,

with it A new method on the other hand brings n ew and

.
, ,

unlooked for difficult ies and often requires changes in other

-

parts of the process as well as in the mere unh a

a
,

,
i ring to make -

it successful A s our knowledge of the chemic l and physical

.

changes involved becomes greater we may look to overcoming ' ’

these obstacles more readily

,

Th e universal source of lime i s chal k or limestone which con

sists of c a
,

l cium carbonate and from which the carbon dioxide ,

is driven off by burning in a kiln Many limestones however

are far f rom being pure c a
.
, ,

l cium carbonate but contain large

proportions of magnesia iron and a
,

l umina the latter perhaps

, , ,

original ly deposited in the form of clay with t he s e dim e n t from

’

which the stone was formed Such Clay limestones when burnt .

yield n atural cements like oolite and other hydraulic limes

‘

, ,

which are capable of setting even under water The presence .

of magnesia and clay is inj urious not only by diminishing the ,

amount of lime present but by making the lime much more ,

difficult to slake and iron oxide though quite insoluble may , ,

 D EP I LA TI ON 1 69

become mechanically fixed in the grain of the hide and may -

be the cause of subsequent stains The burning of lime in the .

kiln is probably not quite so simple an operation as the equations

of the text books wo ul d suggest B y mere heating the carbonate
-

can it is true be decomposed but to do this completely a good

, , ,

white heat is required which is rarely attained in practical ,

burning and it is probable that at least a part of the carbon

,

dioxide present is reduced to carbon monoxide by the com

b u s t ib l e fuel gases and so separated from the lime for which
-

, ,

it has no affinity Carbon monoxide is the cause of the intensel y .

poisonous character of lime kiln gases the pure dioxide being -

irrespirable but not strictly poisonous

Q uic klime Ca
.
,

O on coming in contact with water combines

with it with the evolution of considerable he a
, , ,

t becoming slaked
or converted into hydrate Ca
,

( OH) 2 This change takes place ,

.

rapi dl y and easily when the lime is light and porous such as is
obtained by the burning of ch a
,

l k or good limestone at a low ,

temperature but if it has been too intensely heated or over

burnt or contains silicates or other s a
,
l ts which fuse at the
temperature of the kiln a compact lime is formed which slakes ,

with difficulty and ext reme slowness thus being lost to the ,

tanner or leading to the still more serious result Of b urning holes

,

in the hides by the heat produced by slaking in contact with

them It is stated by Le Chatelier that for dense limes twenty
.
1

four to forty eight hours is frequently required for complete

"

slaking in the cold while magnesia is still more obstinate months

being sometimes necessary for t he co m
, ,

plete hydration o f hard

burnt sam ples ; and mixtures of lime and magnesia are inter -

mediate in their character Slaking is greatly assisted by heat .

,

even heavily burnt magnesia being hydrated in about six hours

a
at 1 00 C Slaking is also much more rapid in a dilute solution
°
.

( 2 per cent ) of c lcium or magnesium chloride From these

'

. .

facts it is easy to deduce the reason why a suitable quantity of

water neither too much nor too little is desirable for the rapid
and effectu a
, ,

l slaking of lime If too little is used the lime is .

,

only partially slaked and it is not easy for further portions of ,

water to gain access to the interior Of the powdery mass On .

the other hand if it is drowned by excess the temperature

“

“
, ,

is lowered the process goes on slowly and the mass does not
, ,

readily fall into powder and so fails to be utilised in the liming

process Of a
,

ll methods of slaking lime the ordinary one of

.
,

tipping it direct into the lime pits is perhaps the most irrational -

1
B u ll . de l aS oc . a
d E n co u r ge men t
’
,
1 89 5 , x .
pp .
52
—
62 ; jo u r n . S oc .

Chem I n d. 1 89 5 , p .
57 5 .
1 70 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E
leading to the formation of unsl aked lumps which may b u rn t he
'

hides and which together with stones and dirt rapidly choke
, , ,

the pits with useless matter The best process is that adopted
by builders and in many Continent a
.

l yards in which a large

quantity of lime is slaked in a sh a
,

l low tank by th rowing o n it

a
.

sufficient water to thoroughly wet it and after llowing it to

, ,

heat and fall for t wenty four hours adding enough water to -

convert it into a sti ff paste In this form it may be kept for .

months without material deterioration When required for u se .

,

a suitable quantity of the paste is dug out and well stirred with ,

water in a tub or tank before running i nto the p it when the stones
a n d sa n d rem a In this way a
_
,

i n in the tank l l nui sance from dust

'

is a
.

l so avoided If lime is stored unslaked it gradual ly ab sorbs

m oisture from the air f a
.
,

l ling and s o on becoming dusty and

, ,

difficult to slake c o mp l e t el y whil e the traces o i carbon dioxide ‘ -

in the air gradu a

,

l ly convert it into useless carbonate .

The solubility of lime in water is very limit ed and the figures ,

determined by di fferent ch emis ts do not agree very satisfactorily .

The foll owing table gives the result of determinations made by

Mr A Guthrie in the A uthor s laboratory and is probably one
.
’

of the most accurate : 1

1 00 of saturated contain grm .

0 1 -

3 42
0
-
1 3 20
0 1 29 3
-

0 1 2 54
-

0 1 21
-

9
0 1 1
-
61
0
-
1 1 1 9
0 09 81
-

0 0 87 9
-

0 07
-
81
0 0 7 40
0 0 69 6

Itwil l be noticed that unlike that of most subst nces the

solubility of lime in water diminishes as the temperature is
a ,

raised It is therefore necessary in employi ng lime water a

. s a -

standard solution to take care that it is saturated at a constant

temperature The results given in the above table are those
.

from pure marble lime Wh ere the ordinary impure limes from
.

limestone are employed a somewhat stronger lime water is often,

-

1
jo u rn . S o c Che m I n d
. . .
,
1 901 , p . 224 .
1 72 P R I N C I P L ES OF L EA TH ER MA N UFA C TUR E

contained an appreciable quantity of iron oxide whi ch might ,

lodge mechanically in the pores of the skin and become dissol ved
in later processes darkening the colour of the leather The lime
was a
.
,

l So under burnt j udging from the amount of carbonat e it

-

contained .

Fo r comparison with this the analysis of a good specimen of

carboniferous limestone lime from Buxton ma
,

y be given
-

C O a
MgO
COZ and moisture
I OO OO
’

D etermin tio n a o practical value of

f aa
A v il bl e Lime .
‘
—The
lime for the tanner is easily determined by drawing a sample b y
breaking o ff small pieces from a number of lumps of the bulk ,

coarsely pulverising them in a mortar and then rapidl y grinding ,

a porti on as fine as possible and transferring it at once to a ,

stoppered bottle for weighing A portion of this, not exceeding .

1 grm is shaken into a stoppered liter flask which is filled up

.
, ,

roughly to the mark with hot and well boiled distilled water and
allowed to stand for some hours with occasion a
-
.

l shaking When .

cold it is fil led exactly to the mark with cold distill ed water ,

well shaken again and allowed to settl e or rapidl y fil tered and

a
, ,

2 5 or 50 c c of the clear liquid withdrawn with a pipette and

titrated with N]I O hydrochloric or sulphuric cid a

. .

nd phenol
phth al ein Each cubic centimetre of N/i o acid equals 00 2 8
If it be desired to determine separately the alka
-

grm Ca
.

O l ies
which may be present standard N/1 0 oxa
. .

l ic acid may be sub

stituted for hydrochlori c and after exact neutralisation a portio n ,

of the fil tered solution may be acidi fied and titrated with stan
dard permangan ate for soluble oxa
,

l ates but it is extremely ,

rare that alkalies are present in such quantity as to j ustify t hi s

trouble The process is unfortunately not applicable to used
.

lime liquors as they contain organic matter which wo uld also

-

reduce the permanganate .

It is generally a very mistaken economy to make use of an

inferior lime for tanning purposes as any saving in cost is di s
counted by the larger qu ntity required the more frequent
cleaning of the pits and the danger of stains and of burns from
,
a ,

imperfect slaking
The action of lime on the h ide has a
.

l ready been spoken of to

some extent It is throughout a solvent one The hardened
. .
 D EP I L A TI ON 1 73

cells of the epi dermis swell up and soften the muc ous or growing ,

layer and the hair sheaths are loosened and dissolved so that on
.
-

, ,

scraping with a blunt knife both come away more or less com ,
”
p l e t e l y with the hair ( constituting scud or scurf Ger Gn eist
0 1 Gr a
.
,

n d) Th e hair itself is very slightly altere d except at its

.
, ,

soft and growing root bulb but the true skin is vigorously acted -
,

on The fibres swell and absorb water so that the hides become
plump and swollen and a
.
,

t the same time the cement sub , , ,

-

stance o f the fibres is dissol ved and they become split up into ,

finer fibrils : the fibrils themselves become first swollen and

transparent and fin a l ly corroded and even dissolved
,
A similar , .

swelling of the fibres is produced by both alkalies and acids and ,

is due to weak combinations formed with th e fib r e substance ‘

which have greater swelling power than the un a

-

1
l tered hide This .

swelling is useful to the tanner since it renders the hide easier ,

to flesh ( i e to free from the adhering flesh ) on account of

. .

the greater firmness which it gives to the true Skin It also .

as sists the tanning by splitting up the fibre int o its individual ,

fibrils , and so exp osing a greater surface to the action of the

a
liquors This is advantageous in dressing leather which is after

a
.

w rds tanned in sweet liquors and which must have the cement ,

subst nce of the fibres dissolved and removed for the sake of

a
flexibility ; and in the case of sole leather i t is necessary for
, ,

s ke of weight and firmness that the hide b e plumped at some

stage of the process ; but it is probable that this e ffect is pro
du c e d with less loss of substance and solidity by suitable acidity
of the tanning liquors Another advantage of lime is that it acts
-
.

on the fat of the hide, converting it more or less completely into

a n insoluble soap
2
and so hin dering its inj urious effect s on the
-

,
‘

after tanning process and on the finished leat her I f stro ng acids ‘

-
.
,

whether mineral or organic are used later on this l ime soap , ,

-

is decomposed and the grease i s agai n set free In sweated or

, .

very low limed hides this grease is a formidable evil causing

a
-

d rkenin g o r grease spots on the finished leather

'

The customary method of liming is simply to lay the hides

horizontally o n e at a time in milk of lime in large pits taking care ,

tha t each hide is completely immersed before the next is put -

into the pit so as to ensure a sufficiency of liquor between

Once a d a a
,

them .
y t least the hide s should be drawn out _

hauled the pit well plunged up to distribute the undis

a
solved lime through the liquor and the hides the n drawn in ,

again set c are being t ken that they are fully spread
'

1
Cp Ch p t e r X a
a a a
. .

2
T h is h s b e e n qu e s t io n e d b u t I h , v ti fi
e s s ed m ys e l f it is c o rre c t .
1 74 P R I N C I P L ES OF L EA TH ER MA N U FA C T U R E

out Neglect of this to save labour is very unwise Ho w

. .

much lime i s required is doubtful but o wing to its limited ,

solubility an excess if well slaked is rather wasteful than

, , ,

i nj urious Great di fferences exist in the quantity of the lime

.

used the time gi ven and the method of working not only
, , ,

for various classes of leather but for the same kinds in ,

di fferent yards Lime as we have seen is only soluble to the

.
, ,

extent of about 1 2 5 grm : per liter ( as 1 cubic foot of water

-

weighs about 1 0 0 0 say 1 1 oz per cubic foot or in an ordinary

lime pit not more t ha
.
, ,

-
n 1 l b per hide
,
Only the lime in solution . .

acts on the hide but it is necessary to pro vide a ,surplus of solid

,

lime which dissolves as that in the liquor is consumed or absorbed

by the hide and this is especially the case where as is genera l ly ,

customary the hides are laid flat in pits so that no circulation

, ,

of liquor is possible Where hides are suspended in lime water .

-

which is constantly circulated and kept up to it s full strength

by agitation wit h solid lime they unhair more quickly than when ,

laid i n milk of lime and the method seems t o be gradually ,

Superseding the older one especi ally in dealing with more

“

soluble depilatories V arious patents have been taken for.

methods of liming by suspending in liquors but the idea is now ,

public property and is largely used on the Continent It is

“
'

, .

necessary that the lime which settles to the bottom of the pit
should be agitated and kept in suspension which may be e ffected ,

either by m oving the hides on a frame as i n suspenders

_
“

( p . or by agitators acting on the principle of p umps and ,

raising the liquor and sludge from the bottom Such agitators .

have been patented in German y but had been in u s e much ,

earlier in the A uthor s tanyard An agitator on the principle of ’

the screw—propeller of a steamship placed near the bottom of ,

the pit and pro t ected by a lattice has been much emplo yed on
, ,

the Continent ( fig .

In England suspension methods though kno wn for many

, ,

years and in use in a few tanneries received but l ittle attention ,

before the war ; but recently the saving of time hide substance ,
-

and labour which can be e ffe c t e d b y suitabl e mechanical sus _ .

pension and agitating appliances have led to their adoption in

many large yards often a s more or less secret or patented pro
,

cesses though it would be difficult to fin d a mechanical device

,

which has not been used in times past Such methods have the
a
.

disadvantage of increased cost of plant n d the use of more pit ,

space than is required by hides lying flat though the latter is ,

largely cancelled by the shortened time of the process and

diminished quantity of lime require d The constantly increasing
1 76 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E
b in e dwith means of mechanically handl ing the hides and r e
moving them from p it to pit 1
.

Skins are frequently limed in paddles or stirred up b y blowing ,

air into the pit The latter method is neither e ffective nor
.

economical in power for loose skins but very convenient for ,

suspended hides .

A s has been noted the solubility of lime and consequently , ,

the strength of the lime liquor is diminished by rise of tempera -

ture but its solvent action on hide substance i s much increased

,
- -

A s a consequence the l oosening o f the hair proceeds much more

,

rapidly in warm limes but the hides do not plump well and , ,

become loose hollow and inclined to pipe in the grain and to

, ,

weigh out badly and for sole l eather t h e m e t ho d is therefore in

,

every way disastrous In the few cases among the lighter leathers
.
,

where a decided softening and loosening of the texture of the Skin

is required it is possible that useful advantage may be taken of
,

this effect but it would be exceedingly d ifficult to regulate the

temperature of an ordinary lime pit with accuracy and better -

results could probably be obtained with suspenders in which the

liquor coul d be constantly c irculated Wh en limes are very
“

cold in spite o f the greater strength of solution the action is

, ,

very much checked and wh ere goods are frozen into pits in ,

severe weather there is but little danger of over liming although

,
-

the usual time may be much exceeded I t is general ly best to .

work limes at about the ordinary summer temperat ure and this ,

is better done in Wi nter by Warming the lime yard than by any -

direct heating of the limes If lime which has cooled after slaking
a
.

is used the water with which l imes are made m y safely be

,

warmed in midwinter to a temperature not exceedin g 2 0 C °

.

a
The quantity of lime used by di fferent tanners and for di fferent ,

sorts of hides and skins is very v riable not onl y according t o , ,

the effect which it is desired to produce and the way i n which ,

it is used but from the arbitrary fancy of the user since its
, ,

limited solubility renders an excess comparatively innocuous .

F o r sole leather the amount recommended vari es from under

,

1 per cent to 1 0 or 1 2 per cent on the green weight of the hide ;

. .

but probably 2 to 3 per cent is all that can be really utilised the .
,

remainder being wasted In order however to utilise the Whole .

, ,

of the lime very frequent handling o r agitation is required to

, _

ensure its uniform distribution It must also be borne in mind .

that the strength of commercial limes varies from above 80 down

to 3 0 per cent of available calcium oxide
. .

Vo n Schroeder has found that a strength of 6 g r m s of calcium .

1
Se e E n g P t s . a . 1 1 7 581 ad
n 1 2 49 92 .
 D EP I L A TI ON 1 77

oxide ( Ca O) per liter was su fficient but in practice much more , , ,

is generally added It is also not eworthy that a perfectly fresh

.

milk of lime is much less rapid in action t han one which has
been used This is parti a l ly due to the fact that some bacterial
action takes p l a
.

Ce in an old lime and that ammonia is formed

which assists unhairing in addition to the effect of the lime
itself and parti a
,

, lly because the lime in old liquors remains in “

suspension for a much lon ger time and is thus more evenly ,

distributed .

A method of liming sometimes known as the B u ffalo method , ,

has been largely adopted for sole leather in A merica , and is now
used in many Continental yards It consists in a very short .

limi ng and the subsequ ent use of warm water The limes are .

also often sharpened by the addition of a little sodium sul phide

or of some other sulphide Thus in one large ya r d in the States .
, _ ,

the hides for sole l eather ( salted packers are l imed for ten
hours only with 2 lb lime and 2 oz of sulphide of sodium per . .

side and after lying overnight in water of a temperature of

,
“

3 5 to 4 5 C are easily unhaired A Continental firm lime two

° °
. .

days in weak fresh limes with a little t ank waste and then treat -

with water at 3 2 C for six to e ight hours when the hides are
°

unhaired and returned to the wa

.
,

rm water for two hours before

scud di ng All sorts of combin t ions between liming and hot
. a
water treatment can be employed The longer and stronger the
. .

liming the lower temperature or shorter time in the water will

,

suffice The method is much to be recom mended for firm sol e

leather but it does not s a
.

,
ponify grease or swell the fibres
thoroughly and usually sulphuric acid is used for the latter
,

purpos e in a later stage The hide goes into the liquors prao
‘

. .

tical ly free of lime and the loss of hide substance is much

'

less than in the ordi nary method of liming .

A point of probably much greater importance than the quantity

of lime used is the l ength o f time during which a lime is worked
without change of liquor A n old lime becomes Charged with .

ammonia and other products of the action of lime upon the skin ,

such as tyrosin leucin ( aminocaproic ac id ) and some caproic

, ,
'

acid the disagreeable goaty odour of which is very obvious on

,

acidifying an Ol d lime liquor with sulphuric acid by which con

sid e r a
-

b l e quantities of partially altered keratin s are at the same

time precipitated ( op p A test supposed to indicate dis
“

solved hide substance in old limes ha

. .

-
s been employed in some

yards in which the liquor is slightly acidified with acetic aci d

and an equ a
, ,

l vol ume of saturated salt solution is added whe n , ,

on standing a precipitate rises to the surface the volume of

, ,

1 2
1
78 [
P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

which is supposed to indicate the dissolved hide substance -

.

( Cp L C
. p . It has been recently shown in the
.

P rocter International R esearch Laboratory that actual dissolved

hide substance is not precipitated under these conditions n d
-

, a
t hat the precipitate formed is entirely derived from the
al buminoids ( keratins) of the hair and epidermis which it is ,

the definit e obj ect of liming to dissolve 1

.

Lime has considerable antiseptic power and a new lime is

'

practically sterile but y ery old limes especially in hot weather

, , ,
“

often contain large numbers of active bacteria which may be ,

seen in the microscope under a good inch obj ective Their -

.

presence is always an indication that putrefaction is going for

war d and if their number be very excessive the leather out of
such limes will generally prove loose hollow a
, ,

n d dull g rained , ,
-

and in e xtreme cases hides may be totally destroye d Spherical

concretions of calcium ca rbonate may a
.

l so be s een un der the

microscope resembling on a sm a l ler scale those found in P ermian
limestone and C au sed perhaps in both cases by cryst a
,

,
l lisation
from a liquid containing much organic matter It is hardly .

probable that in many tanneries the ammonia would pay for

recovery from the l ime liquors though it c ould be easily done b y-

,
-

steaming the old limes in suitable vessels and condensing the ,

ammoniacal vapours i n dilute sulphuric acid It s quantity rarely .

exceeds 0 1 per cent of NH3 Fo r methods of estimation of

-
. .

ammonia see p 3 0 and p 39 .

,
. .

U p to a certain point it is found that o l d limes unhair much

m
a
ore readily and have a greater softening effect than new ones
, ,

which i s often advant geous for dressing goods ; though for sole
l eather where weight and firmness are of pri mary importance
, ,
,

the use of stale limes must be kept within the narrowest limits .

I n the finer leathers al so such as kid and mor occos and colour ed ,

calf where a sound and glossy grain is desired the e ffects m e n

, ,

t io n e d are g enerally better Obtained in other ways such as by ,

the use of sulphides On East India kips and other dri ed hides
.
,

which are di fficult to soften and which have great power of ,

resistance to the action of lime o l d li mes are distinctly useful , ,

but even there there are limits which Should n o t be passed

, , ,

and the tendency of modern practice is against their use .

Probably no lime ought to be allowed to go for more than

three months at the outside limit without a change of liquor
and the system of allowing a
,

ll the limes in a yard to run for

“

twelve months and then cleaning them all together is almost

the worst which can be planned A very much better Wa
, ,

y is to .

1
Th o m p s o n ad A t ki
n n, 1 9 20 , p . 1 5 .
1 80 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

The part s taken by the purely chemica l activity of the lime ,

and by the action of bacteria and bacterial ferments in the u n

hairing process must still be r egarded as uncertain The late
Professor von Schroeder c a
.
,

1
rried out a series of experiments on
'

li m ing and sweating which were characterised by his usual care

and thorou ghness and which tend to prove that the chemic a l
action is fa r more important than the bacteri a
,

l He had fresh .

hides well Washed in a t annery immediately after slaughter and ,

fleshed The butts were then cut into pieces or about 1 0 cm

sa a
. .

(4 inches ) square and l te d in brine repe te dl y changed and

fin a l ly preserved for use in glass j ars in saturated s a
, ,

l t solution .

He found that when washed free from salt and p laced in a moist ,

chamber at a temperature of 1 6 C the hair was su fficiently °

loosened by bacteri a
.
,

l action in fo ur to five days Pieces placed

in t he moist chamber without previous remova l of the s a
.

l t only
showed signs of sweating after about ten weeks exposure ’
.

Liming experiments were made with Similar pieces of salted hide

both after three days wa
,

shin g t o free them from salt and n u

’
.

and in both cases the pieces unhaired freely in three -

to four days These experiments were vari ed by using 6 1 8 and

.
, ,

3 0 grm s of lime per litre of water in whi c h about 2 00 gr m s of

. .

hide were placed but neither in the washed nor unwashed portions
was there any materi a
,

l difference in the time required to loosen

-

the hair A ddition of 1 vol of used lime liquor to 3 vols of

water in making up the limes was equ a
-
. . .

l ly without perceptible
influence and careful bacteriologic a
.

l examination of hide and

liquors showed that the former wa
,

s almost steril ised by t he

intense salting and that the lime liquors were practic a

, l ly free -

from bacteria
Vo n Schroeder s conclusion t hat no gain a
.

’
rises from the use
of excessive quantities of lime so long as the solution is kept ,

saturated is fully j ustified both by experience and scientific

,

reasoning but his resul ts with regard to the e ffect of o l d liquors

and bacteria contradi ct the conclusions both of practic a
,

l tann ers
and of other scientific experimenters
The di fferent effects of old and n e wlimes are too well known
.

to practic a l tanners to be discounted by laboratory experiments ,

even if they were not confirmed not only by Eit n er s resul ts but ’

by a considerable amount of work done in the A uthor s labora ’

tory and elsewhere while the necessity of bacteri a l action is at

least rendered probable by the fact that soda solutions which are
completely sterile to bacteria fail to unhair hides which have not ,
'

previously undergone some putrefaction ( see p In some .

1
Ger be rei Chemie B e r l in ,
-

,
1 89 8 , p 6 46. .
 D EP I L A TI ON 1 81

experiments undertaken at the suggestion of t he A uthor it was

a
found that a perfectly fresh and sterilised calf skin which was not
unh ired after ten days liming in sterilised lime liquor unhaired
rapidl y on the addi tion of a bacteri a
’

l culture to the lime I t is

-

extremely difficult to exclude bacteria and even where perfectly ,

fresh skins treated with ch loroform or carbon di sul phide were

employed bacteria were always to be recognised when the skin
,

was ready for unhairing Vo n Schroeder s work was however so .

’

, ,

painstaking and reliable that these di vergent results m ust be

explained as other than experiment a
,

l errors With regard to .

old liquors it is known that ammonia is a powerful aid to the

,

unhairing process and it is not certain to what extent the liquors

,

he used were charged with it It is also ce rtain that old limes

containing much organic matter support bacteri a
.

l life freely ,

while 2 5 per cent of a possibly not very Ol d liquor woul d probably

.

be steril ised by the addition of lime and 7 5 per c ent water In . .

order to test the matter fairly under exact tannery c o nditions .

,

the lime shoul d have been made up entirely with old lime liquor
“

well charged with ammonia and organic matters instead of with

water It is also probable that the hides had under gone a su fh
.

cient amount of bacterial change in the tannery before they came

into Vo n Schroeder s s a l t solutions and it is not at all unlikely
’

that the s a
,

l t solution itself exercised some specific e ffect on the

unhairing It is a l so possibl e that his bacterial cultur es were
.

made on gelatin media unsuitable for the gr t h of alkaline

bacteria and therefore gave blank results Under these circum
,
.

stances it is scarcely possible to arrive at any very definite con

cl u sio n s an d it is obvious that further experiments On these
,

a
points are extremely desirable
S odiu m n d P o ta ssiu m Hy dr a
.

tes —From the earliest antiquity .

,

wood ashes consisting mainly of potassium carbonate have been

-

, ,

used for unhairing either al one or in conj unction with lime

, ,

and indeed the German name of t he process (A eschern ) is d erived

from the fact In more recent times caustic soda either ready
formed or c a
.
, ,

u s t ic ise d on the spot by the ad di tion of lime has ,

often been recommended as a substitute for lime It s action is .

very simil ar to lime but from its greater solubility is far more
po werful a
, , ,

n d probably this has hitherto formed one of the

,

greatest obstacles to its use since a solution of the strength of

.
,

lime water is almost immediately exhausted while a much

-

stronger one is too violent in its action on the hides Some .

experiments made in the A uthor s laboratory appear to show that ’

caustic soda in solutions of the same strength as lime water

a
-

, ,

dissolve consider bly less hide substance than the latter but it is -

,
1 82 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E
more antiseptic than lime and does not unhair readily Wi thout ,

the aid Of bacterial action ( Cp p It also swells more

violently and it is difficult to keep the grain smooth a
. .

,
nd
unwrinkled and from its rapid action and the necessary
, ,

dilution of the solution used should only be employed in ,

suspension limes or other ap pliances for rapid circulation of

-

liquors .

Wilson p oints out th t the compounds of monovalent bases

1

s uch as soda pot sh and ammonia are likely to be more ionis able a
a ,

, , ,

and more soluble than tho s e o f divalent bases such as lime and
baryta and therefore to produce greater swelling and more
,

solut ion of hide substance and this view is in accordance with

“

known facts J Loeb has recently shown ( l bc cit ) that the swell
. . . .

ing power of acids and bases is inversely as the valency of the

anions or kations respectively Fo r example in solutions of .
,

equal hydroxyl ion concentration caustic soda exerts twice the

swelling power of li me Since Nais a monovalent and Ca a
-

, ,

divalent kation Similarly hydro chl o ric acid has twice the e ffect
.

'
-

of sulphuric acid in s o l u t io n s o f equal hydrion concentration .

This work no doubt a p plies directly to hide and other proteins

'

A mmonia it is true swells less than lime because of its

,
weak ,

ness as a base which renders the actual concentration of ,

hydroxyl ions in an ammonia solution much less than in one of

-

lime of equivalent concentration but notwithstanding this it , ,

.
,

dissolves more hide subs t ance -

.

Caustic soda has the great advantage that from its solubility
and that of its carbonates in water it is much more easily a
,

a
nd ,

completely removed by washing fter neutralisation than is the

case with lime It has been successfully applied in some instances
to soften skins of which the texture is natur a
.

l ly too compact for

moroccos and the softer leathers and is usefully employed in ,

softening dried goo ds ( p Wh ere caustic soda is required .

merely to sharpen limes it is best added in the form of

“ ‘

sodium carbonate ( soda ash or crystals) which are c a

,

u s t ic is e d by

the lime in the pits On e quarter or one h a

-

l f per cent on the .

-

weight of hides added in this way decidedly increases the plump

ing power of the lime Some natural waters in Y orkshire con .

tain sufficient sodium carbonate to produce this e ffect It may .

be noted that in the use of sodium sulphide in conj un ction with

lime caustic soda is one of the products of its decomposi .

tion and is one great cause of the difference of e ffect of this

,

1
Th e o r ie s of Le a
t he r Ch e m is t r y 1 9 1 7 p 1 1 2 Se e a
l so

ad m ay at p i at i l al y h ap
.
, , .
,

on t his n n o t he r im p o r t n o n t s, p r cu r s r e n in g o f l im e s ,
E . S t ia y G b
sn ,
er er , 1 9 06 , t r a la
t d i
ns e n 1 9 1 9 , 4 p
, . 1 29 .
1 84 P RI N C I P L ES OF L EA TH E R MA N UFA C T UR E

paddles and that the caustic soda should not exceed a strength
Th e hides or c a
,

of 1 lb in I O gallons ( I per
'

. l f skins -

remain in this for about forty eight ho urs during which they are -

once drawn and returned by which time if the putrid soaking , ,

has been properly done the hair shoul d be fully loosened The ,
.

hides are then drained for two hours and passed into another
pit containing a solution of calciu mchloride which should be
,

slightly stronger than the caustic soda say of about 1 5 lb

per I O g a
-

.
, ,

l lons Th e goods remain in this for about forty— eight

hours during which they a
.

,
r e drawn once and are then well ,

washed in soft water ( free from temporary hardness) in which ‘

they m a A s the c a
,

y be kept for s ome time without injury ustic

soda and the c a
.

l cium chloride solutions are quite sterile to

ordinary putrefactive bacteria both can b e used for an almost
unli mited time and they a
.
,

y kept up to strength
’

r e c o n ve n ie n t l
,

by the addition of strong stock solutions These may be

which give s astrength of
-
.

m ad e of a s p gr of 1 4 ( 80
°
. .

about 5 5 lb of causti c soda and 5 § lb of calcium chlorid e per

ga
-

. .

a
l lon :
In addition to the advant ge o f consi d erable saving of time ,

the effects can be much more easil y regulated than in ordinary

a
l iming and the amount of soda ( and subsequently o f lime )
,

absorbed by the hide c n be exactly determined b y titration of

the liquors Grease is better removed than by Ordinary liming
.
,

as soda soaps are soluble in w ater but if this result is to be

-

obtained the soap must be worked out before passing into the
,

calcium chloride sol ution which would otherwise convert it into ,

an insoluble lime soap A great gain in many districts is that

-
.

the process yields practically no effluents and no lime slab ,

both o f which are frequently very difficult to dispose of The

serious disadvantages of the st a
.

l e soaking however ; have ,

already been mentioned and the meth od has n o t come much ,

into use
I n place of applying the caustic soda first and the c a
.

l cium
chloride subsequently hides may be first treated with c a , l cium
chloride solution and then Wi th caustic soda or the caustic soda
may be applied to the flesh side of the hide by p a
,

inting
A lka lin e c a r bo n a tes are m
.

uch milder in their action on hide

than the corresponding hydrates as they owe their effect to the ,

small quantity of hyd rate formed in their solutions by hydrolysis .

As this is an equilibrium reaction and the hydrate is only repro

d u c e d as it is consumed the effect is automatic a
-

l ly self regulating
,
-

like that of the limited solubility of lim e The unhairing action

is somewhat slow and the swelling moderate and they deserve , ,
 D EP I L A TI ON 1 85 .

more attention but the best conditions for their use have not
,

been sufficiently studied In presence of lime they become

ca u s t ic is e d and act like an addition of Na
.

, OH .

Sodium carbonate occurs in commerce in three forms soda

”
ash a more or less pure dry sodium carbonate soda crystals
or washing soda Na
, ,

2C0 3
1 0 A q containing 62 9 5 per cent of -

water of crystallisatio n and e fflo r e s c in g in the a

.
, , .

ir and Gaskell '

and Deacon s cryst a Na

,
”
l soda 1 A q containing only
’

z C0 3 , ,

1 4 5 per ce nt of water of crystallisation

. .

S u lphides — The practice of using realgar or red s ul phide of

arsenic ( Ger R sma a
,

) as an addition to limes for fine leathers is

.
,

one of considerable antiquity It has the property of loosening .

the hair and epidermis structures with less solution of cement

substance than lime a .
l one and hence produces a leather of ful ler ,

and cl o ser t e x t u re It will however be convenient to defer the .

, ,

consideration of this agent till after that of some of the more .

a
mo dern and simpler substitutes such as the sulphides of sodium
and c a
,

l cium Sulphides of the l kalies and alkal ine earths if

“

.
,

us ed in strong solution say 5 per cent or upwards have the

“

.
, ,

e ffect of very rapidly reducing the harder keratin structures -

such as hair and wool to a pul p attacking first the interior cells , , ,

so that each hair crumples up like a string of sausages and in a ,

few hours or even with very strong solution in a few minutes

, , , ,

the whole mass becomes so completely disintegrated than it can

be swept o ff the hide with a broom or washed o ff in a tumbler , .

A t the same time the action on the sub stance of the hide and
especi a
, ,

l ly on the ce m enting substan ce is very slight t hough the , ,

grain is swo llen and temporarily rendered somewhat tender On

a
the other h nd when used in we a
.

k so l u t io n s say 4 per cent and

‘

.
, ,

under in conj unction With lime the hair is but little in j ured
, , ,

while the hair roots and di rt are rapidly loosened and resul ts
-

are obtained very similar to those with red arsenic

— Fo r the methods of va lua
.

S odiu m s u lp hide
tion and determination of sodium sul phide se e p 28 , .
,

and p 32 . .

It is very soluble in water of which it combines with 1 mol

forming equ a l amounts of Na SH and Na
.
, ,

OH .

Hides suspended in solutions of sul phide of so dium of 2 to 3

p er cent strength unh a
. ir rapi dl y .

Fo r the commoner classes of sole leather hair is frequently ,

removed by painting on the hair side with a 1 5 to 2 8 Tw ( 30 ° °

.

1
In t he La
b o ra
t o ry B o o k t he w t er a o f c r ys t a
l li a
ti s i s g iv e n s 1 0 A q
on a
La ah a a a
.

t er r e se rc e s sho w t h t p u r e c r ys t l s of t he c o m m e r c i l s u l p h id e o n l y

co nt a
i 9 n A q, or 6 7 5 p e r c e n t of w t e r
.
. a .
1 86 P R I N C I P L E S OF L EA TH ER MA N U F A C T UR E

to 40 per cent ) solution of ( crystallised) sul phide of sodium

.

thickened with lime applied with a fib r e brush and folding the ,

-

hide in cushio ns in a damp place or packing in a tub The hair , .

is reduced to paste in a few hours The same effect is produced .

“

by drawing the hides through a similar solution without lime of ,

which sufficient is retained by the hair to destroy it The work

men m u st b e provided with in dia
. .

r u b b er gloves to prevent the

‘

caustic e ffect of the solution on the skin and nails Skins and .

lighter hides are conveniently unhaired by painting the mixture

on the flesh side when it wil l l o o se n the hair or wool in a few hours
,

without destroying it .

Fo r dressing leathers and the finer sorts of sole sodium sulphide

is best employed as a n addition to ordi nary limes to the extent
of 3 to per cent on the weight of the hides or skins when the
1
‘
.
,

hair is loosened more rapi dl y than with lime alone and with less ,

loss of hide substance -

.

Mixed with water to the extent of 2 to 3 lb per gallon and .

,

thickened With lime to a soupy consistence it is much used for ,

u n wo o ll in g sheep skins The wet skin is laid fl e sh up and painted

-
.

with the mixture care being taken that none of it touches the “

wool which it wo ul d destroy The s kin S a

,

r e doubled down the

a
.
,

back and l id on loose boards so as to allow of drainage the back

, ,

of each skin being placed on the flank of the preceding like the ,

slates on a roof and after lying overnight the wool is readily

.
,
“

pulled and the pelts receive a further liming to loosen the wool
,

on the edges and complete the process .

It has been suggested by the A uthor that calf and ot her skins ,

which when chromed often prove loose on the flanks might ,

profitably be painted on the thicker parts on the flesh possibly ,

with a weaker solution than that j ust given and after lying a ,

short time might be limed in t he ordinary way to an extent o nly

,
,

sufficient to loosen the hair on the thinner parts so leaving them ,

in a firmer condition .

Fo r some classes of skins the powerfu l swelling e ffect of the

sodium hydrate formed by reaction with water and the further ,

quantity by reaction of the sodium sulphydrate with the lime ,

1

is obj ectionable as causing too much swelling and the use of

, ,

arsenic sulphide which does not produce sodium hydrate is , ,

preferred The difficul ty can however to a large extent be

.
, ,
‘

1
P r o fe s so r vo n Sc h r o e d e r e x p r e s se s t he o p in io n a
t h t l im e ad n s o d iu m

s u l p h yd r a
t d e o t h is w y b u t
not re a
c c o r d in g t o m o d e r n v ie w s , it
ct i n a a
ly a a a
, ,

is o b v io u s n e
qu il ib r iu m r e c t io n d e p e n d in g o n t h e c o n c e n t r t io n s o f
-

a a a
,

t h e io n is e d p o r t io n s o f b o t h nd t l e s t s o m e p r o p o r t io n m u s t e x is t in
a l id f
,

s o l u t io n , if not in so , o rm .
1 88 P R I N C I P LE S OF L EA TH ER MA N UFA C T UR E
dioxide a l ways present in the gas forming carbonates Lime ,
.

has nearly gone out of use for purifying gas its place being now ,

taken by iron oxide but formerly gas lime was a good deal ,
-

used for u n wo o l in g the s mall lamb skins used for the commoner
sort of glove kid usu a
-
.

l ly by painting a cream of it on the flesh

-

side but sometimes by immersing in a strong solution which of

, ,

course destroyed the wool It s place is now taken by a solution .

of sodium sulphide of I 5 to 1 8 Tw ( approximately 3 0 to 3 5 per °

cent cryst a
.

. l s ) thickened with lime to a soupy consistence the

, ,

use of which is much to be recommended for u n wo o l in g sheep

skins by painting on the flesh
, .

The tank waste from the Leblanc proc ess consisting princi
-

pall y o f calcium sul phide is when fresh quite insoluble and has
-

, , , ,

no depilatory powers ; but when exposed to air and moisture

decompositions take place resulting in the formation of sulp hy
dr a
,

t e s and polysulphi des which form a solution which has been

'

the subj ect of several patents for u n h a

,

1
irin g Po l ys ul p hid e s .

alone have probabl yno unhairing effect but l n conjunction with

lime s ul p hydr a
,

t e s are formed which rapi dl y loosen the hair

This fact was the basis of an ingenious and e ffe c t ive u n h a
.
,

irin g l

process used very many years ago by Mr John Muir of Beith ,

who after liming for twenty four hours in the usual way sub
,
-

m it t e d the hides to a pretty strong solution of Weathered tank

waste for twenty four hours and fin a l ly to water for twenty four
-

,
-

hours to re move the surplus lime and sulphides The sul p hy

dra
.
,

t e s formed in the hide attacked the hair roots with little -

inj ury to the hair itself and the hides c o n tained so little lime that
“

they could be tanned for d ressing without bating and made , ,

about 1 0 per cent more weight than those treated in the ordinary .

way Some trouble was occasioned by stains caused by impurities

.

in the tank waste

A somewhat similar unhairing mixture t o tfi a t obt a
-
.

ined from fi‘

tank waste which is now seldom to be got since the introduction

-

,
'

of the ammonia soda process was patented by Professor Lufkin

-
2

who mixed equ a

, ,

l parts of sulphur and soda ash with a little -

water till combined and then added 8 to I O parts of lime slaked , ,

a
and still hot Schultz 3 states that su ch a mixture containing
I O lb of sulphur will unh ir fifty hides in the same way and in

a
.
,

about the same time as an ordin ry lime the pelt being little .
,

plumped and easily reduced without bating by a few minutes ’

wheeling in warm water B y boiling lime and sul phur with .

a
water a yellow solution is obtained which can be used in the
1
Squ ir e En g P t a 7 56 1 8 5 5 ; Cl a
u s, En g r P t 1 9 06 1 85 5
a a a a
. .
, , .
, .

2
En g P t . . 2 05 3 , 3
Le t her M nu f etw e , p .
35 .
 D EP I LA TI ON 1 89

same way as that from the tank waste A further qu a n tity of

water can be boiled on the same materi a

-
.

l s more lime and sulphur ,

being added as required P olysul phides appear to have a marked .

effect in preventing or reducing alkaline plumping and apparently

could be used in some cases with advantage a s ba
_ ,

t es On acidi
'

fic a
.

t io n they give o ff SH2 and precipitate sulphur so that if used

for neutra
,

l ising one bath c hrome leather they deposit sulphur

'

on and between the fibres and imitate that of the two bath ,
-

process where sulphur is deposited by the decomposition of the

thiosul phate Sodium or potassium polysul phide can a
,

l so be
'

used for reducing in the two bath process in place of thiosulphate

‘

-
.

Sodium polysul phide is produced by boiling sodium hydrate ,

carbonate or sulphide with excess of sulphur It is a clear yellow

, .

solution with a smell of hydrogen sulphide 1

Ba r ium s u lp hydr a
.
,

te has been put on the market experimentally

as an unh airing agent in the form of a strong soluti on containing
yellow polysul phides and which d eposits crystals o f sulphydrate
,

in cold weather It is more stable than calcium sulphydrate

but on the whole does not seem t o present a
.
,

, ,
n y great advantage

over so di um sulphide though it is quite effecti ve as a depilitant

R ea lga r or r ea l s u lp hide of a
.
,
'

rs en i c A 5 28 2 is made by fusing
arsenious acid a
, , .

n d sulph ur and is of somewhat indefin ite com ,

position Mixed with lime it produces calcium sul phydrate and

possibly hyp o sul p h a
.
,

r se n it e To produce a rapid and complete .

reaction it must be mixed with hot lime and the hotter the ,

mixture is made the more powerful is its unhairing action .

Mil der forms may be made by mix in g c o l d or with the aid of hot '

water o nl y It is used with great a

,

. dvantage in conj unction with

lime in varying proportions for unhairing lamb and kid skins -

for glove kid and other fine leathers to which it gives the necessary
stretch and softness and cl e a
-

n rres s of grain without the loo sening ,

of texture and loss of h ide substance which Would be caused by

a
-

an equiva l ent am ount of or di nary liming Fo r glove kid about .

-

o r to 0 3 per cent -
of realgar n d 5 per cent of lime is used
. .
,

reckoned on the green weight of the skin Th e mixture is added .

to the ordinary limes according to the j udgment of the tanner ,

-

and the ch aract er of the s kins .

Fo r pai n ting the flesh side of calf and lamb —

-

skins one part of

re al gar is mixed with ten parts of hot lime made into a paste ,

with water Calf will unhair in eight or ten hours

Orp irn en t ( a a
. .

rip igmen tnm) A s 2S3 is the yellow precipitate pro , ,

d u c e d in arsenical solutions by sulphuretted hydrogen and is a

b y product of the de a rse n ific a
,

-
t io n of sulphuric acid made from
-

S e J E P i kl 1
e 9 6 p 45 6
. . c es, 1 1 , . .
1 90 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

arsenical pyrites It is consequ ently generally cheaper than .

realgar and experiments in the laboratory of the Leeds Leather

,

D epartment showed it to be more powerful as a depilatory as is ,

to be expected from its larger proportion of sulphur but tanners .

,

for some reason o r very probably from prej udice have generally , ,

refused to use it .
1

A n unh airing solution has been sold under the name of

Ino ffensi ve which contained a large quantity of arsenic
sulphide apparently dissolved in caustic soda a l though Moret s
’

origin a
,
'

l patent claimed the u se o f wo o l sweat potash only " -

W R Earp has suggested the use of comp o unds of s ulphur

2

and arsenic ( t hio a rse n a

t e s t hio a
. .

- r se n it e s , etc ) in 5 per cent ,

-
. .

alkaline solution H e prefers to add the compounds to the .

ordinary lime liquors or to manufacture th em in sitn by adding

t he proper quanti t ies of arsenious or a rse n ic a
-

c id mixed with
'

one third of its weight of sul p hur to a solution of an a

-
l kaline
sulphide in lime liquor The pelt is not bated or drenched in -

the ordinary way but after u nhairing is passed directly into , , ,

.

the tanning liquor to which sulphurous acid has been previously ,

added .

There 1 s more danger of injury to t he hide from the very

prolonged action o f weak solutions of sulphides which tend
u l t im a
,

t el y t o destroy the structure and reduce the fibre to a

gelatinous condition than there is from too concentrated solutions , .

No danger need however be apprehended in t he course of any , ,

ordinary liming A rsenical limes are not suited for tainted skins .
,

and they sho ul d not be made so strong as to destroy t h e hair

or wool .

All these arsenical compounds are very poisonous and should ,

go out of use for depilation as they do not appear to be necessary ,

.

A lkaline solutions of arsenious acid are however useful in pre , ,

venting insect damage to dry hides though they have little or -

,
'

no antiseptic e ffect either for that purpose o r in limes ( see ,

p .

Dr R ohm the in ventor of oropo u ( see p,

has recently .

patented the use of the tryptic enzyme for unhairing as well as

for puering There is no reason that it should not do this quite
.

e ffectively as it digests epidermis matter without attacking the

,

fibre of the hide but it has not been sufficiently tried yet to ,

enable us to pronounce on its commercial value 3

.
.

Fo r the analysis of both old and new lime liquors see -

1
Se e on t he at ic on of a
r s e n ic s u l h id e s ,
p E St i ay
sn loc cit

a
.
, , . .

2
En g P t 20 52, Fe b 1 2, 1 8 86
a ad
. . . .
1

3
D R P . . 268 , 87 3 . Se e l so H o ll n er, 1 9 20 , p .
47 7 .
1 92 P R I N CI P L ES OF L EA TH ER MA N UFA C T UR E

sphere quickly carbonates any lim e contained in the surface of

the skin forming ch a
,
l k and leading to uneven tanning at a ,

later stage .

Wh en hide has been insu fficiently limed it is often easy to

remove the longer hair but excessively diffi cul t to get rid of the
short under gro wth of the young hairs which even in properly
-

,
\

limed skins can sometimes only be removed by shaving them with

a sharp h a n dkn ife This difficulty is cau sed partly by the small
.

resistance which the short hairs o ffer to the unhairing knife and -

partly by their being more deeply rooted in the skin than the
older hairs ( see p .

V arious machines have been devised to accomplish the removal

of the hair but o wing to the rapi di ty with which it may be
,

worked o ff by hand and the fact that the work is not difficult
_ , ,

they have hardly as yet come into general use H and work has
-
.
-

the further advantage that in those portions of skin where the

ha i r is tighter than usu a l it may be removed by greater pressure
of the knife or by hand shaving whereas after goods have been -

unhaired by machine they must generally be examined and any ,

patches of hair removed by hand on the beam The edges .

often require to be gone over by hand .

Several machines with spiral knives hav e been introduced for

the purpose but the great diffi culty was the rigidity of the b ed
,

or beam on which the hide was supported which often led to ,

damage to the grain throu gh any lump of flesh left on the hide
a
.

In this respect a great improvement h s been made by the use of

pneumatic rolls on the principle of the motor car tyre into which
,
-

air is continuously forced by a pump attached to the machine ,

the surplus escaping by a relief valve loaded to the pressure to

which it is desired to inflate th e roll ( see fig .

A nother successful device is the Le idgen unhairing machine 1

figs 3 2 33 in which the hide is supported on an apron of stretched

.
, ,

canvas While the spiral knife roll not onl y rotates , but sweeps an
,
-

arc down the hide which is held in position during the traverse
of the knife by a
,

n automatic clamp

Occasion a
.

ll y goods are unhaired b y full in g in the stocks '

but the saving in labour is more than counteracted by the loss

of weight caused by submitting the hide while its gelatin is in a , _

partiall y dissolved conditio n to such rough usage , .

The use of the wash wheel ( see pp 1 5 8 1 65 ) for the same pur
-
, .
,

pose is much more satisfactory and may be profitably employed ,

for common goods when the hair has been destro yed by painting
with a sulphide mixture
1
E H
.
.

. Mu n k wit z Mil w , a uke e .

 D E P I LA TI ON

If a strong sul phide solution has been used it may even be ,

swept o ff with a sti ff cane broom .

A fter unhairing the greatest care must be taken to avoid

exposing the hide to the air which a
,

a
l ways contains carbonic
,

more to w t er c ont aining t empo rary hardn ess or “

“

FIG .
32 .
— L e id e n U n h ir in
g a
g Ma
c hin e .

fre e CO2 and it is best to return them immediately to a pit of

,

water which has been softened with added lime liquor or which
“

has been only parti a

,

l ly renewed after use for a previous pack ,

and let them remain there till required for fl e shin g

A fter being unhaired the hides a
.

re,
fleshed on the beam
or by machine This work which consists in removing the
.
,

loose subcutaneous tissue and any flesh and fat left on the inner
side of the skin should be carefully and thoroughly done but
,

the closeness of the fle shin g required is dependent on the purpose

'

to which the hides or skins are to be applied .

1 94 P RI N C I P L ES OF L EA TH E R MA N UFA C T U R E
is n c c e ss a
It r y not o n ry to remove those portions of fat which
’

are easily visible but also to force out that contained in the loose
,

areolar tissue The form of knife used in England in fleshin g is

.

FIG .
33 . a ah i
— L e id g e n U n h ir in g M
'
c ne .

shown in fig 34 It di ffers from the one used on the beam for

. .

unhairing in being somewhat broader and heavier and both its

e dges a
,

re sharp so that where the flesh is too tight to remove

by mere friction of the knife it m ay be actu a
,

l ly cut away by ,

holding the knife almost flat on the beam and using the convex
sharp edge The knife is ground hollow on the surface next the
.

hide The strokes in cutting must not be too broad or from the
.
,

convexity of the beam the substance of the hide will be cut into
in the middle or flesh will be left at the edges of the stroke
' ‘

, .
1 9 6 P RI N C I P L ES OF L EA TH ER MA N UFA C T UR E

certainly originated the semi cylindrical beam which forms a ~

,

very i m portant feature It s construction will be seen from .

fig 3 5 . .

It will be easily noticed that if a hide be th rown over the

a
h lf cylinder so that one half hangs outside it and the other
-

half falls in its hollow and it be then rotated the hide is first , ,

caught fir ml y b y a spring clamp which has been supported above

‘

a
-

the edge of the h lf cylinder by blocks attached to the frame

-

A s t h e edge rises it lift s this clamp o ff the blocks and thus carries
the hide under the spi ra Th e blades of this spir a
,

l kni fe cylinder l -
.

knife cylinder are ground to a sharp r ectangul ar edge and partly

scrape a
-

n d partly cut the loose tissue of the flesh When the .

half cylinder has made a semi revolution it returns to its original

- -

position a nd the sizes of the driving pulleys are so arranged that

'

the cylinder tr a vels downwards more rapidl y t ha

,

n it rises in
‘

order to economise time though in both cases the hide is worked

upon by the knife spir a
,

l which i s rotated at a still higher speed

n d the other h a
-

Th e hide 1 8 then turned on the beam cylinder a

, .

lf -

is similarly fleshed The beam—cylinder reverses automatically

or may be reversed by hand and its nearne ss to the spira
.
,

l knife
is also under control It is usu a
,

.
l ly c overed with a thick sheet of
.

rubber .

I t is obvious that machi nes of th 1 s type can b e used not only

for fleshin g but for unhairing and scudding by t he su bstitution
.

of suitable knife cylinders -

.

Th e V aughn machine is frequently used in A merica for ,

fle shin g hid e s after soaking but before they go into th e limes

'
'

and much is to be s a id in favour of this method as the remova

,

l ,

of the flesh permits even and uniform action of the lime It is .

,

however a distinct disadvantage to the method t hat the flesh

,

appears rough —looking aft er tanning and the method is mos t ,

suitable in conj unction with the A merican system o f sp lit t in g '

'

the tanned leather .

In the production of sole leather fl eshin g machines have not

as yet come into very gener a l use Th is may be accounted for .

by the fact that if used before liming a rough flesh is produced ,

which is unsightly on sole leather and which cannot well be ”

,

afterwards improved whil e something of the same obj ection ,

attaches to fle shin g after liming with the added disadvantage ,

that the hide i s too much pressed and is not easy to plump ,

again so as to make a satisfactory sole leather

What is re a l ly wanted is a machine which Wil l re a
.

l ly cu t the
flesh as the knife does A machine which did this was invented .

by the late Mr E Wilson in which cutters something like the

.
,
1 98 P R I N C I P L ES OF L EA TH ER MA N UFA C TUR E

blades of skew planes were attached to an en dl ess band which

-

Worked above a cylinder carrying the hide and cut o ff t h e flesh

a
,

l most like a splitting machine It did excellent work but was

’

.
,

not much more rapid than hand fle shin g D ressing hides are ‘
.
-

often fleshed in the States in the tanne d condition by passing

them through the band knife splitter flesh side up and with the
-

machine so adjusted as to take a very thin skiving the splitting ,

proper bein g afterwards done in

the ordi nary way gra i n side up -

I t is doubtful b ut possible that , ,

S a u o u uo s this might be done in the limed t

state with a machine with a

grooved feed roller such as is
used for splitting o ffa
-

l from the
limes Th e writer a l so suggested .

many years since that fle shin g .

could be done by a machine like

that used for shearing cloth in , ,

which a spiral knife works against

a fixed ledger blade with a scissors -

l ike action Th e loose flesh woul d

'

g a
F I G 3 6 — D ia
.

m o f H id r
be drawn up by the rotating knif e
e .

and cut o ff while the firmer corium ,

wo ul d pass under it but so far as he is aware the idea has

, , ,

not been practically tested In any case at the present price .

,

of labour machin e work is sure to come more into use

,
-
.

a
In A merica both sole and dressing leathers are us u ally tanned
,

in sides the hide being cut down the centre of the b ck In

England the hide is usu a
.
,

l ly rounded for sole leather into

butts or bends (h a l f butts ) and o ffa
l
”
as sho wn in ,

fig 3 6 Th e rounding is done by hand with a sharp knife on a

. .
’

table and in some of the best tanneries frames made of wood

or met a
,

l are employed to mark the sizes required Th e chie f .

advantage of rounding before tanning is that the various parts

of the hide c a n be di fferently tanned and appropriated t o the
purposes for which they are most suitable The offa
,

l is now .

frequently split either from the limes or after t annage and worked.

up for light leather or in other cases is tanned with a cheaper

a
,

and more rapid tann ge than the butts .

D ressing leather is more frequently rounded after tanning ,

according to the purposes for which it may be required .

A considerable improvement has been made in recent times to

fle shin g and some other leather working machines by s u b s t i
,
-

tuting for a rigid or simply rubber covered roller supporting the

,
-
 C HAPTER X IV

DELI M I N G ,
B A TI N G , P UE R I N G , A ND D R E N CH I N G 1
"
A LTH O U G H lime is in many respects a most useful and satis
factory means o f loosening hair it is important that it should ,

be completely removed at least from the grain s u fac e when ,

r

it has done its work since its action on tan nins is most injurious
and it is often harmful in tawing Fo r soft leathers it is a
, ,

l so .

necessary that the skin should be brought from a swollen to a

soft and flaccid conditi on
a
.

All the processes mentioned under the he ding of this chapter

have the remova l of li me for one o f their obj ects but except in
'

that of deliming with acids they a

, ,

l so ful fil other functions such , ,

as bringing down the alkaline swelling and removing certain ,

constituents of the skin which are not required in the finished -

leather A ll the older process e s did this by mean s of bacterial

.

fermentation but it is now understood that it was by the agency

,

of the enzymes or digestive ferments which the bacteria produced .

,

and several modern bating preparations utilise the tryptic or

pancreatic enzymes derived direct from anima ls .

The enzymes form a curious link between living and dead

matter V ery small quantities r e capable of breaking down
. a
large quantities of prot eids into their simpler forms and ulti ,

mately into their amino acids and they do this without them
,
-

selves apparently su ffering change They are very selective in .

their action— the tryptic enzymes at t ack epidermis matter and -

emulsify fats but are unable to attack the unaltered hide—fib r e

,

itself while pepsin digests the latter but does not attack the
epi d ermis nor fats Most natur a
, ,

l enzymes are mixtures and it

.
,

is quite possible that if we could completely separate them we ,

might find that each single enzyme could only digest o n e species
of proteid and if we knew exactly what we wished to remove
from skins we might sel ect the enzymes which woul d do it without
touching anything else The enzymes a re a
,

l so very particular
as to t h e exact degree of acidity or alk a
.

l inity of the sol utions in

a
which they work and each has an optimu m hydrion concentra
,

1
Se e l s o T he P u er i ng B ti n g ,
a ad ,
n D r en c hing of S kin s , b y J . T . Wo o d .

Sp o n s ,
1 9 1 2 .

200
D E L I MI N G ,
B A TI N G P UE R I N G D R E N C H I N G , , 20 1

tion ; thus the pepsins will o nly act in faintly a cid solutions ,

while the trypsins require alkaline media .

”
A s regards the extrem e pul ling down effect of many of these ‘‘

fermentat ive processes no adequate explanation has yet been

‘

given but it i s a plausible if as yet unproven hypothesis that

they automatic a
, , ,

l ly bring the alkalinity or acidity of the solution

towards the isoelectric point ( Cp p 3 7 0 ) of collagen which is the . .
,

point of minimum swell ing A s the proteids are broken down .

1

towards amino acids their capacity for combining with acids or -

alkalies is vastly increased by the added number of free ( terminal )

amino groups and carboxyls and as t h e a
-
m in o acids themselves ,
-

are very weak either as bases or acids they must ul timately , ,

.

bring down the hydrion concentration of t he solution to a point

very near neutrality No decisive opinion can however be given .
, ,

till much more electrometric work with the hydrogen concentra

tion cell has been done on these liquids

a
.

Th e older methods may be described as follows :

Ba ting consists in han ling or steeping the g oods in a we k
d
ferm enting infusion of pi geon or hen dung for a time usu a l ly
, , ,

extending over some days a

-

n d is applied to the heavier classes ,

of dressing leather such as common and shaved hides kips

“

, , ,

and calf skins

P u er ing is a very similar process applied to the finer a
-
.

a
nd ,

lighter skins such as glove n d glac é —kids and moroccos in

, ,

which dog dung is substituted for that of birds and as t h e

-

, ,

mixture is used warm and the skins are thin the process is
genera
,

l ly complete in a few hours at most Neither bating nor .

puering are very e ffective in removing lime and seem to act

princip a
, ‘

l ly by some direct e ffect of the bacterial products on the

swelling of the pelt
D r en chi ng is occasion l ly u sed ( e g on calf kid) as a substitute
for bating or puering but more frequently follows the latter
.

,
a . .
-

and serves to cleanse and slightly plump the skins before tanni ng
and complete the remova
,

l of lime Th e drench — liquor is an .

1
Wo o d in f o r m s m e t h t h e h a l at i f t h b a t i a af s o und t he u su re c on o e e s

P =7H ad t h p tii
~o
n t ati f th
e at i
o f t yp i
n u rn a t c o nc en r on or e c on o r s n

lla h ab
,

37
°
C i P 9 7 Ths i l t i p i t
H f g e h w t b so e e c r c o n o co en s ee n s o n o e

a ti a l w it h t h a f g la wh i h i a
. .

lm t id os t
en ti c b t P N/ o e n c s ou H or

ad t h l igh t l y t h aid id f t a
,

n us s l it y ; b t wh il
on th w lli g
e c s e o n eu r u e e s e n

c u r ve i a p id l
r se s th aid id it i
r ly
y y g a
on d a ll p t e c s e, r ses on v er r u y u o

ab t P =9
ou th a Hl ka l Ba t ad p
on a a e ll y f ai t ly a id a t
in e es n u er s re u su n c

t ad a d a l ka
.

th t
e ou se ly d n li b y t h l im
re o n m d f m th r en ere ne e e re o ve ro e

ad t h w l l i g i i fl ad O H
,

H
’
ski n s, n d b y th
e s i e b id n s n uence o er ons es e + n

Na am h ait q i a t f Ca ta
.

O H w h i h w ll t w i c s l
e s ( OH ) i i l
ce s uc s s e u v en o 2,
s ce r n v

d i ba t i g ad p
,

re m ove n i g n n u er n .
202 P R I N C I P L ES OF L EA TH ER MA N UFA C T URE
'

in fu
s io n bran made with hot water and allowed to ferment
of

under the influence of speci a l bacteria which are a

“

l ways p r esent ,

in vats used for the purpose and which develop lactic and acetic ,

acids
It will be noted that a
.

l l these methods are fermentative and

their e ffect is not simpl y the chemic a
-

l one of removing the lime

but the bacterial action leads a
,

l so to solution o f the cementing -

substance of the hide fib r e s and produces a marked softening -

effect on the leather together with considerable loss o f hide

a
a
, _

substance In the manuf ct ure of the softer leathers this effect

.

is generally desired n d no process would be satisfactory which

,
-

did not produce it but in oth e r cases s uch as harnes s and

strap butts firmer a
,

nd heavier weighing leathers wo ul d be pre

,

ferred if it were known how to make them The putrefactive .

processes would be gladly relinquished if satisfactory substitutes

co ul d be found not onl y on account of their offensive character
, ,

but because of their uncertainty and danger to the goods and

even if lime only were removed the necessary softness could ,

often be obtained by appropriate liming and t anning

It will b e best therefore to de a l first with the purely chemic a
.

l
methods which a i m only at remova
_ , ,

l of lime before consideri ng

those involving bacterial action Unfortunately the chemical
problem is not so simple as it might at first sight a p p ea
.
,
'

r Th e
alk a
.

l ine lime clings obsti nately to the hide fib r e and can only be _
-

removed partially by mere washing with water On the other .

hand the use of any considerable excess of strong acid is pre

,

cluded because of its powerful swelling effect on t h e pelt in the

, ,

tanning of which it woul d prove even more inj urious than the
'

lime making dark coloured and brittle or tender leather This

,
-

, ,
.

e ffect is not to be avoided by the use of even very dilute solutions

of strong acids if u sed in excessive qu a ntities since the ,

a
affinity of hide fib r e for them is so great that it will abstract
-

practicall y ll the acid from even a decinormal solution leaving ,

it quite neutral Wh at is required is an acid of ext remely weak

affinities forming soluble lime s a
.

,
l ts and obtainable at a low ,

cost or on the other hand a salt of some weak base which

, ,

could be displaced by lime and which would not act inj uriously
a
,

on t he pelt With certain precautions and in special c ses

.
, ,

however the stronger acids may be used successfull y

,
.

I n the cases of sole and belting leather no softening is desired

and formerly tanners usu a
,

l ly contented themselves with a very

perfunctory washing in water trusting to the acids present in the ,

liquors to complete the removal of the lime Even pure distilled

water e ffects this removal very slowly a
-

. .

n d imperfectly owing to ,
204 P RI N C I P L ES OF L EA TH E R MA N UFA C T UR E

gre yish P robabl y a very good method would be to s u sp e n d t he

.
'

butts in a deep pit preferably provided with some means of

,

agitation in a solution of sulphurous or some other acid of about

N/2 o strength sufficiently long to remove a
,

, l l lime from the

surface and slightly to plump but not to penetrate to the centre
of the hide which shoul d t hen be suspended in water until any
a
,

e x cess of cid had been taken up by the unneutralised lime still

pre sent in the middle of the butt which at the end of the opera ,

tion should be rather alkaline than acid The course of this or

a
.
,

any other delimi ng operation c n be followed by cutting the

“

hide and moistening the cut surface with alcoho lic solution of
,

phenolphthalein which is turned red or pink by the least trace

, , ,

of fr ee lime

a
.

In using mineral acids it is of great importan ce that they

should be perfectly free from iron n d that the va t employed ,

should contain no iron which could become dissolved since if , ,

present in the bating liquid it is sure to be fixed by the hide

especi a
,
, ,

l ly if the quantity of acid use d is in s u ffic ien t to neutralise -

the whole of the lime

B esides the di rect use of miner a
.

l acid which has been described

sulphuric or still better o x a l ic a
,

,
c id may be very advantageously
,

employed in precipitating lime f rom used bating liquids contain '

ing weak organic acids or other lime solvents so as to restore

their origin a
,

l activity No t only is the bate economised by being

.

used repeate dl y but some of the organic products dissolved from

,

the hide have themselves considerable power of removing lime .

Putrefaction should not be allowed to take place but many of

the organic acids which have been proposed for bating belong
to the aromatic series and have consider bl e antiseptic power , a “

Where organic acids are employed the presence o f their neutral ,

\

lime salts in the liquor resulting from previous Operations will ’

- f
, ,

reduce the swelling action of the acid on the skin without

diminishing its power of removing lime but neutra l sa l ts of ,

strong acids have little effect on the strong acids ( Cp p . .

Ordinary sodium bisul phate has the disadvantage of leaving

practic a l ly the whole of the lime in the form of c a l cium s ul phate , ,

in the hide and therefore is only suitable for sole leather but it
, ,

can be used for the purpos e and its action is more mild than ,

that of sulphuric acid itself but great care must be taken that , .
-

no nitric acid is present as is frequently the case in the crude ,

product obtained in the manufacture of nitric acid from sodium

nitrate and known in commerce as nitre cake
,
Th e presence -

of a trace of sodium chloride would not be disadvantageous for

dressing leather but wo ul d tend to prevent plumpness in sole
, .
D EL I MI NG ,
B A TI N G P UER I N G , ,
D R EN C H I N G 29 5

P al
e ss e r and A p p el iu s have shown that raw hide absorbs sul1

p hu ric acid from s o dium bisulphate leaving the neutr a l sulphate ,

in solution .

B oric ( boracic) acid though used to a slight extent for a ,

number of years past has recently come much into favour as a ,

deliming agent for which purpose it is in many respe cts par

t ic ul a
,

r l y suitable Sole leather may be impr o ved in colour by

.

giving a short bath in 1 1 to 2 per cent boric acid solution to .

remove surface lime In this case t h e acid is best applied j ust

before the hide enters the suspenders B oric acid may a
-
.

l so be .

suitably employed on hides which have been bated It then .

acts as a drench and removes traces of lime still left in the hides ,

so that the li quors have a more even e ffect on them Experience

has shown that the skins should never be a
.

l l o we d t o lie for any

‘

'

length of time in the boric acid solution in a motionless condition

as this tends t o produce patches of parti a
,

l ly delimed skin which ,

cause irregul ar colour It is best to keep the skins in fairly

a
.

constant motion in a paddle or b y frequent handl ing B oric ‘

acid has considerable influence in preventing drawn gr in in the

-

early liquors but if it gets into the forward liquors it renders the
,

leather loose and light p 3 7 0 and p 3 7 and .

, .
,

p .

B orax has also been sug gested as a deliming agent and as it is

'

chemic a ll y an acid s a
,

l t it has naturally some d eliming effect

, ,

but it cannot compare with boric acid in either price or efficiency .

B oth boric acid and borax are antiseptics ( see p .

I n the employment of either sulphuric boric or any other , ,

acid forming calcium salts of limited solubility it must be borne ,

in mind that if the solution is repeatedly r e strengthened it will

become saturated with the lime s a
-

l t and although the acid will

still combine with the lime and render it neutr a
-

l it will n o longer ,

remove it from the hide U nder these conditions sul phuric acid
may cause the deposition of crystalline c a
.
,

l cium sulphate in min ute

nodules b et ween the fibres Calcium borate may be similarly .

deposited and has the further disadvantage of becoming de c o m

posed by the tanning liquors which form d a
,
fi

r k compounds with

the lime In using sul phuric or boric acid a

,

. l one it is theref ore

best to renew the water each time When it is used in con
junction with some other acid forming very solubl e lime sa
.

l ts
this danger is not to be apprehended whil e ox a
-

, ,

l ic aci d pre
c ip it at e s the lime a
,

a
l most completely from the solution
It is to be borne in mi nd that in a
.

.
ll cases of using cids any ,

carbonate of lime present on the pit sides or elsewhere will be

1
Wi s s e n s c ha
f tl i c h -
Tec hn i s c he B e il g e d e s L e de r rna akt r ,
1 901 , p . 1 0
7 .
206 P RI N C I P L E S OF L EA TH E R MA N UFA C T UR E

decompos ed and the carbonic acid Will become dissolved in the

, ,

liquor and unless acid is used in su fficient quantity to remove

the whole of the lime may ten d t o fix the remainder as carbon a
,

a
, te _
.

In the case of dressing leather there is less d nger of this as

warm water is genera
,

l ly used in which little carbonic acid dis ,

solves It is probable that some of the coal tar sulphonic acids

.
-

which have b een advertised for bating dressing leather might be

advantageously employed for sole and if the liquor were r e
generated by the addition o f sufficient sul phuric acid to neutr a
,

l ise
the lime dissolved fro mt h e hide might be used repeatedly and , ,

woul d not then prove expensive while their sterilising power

would be very advantageous to the proper swelling of the butts
in the handlers since nothing tends to check plumping so much
,

as putrefactive action .

Turni ng from sole to dressing leather mineral acids are very ,

”
successfully employed for pull ing down the goods bein g
thrown into a paddle containing warm wa
.
, '

t e r o f ab out 3 0 to 3 5 C
‘
° °

and the c a l culated quantity of sulphuric or hydro c hl o r ic a

.

c id ,

previ o usly largely diluted with water is then added in su c c e ssive

portions at interva
,

l s and more gradually and slowly the thick e r

,

the hides The acid must in no case be sufficient to neutralise

.
,

quite the whole of the lime Goods treated in this way can be
a
. .

further bated puered or drenched s required by the ordinary

, , .

methods if they are not su fficiently soft If too much acid has .

been used and the skins show signs of swelling they must be
brought down by the addition of a little a m m o n iao r even
, ,
'

soda as if swollen with acid they will not bate with an enzym e
,

bate
In m a
.

.n
y cases the addition of salt in small quantity to the
acid liquor will tend to deplete the hides and at the same time ,

prevent any inj urious action of the acid A mmonium chloride '

may a
.

l so be used with advantage ( see p A solution con

taining about 1 5 per cent of s a
.

l t and 0 3 per cent of sul phuric -

acid with some molasses has been a good dea

. .

,
l used in the States
,

as a deliming agent and seems to answer well on some classes of

goods but the acid and s a a
,

,
l t are apt ultim tely to find their way , ,

into the liquors and destroy tannin The process is well suited
for ch rome leather a
.

nd may also be usefu lly applied in cases

,

where goods have become wind blasted or otherwise 1 m p r e g ‘

t e d with carbonate of lime smee l n presence of s a

-

na l t the acid ,

can be use d in sufficient excess to dissolve the carbonate Ve ge

table acids may o i course be used in conj unction with s a
.

, ,
l t in the
same way The salt does not neutralise the acid but simply
.
,

controls the swelling of the skin and if acid has been used in ,
 29 8 P RI N C I P L E S OF L EA TH ER MA N UFA C TUR E

has been shown in the P rocter Internation a

It l R esearch
Laboratory that the lactic anhydrides always present in com
l lactic acid are of equal va
m e r c ia l ue to the acid itself for deliming
'

and become converted into the acid on dilution Their separate .

estimation is therefore useless 1

In fact Dr G Eberl e proposed . .

the use of such anhydrides for deliming purposes for which ,

they would be very suitable in cases where it was desirable

to keep down t h e amount of free acid to a minimum The .

anhydrides of acetic propionic butyric and lactic acid as well as

the lactone of y—oxybut yric acid a
, , , ,

nd the lactide of lactic acid ‘

are sp e cifie d 2

Formic acid in 60 per cent solution formed synthetic a

.

l ly by
the combination of c a
.
,

rbon monoxide with caustic soda and the

subsequent decomposition of the sodium formate so produced
ha
a
,

s been brought into commerce at a cheap rate and forms a ,

satisfactory substitute for cetic acid in the deliming hf hides

'

and many other tech nical operations Formic is about ten times .

stro nger than acetic a cid Wood ( l oc cit ) says that a mixture
of equ a
. . .
_

l parts o f formic and acetic acids acts better t han either

'

alone It is said that the format e of lime formed has a pulling

.
-

down action and that less than the theoretical quantity is

,

therefore sufficient .

B utyric acid produced by the proce ss of Dr Effr ont of B russel s

’

, ,

was on the market commercially before the war It is a still .

-

weaker acid than acetic and as was t o b é expected ,dissolves

'

l
, ,

still less hide substance and if it can be produced su fficiently

cheaply sho u ld prove very va
-

l uable to the tanner

Th e following table calcula
.
,

te d in 1 9 1 1 on the then price of

commercial acids gives the cost of neutr a
,

l ising 1 lb of lime
a
.
,

( C O ) with each and though of course the present prices di ffer , ,

considerably the relative cost probably remains much the same

a
,

The very gr eatly heavier cost of the weaker org nic acids shows
the importance of liberating them again after use by the addition
of sulphuric acid The cost per lb of lime is calculated by the
. .

pence per cwt x 1 0 0 X e q . .

formul a
1 1 2 X 2 8 X per cent strength . .

1
Th o m p s o n ad S z
n u u ki , 1 9 1 8, p 1 1 5
a a
. .

2
Verf hr e n a z m B i e z en d er H ti te n , L e d e r t echn i s c he R u n ds c h
'

aN u, r . 24 ,

1 9 1 0 . Co l l , 9, 1 9 1 0, p .
37 2 .
D EL I MI N G ,
B A TI N G P UE R I N G , ,
D R EN C H I N G 209

A CI D S NE U TR ALI S E 1 LB . or LI ME .

Cost
K= 1 00 13 . per cwt .

s . 52 .

V ery large 3 3
V ery large 4 o
0 1 30 4
-

00 21 4 35 0

o o r38
~
26 o
o ~o o r 8 1 8 0
00 01 1 5 21 0
0 0 000000 1 27 0

k is the disso c ia t io n c o n s t a
nt of the ac id and indicates its
~
,

chemical strength Note the excessive weakness of boracic

.

acid which will not even redden l itmus ( 075 p

,
. .

A ttention must here be drawn to a very important paper by

S t ias ny
1
on the applications of the law of mass action to deli m ing -

and neutralisation of chrome leather processes similar in principle ,

though apparently very di fferent

I nstead of acids many neutr a l sa
.

,
l ts may be used to neutralise
lime and in sole leather it is not generally disadvantageous to
,

leave the lime in the hid e so long as it is in an insoluble and ,

.

fixed con di tion and combined with an acid which cannot be

,

displaced by tannin Thus phosphates or oxalates of sodium

.

or ammonium will convert the lime into insoluble phosphate or

ox a late setting free sodium or ammonium hydrate which f orms -

a
,

soluble tannates and other salts which are easily washed out of
the hide Z inc sulph te will form sulphate of lime and zinc oxide
.

in the hide and seems worth further experim ent for sole leather
but must be free from iron It has some tanning effect and h a
, ,

a
.
,

been used in conj unction with vegetable t annins Alum or

sulphate of a
.
,

l umina wo ul d similarly form c l cium sulphate and

"

alumina but the tanning effect of alumina s a

,

l ts is too great to
admit of their gener a
,

l use for bating though they are very suit ,

t

able for chrome leather A mmonium sulphate will form calcium . ,

sul phate with liberation o f ammonia .

F o r dressing leather the use of ammonium chloride is still

“

more advantageous and it is a powerful bating material con

, ,

verting the lime into calcium chloride with the evolution of

ammonia which is a very weak base and has but little plumping
, ,

power and is easily washed out A mmonium chloride has been

, .

1
p .
30 1 .
21 9 P R I N C I P LE S OF L EA TH E R MA N UFA C T URE

aa a
I

very succ essfully used in calf kid m n u f c t ur e a s a prepar tion -

for drenching instead of puering which was formerly in vogue

A s however only about 3 oz per dozen skins Wa
.
,

, ,
s employed the .
,

cleansing must have mainly depended on the warm water with

which it was used and the free a mmonia evolved Wood states .
1

that ammonium chloride shou ld not be used in greater c o n c e n

t ra t io n than 0 7 to 1 0 grm per liter or the skins become leathery
- -

and do not f a It is a
.
,

l l properly l ways us ed in conj unction with

.

pancreatic bates in which it serves the double purpose of re moving

,

lime and of activating the trypsi n ferment

"

Th e use of ammonium chloride as a bate was patented by .

Z o ll ic ko ffe r in 1 8 3 8 .

A bating liquor which was proposed by the writer and which ,

has been used with some success on harness leather is made up ,

with 3; lb of good white ammoni um chloride ( sal ammoniac )

1

and 1 lb of Bo a
.

”
. kes metabisul phite of soda per hide and ,
‘

for successive packs su fficient sulphuric acid is add ed to

neutra
.

a
l ise the ammonia formed together with a smal l quantity of ,

metabisulphite and ammonium chloride to rest re that carried

out by the hide s It is probable t h a t t his would also ans wer well
for deliming sole leather a
r

s it entirely removes li me without pulling

down the hides much a

,

n d t he
y would remain still plumper if
,
.

ammonium s ulphate were substitut ed for ammonium chloride ,

while the sulphuric acid might be safely increased till t h e liquor

‘

was but slightly alk a l ine when the bating was finished A bout .

2 to 4 oz of good white oil of vitriol is required per hide but

.
,

the exact quantity will depend on the mode of liming and the
amount of washing the hides receive before going into the bate ,

and can therefore be only ascertained by experience A s no .

free sulphuric acid can exist in the liquo r so long as the quantity
of metabisul phite is maintained there is no practic a l danger o f ,

spoiling the leather if the acid be in slight excess Th e quantit ies .

given may in most cases be advantageously di minished since it ,

a
is not always advisabl e in practice to remove the whole of the
lime which in sm a
,
l l quantity renders tannage n d penetration of
the liquor much more rapid either by acting as a mord ant to ,

the tannin or by temporarily neutralising it and dim inishing its

,

astringent action on the hide fib r e -

.

Tur ning to dressing leather we find that t h e use of cold water

alone has been practic a
,

l ly abandoned in this country though

the finest French c a
,

l f is produced by repeated soakings in cold

water with a l ternate workings over the beam sometimes extend ,

ing to nine or more In this case fro m the lengthened exposure

.
,

1 u
P u er i n g B t i n g , a , ad Dn ren chi ng ,
'

p .
47 .
21 2 P RI N C I P L ES OF L E A TH ER MA N UFA C T UR E

certainly quite uninj uriou s to the hides a

,
n d it was claimed that ,

it enabled the grease and dirt to be better removed than by the

ordinary methods Further experience has shown however that
the remova
.
, ,

l of the lime is far from complete since for success

'

.
, , ,
.

it is not only necessary to bring it into s olution but to wash

it out with carbonic a
.

c id so l u t io n under pressure as on expo sure

'

to the air ?solutions of lime in excess of carbonic acid rapidly

deposit calcium carbonate The onl y tannery in which to my
knowledge the process h a
.

s been e xt ensively used is that of Messrs

Mossop and Garland o f Cap etown who stated that it answered , ,

very well for harness leather when a pure lime made by c alcining
'

sea shells Wa
-
s used for l iming but wa s not satisfact o r y with ,

ordinary stone lime It is difficul t to account for this o n chemical

grounds Gl u est u ff m a
.

y be treated very sa t isfactorily by simply

blo win g carbon dioxide or washed a
.

nd cooled lime kiln o r -

a
, ,

furnace gases into an open pit in which the material is kept

-

, ,

agitated In this case ho wever there is no need for the actu l

_

.
_ , ,

removal of the li me so long as it is carbonated and its caustic

a
,

char cter destroyed Carb onic acid do es not decompose lim e

soap and hence sets free no fa
.

,
tty acids which together with , ,

grease are the main cause of the turbidit y of glue and the
, ,

process therefore yi el ds a more brilliant though d arker c oloured

glue than does treatment wi th sulphuro us acid ;

Several acids o f the aromatic series have been from time to

’

time recommended as deliming agents and generally possess ,

‘

the merit of act ing at the sam e time as powerful antiseptics In .

this connection it may be well to mention the s olution of 1 per ,

cent of phenol and 2 per cent of boric acid used by Dr P arker

. .

and the writer for preparing and preserving skins for colour tests
p 1 33 p This ans w ers very well as a ‘

bate even when much diluted arid m a

. .
,

ybe rendered cheap enough

for use in practice by the employment of a good commerci a
,

l
carbolic acid instead of pure phenol and the use o f sul p huric acid
“

to remove lime from the solution renders it capable of repeat ed

employment The carbolic acid shoul d not b e too dark in colour
.
,

and should be carefully dissolved o r carbolic stains will ,

.

result .

Cresotinic acid a mixture of impure acids obtained from “

cresol s in the same way as s licylic a a

,

ci d is manufactured from
pure phenol was introduced as a bate and unhairing and d eliming
,

agent by J H au ff of Feuerbach 1 He also claimed the use of

.
, .

hydrochloric acid to liberate the acid after it had been combined

1
En g P t s . a . ad n j o ur n . S o c Che m I n cl
. .
,
1 889 , pp . 1 24,

80 9 ; 1 89 0 , p . 85 .
 DEL I MI N G EA TI N G P UE RI N G , , ,
D R EN C H I N G 21 3

withlime in the deliming process It is onl y soluble to the extent .

of abou t 1 in 80 0 of water so that even if used in e xcess no , , ,

dangerously strong solution is formed but it has a tendency to

1
,

swell slightly and somewhat harden the hides or skins so that

, , ,

it is perhaps more suitable for sole than dressing leather It has .

also p owerful disinfect ant properties H au ff afterwards patented

1
.

the use of oxynaphthoic acid the corresponding mixed naphthol ,

acids Oxynaphthoic acid is o nl y soluble in

. to
times its weight in water
A mixture of the aa
.

n d 3 mono and di su phonic acids of

[ l
naphth a a
-

l ene has l so been patented by B urns and H ull 2 and

,

later H au ff patented a mixture of vario us impure sulphonic

3

acids of cresols and hydrocarbons All these patents are no w

expired Cresol —sulphonic acids a
.

r e the first stage in the manu

facture of St ia
.

sn y s syntans and are afterwards condensed ’

with form a
,

l dehyde
these co a
a
.

All l tar bates are to replace drenching

‘

rather than bating or puering s their e ffect is mai nl y that ,

of removing lime From their antiseptic character they are very

useful in stopping the effects of p u t r e fa
.

c t ir 1 and preventing .

ferments being carried into the tanning liquors and skins may ,

safely be kept at least for some days in weak solutions but any ,

necessary fermentative puering or bating shoul d usuall y be done

before and not after their use I f used before puering they would .

no doubt stop any direct bacterial actio n on the skin if not in ,

the puer liquor but they probably woul d not prevent the action
of the bacteri a l enzymes a
,

l ready formed and their use might ,

afford a means of using bacterial enzymes without the danger

inseparable from actu a l bacteri al puering or bating .

A writer in the Gerber 1 87 5 p 2 7 9 recommends the use of

dilute solution of sulphide of so di um as a
.
, , ,

bating agent: P ossibly '

it removes lime as sulphydrate and the writer named seems to ,

have obtained good resul ts with glove lamb skins but e x p e ri -

ments made at Leeds were not successful P ossibly what he

re a
.

l ly used was a polysulphide P olysulphides such as

. liver of .
,

sulphur or the yellow solution obtained by boiling dilute sodium “

sul phide or so di um hydrate solution with excess of sul phur have ,

great power of bringing down the pelt and seem well worthy ,

of experiment as bating agen ts .

1
En g P t a 1 888 Cp a
l so jo urn S o c Che m I n cl , 1 8 8 9 , p ‘

9 54
ad a8
. . . . . . . . .

2
B u rn s n H u ll ,
En g . P t . 09 6, 1 89 1
j ou r n S oc Che m I n d
. . . .
,
1 89 2 ,

p 48
aff a
. .

3
J . H u ,
En g P t . . 1 89 4 jo u r n . S o c Che m I n d
. . .
,
1 89 5 , p . 1 70 ;
G er b er ,
‘
1 89 5 , p . 1 33 .
21 4 P R I N C I P L E S OF L EA TH E R MA N UFA C T UR E

the pods of the babool ( A ca

In I ndia ci a r a
bica) are much a
used as a bate the infusion being al lowed to ferment In their
, .

dry state they contain about 1 2 per cent of an easily changeable

tannin which does not precipitate lim e water a
.

,
nd which by -

fermentation is very probably converted into gallic acid The .

use of gallic acid itself as a bate has been patented by Albert

Hul l a n d would undoubte dl y accomplish the removal of the
,
1

lime if used in sufficient quantity but as he only uses a solution

of 2 5 mgr per litre ( o n e part in any effect must be mainly
a
.

due to the washing with w ter Gallic acid forms dark oxidation .

products with lime .

Of the fermentative methods of removing lime drenching ,

with fermenting bran infusions is the simplest in theory and has -

“

FI G .
38 .
—B at c e r iu m f u rf u r is a. FI G .
3 9 — B . at c er i u m f u rf u r i s 6 .

been very carefully investigated by Mr J T Wood It will . . .

2
,

therefore be convenient to consider this process first although

, ,

it is frequently employed as a means of cleansing and slightly

plumping the skin after the lime has been removed by puer
ing or bating In calf kid manufacture however it is used .
-

, ,
,

without previous puering and in som e other cases it is substituted ,

a
for the use of dung bates The mo st important of the active “

ferments r e two species of bacteria named by Wood B a

.

ct er iu m ,

f fu r u r is aand 6 which are very similar in their form and action ,

( se e p but produce a somewhat better fermenta

.

tion together than separately They are shown in figs 3 8 and 3 9 . . .

Neither species has any direct action on the hide substance but -

ferments the glucose produced by the action of the cerealin of the -

bran on the starch which is present A considerable quantity .

1
En g P t . a. 1 88 9 .

2
jo u r n S oc Chem I nd 1 89 0 p 2 7 ; 1 89 3 p 4 2 2 ; 1 89 7 51 0 ; p
a a a
. . .
.
, , .
, .
, .

B r i t A sso c R ep 8 9 3 p 7 23
1 S e e l s o T he P uer in g E t in g n d D ren c hi n
. .
, , . .
, , g
o
f S kin s , b y J . T Wo o d . E . . F N Sp o n Lt d
. . 1 9 1 2
, .
,
. .
21 6 P RI N C I P L E S OF L EA TH ER M A N U F A C T UR E

of ammonia soda or whitening to the water in which they are

, ,

placed preferably in a pad dl e and if they are insuffi ciently

, ,

drenched they may then be paddled in tepid water thou gh this ,

is hardly likely to be needed as the effect of the acid is to remove ,

the lime very completel y The obj ection to the use of whitening .
,

which otherwise is the safest and best material to employ for

a
removing cid from pelt is that it is apt to become mechanical ly
a
,

fixed in the grain n d thus to produc e bad colo ur with vegetable

,

tans Fo r white or chrome leather it wo ul d do no harm Pr e

. .

cautions to prevent the recu rrence of the inj ury are to keep the
t emperature of the drench low and to free t he bran from flour ,

by washing in two or three cold Waters before adding to it the

hot water with wh ich the actual drench liquor is made since the -
.

flour or at least its starch is the source from which the butyric
, ,

acid as wel l as the lactic is formed This troubl e is rare in the

,
‘

,
.

comparatively cold climate of England and indeed the writer ,

has never seen a case or had the opportunity of investigating one

I t is hardl y probable that it is re a
.
,

l l y due to butyri c acid since it ,

is now known that butyric acid is an extremely mild one milder ,

than acetic or lactic though of course in very large quantity it ,

could produce the effect It may be due to the production of .

some other acid or possibly of some bacterial pep tic enzyme

, ,

which liqu e fies and digests the hide fib r e In col d weather

'

where dre nching is proceedi ng in a norm a

-

.
,

‘
l way the flour is useful , ,

since it is the natural nutriment of the drench ferment ; and in ,

England flour is frequently added purposely to the bran t o

,

increase the activity of the drench To retain the flour the bran .
,

may be washed first with boiling water which gelatinises the ,

starch and makes it adhere to the b ran and according to Eitn er , , ,

removes a sticky fat like matter from it and fits it better to -

remove the fat of the skin A fter soaking in hot water for t wo
hours it is washed in sever a
.

l cold waters and infused at about

40 C for use
°
. Many tanners use the bran With out previous
.
1

washing but if much flour is present it rises to the top with the
,

gas evolved by the fermentation and forms a pasty mass on the ,

skins whi ch interferes with even drenching

, .

a
Th e q u antity of bran used in ordinary drenching is very
variable but bout 4 p a
'

r t s p e r 1 0 0 0 of water used and from

, 5 to
1 0 p er cent on the weight of pelt may be taken as an average
.

quantity more being frequently employed The temperature

, .

may vary from 1 0 up to about 3 0 to 3 5 C and the time in ° ° '

°
.
,

v e rs e l y from days or weeks down to two or three hours accord ,

ing to t he temperature of the drench the amount of ferment ,

1
G e rb e r ,
1 88 2 , p . 2 46 .
D EL I M I N G ,
B A TI N G P UE R I N G D R EN C H I N G
, , 21 7

present and the thickness and character of the skins The skins
are usu a
.
,

ll y thrown into the freshly prepared drench to which ,

a few pailful s o f old drench liquor is frequently added as a

'
-

ferment Fermentation soon sets in and the gas evolved causes

the skins to float to the surface this is c a
.
,

l l ed the working of
the drench Thin skins ma .
y be su fficiently d renched after once
rising while thick ones require to be put down two or three
,

times A certain sign of sufficient drenching is the appearance

.

of smal l blisters on the grain caused by the evolution of gas in ,

the substance of the skin When these are seen t he dr en c hin g

‘

should be at once discontinued as otherwise the blisters will in , ,

crease in number and burst through the grain causing minute ,

holes or pricks ( one of the many forms of the complaint cal led
,

in German P ikir en or P i qu ier en ) Wh en a bubble of air is enclosed .

in a fold of the su fficiently drenched skin and pressed ; it raises

the grain without actually separating it from the substance of the
skin The properly drenched skin a l so falls easily in folds when
held between the hands either l en gt hwa ys o r crosswa
.

ys and if
'

thin the skin tightly stretched over the hand shows grains of
bran underneath it as little lumps round which the skin clings ,

to the hand The drenched skin shoul d not b e transparent but

.
,

white and soft and when pressed sho ul d retain the mark of
,

the finger Some experience is required to determine certainly

.

the point of sufficient drenchi ng which of course varies with the , , , ,

character of the skins and the kind of leather which is to be

produced and the feel of the skin to a practised hand is one of
,

the most important criteria .

A writer n the Gerber

i
1
divides dr enching for glove lamb into
‘‘

a
-

”
three classes sweet l coholic . and sour , Sweet drench , .

ing is done in a bath of tepid bran water made by infusing in hot -

water and drawing the clear liquor o ff the bran which settles to ,

the bottom The skins are only allowed to remain in two or

.

three hours or not long enough for ferm entation to set in Th e

, .

process is only suited for very thin or soft skins which will not
stand any further loosening The use of bran water has the .
-

”
advantage of saving the labour of branning or removing ,

adhering bran with the knife on the beam b ut it is doubtful if

unfermented bran has much actu a
,

l effect B ran water can how .

-

ever be used for drenching by fermentation and for small glove

, ,

lamb has largely superseded the older method The mechanical .

action of the bran in cleansing the pelt is howe ver often useful
I n sour drenchi ng the bran is a
.

l l owed to steep and soften in cold

wa ter for many hours and boiling w ter is t hen added till t he,
a
1
G erb e r ,
1 88 8 , p . 257 .
21 8 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

temperature is raised to 7 5 C and it is allowed to infuse with °

.
,

frequent stirring for some hours and after cooling to 45 a con °

s id e r a
,

bl e quantity of old drench liquor is added as a ferment -

.

I f the drench is used warm ( 3 0 to or in cold weather even °

,

40 C ) the skins only remain in one to three hours but if cold the
°
.
,

drenching can be extended over a period of two to three days the ,

skins bei ng frequently handled This modification is suitable for

glac é kid and the harder sorts of skins but glove lamb are a
.

aa
-
l ways ,
-

treated by t he w rm n d rapid process Wh at the writer in the

Gerber describes as t h e a
.
.

l coholic bran drench is probably -

the method of fermentation investigated by Wood in which

inflammable gases but no a
‘

l cohol are produced , , .

A normal drench plumps the goods slightly but if it contains ,

much of the putrid ferments carried in from t he bate or puer

the skins fall i n it as they would do i n a bate To i ncrease this .

effect putrid soak liquor i s sometimes added to the drench but

,
-
,

with doubtful advantage .

I n drench liquors the t otal acidity may be determined by

“

titration with lime water or N/I O caustic soda with phenol -

phthalein as indicator and the volatile acids may be distilled

o ff as described under the an a l ysis of tanni ng liquors
p . Fo r more complete meth ods of an a l ysis the reader is
referred to Wood and Willcox s paper on the Nature of B ran ’ “

Fermentation
D renches are s id to work somewhat better if made with a _

water containing nitrates and this is quite probable but the ,

necessary nit rog en can easily be supplied if required b y the

addition of a very small quantity of saltpetre .

Wood is of the opinion that the ferments found in bran do not

originat e in the drench itself but come from the bated skins as '
, ,

the drench bacteria soon die o ut without finishing the ferment a

tion and constant renewing of the nutrient materi a
-
s

,
l is ne cessary
Cp p
(
Ea
. .

ting and p u ering though differing practically in many ways , ,

are identical in theory and most of what follows applies to both ,

of them The action is much more complex than that of the

drench involving both chemic a
.

,
l reactions and those of organised
and unorganised ferments and it is a matter of no little diffic ul ty ,

to say what proportio n of the observed effect shoul d be ascribed

to each of these agencies
Formerly the princip a l e ffect was attributed to organic s a
a
.

,
l ts
of ammonia and its homologues and to amino cids which com ,
-

1
j ourn . S oc . Che m . Ind .
,
1 89 3 , p .
422 . Cp . a
l
so P u e r i ng , a ad
B ti n g , n

D r en c hi n g f
o Ski n s , p . 233 .
229 P RI N C I PL ES OF L EA TH ER MA N UFA C T UR E
-

from the stomach in the bate may be neglected The peptic .

enzymes of the larger intestine which are more likely to be found

in dung are bacteri a
,

, l in their origin and though 0 2 per cent of , .

H Cl is the o ptim u m for the pepsin of the stomach it is too high ,

for those of the intestine

Tryp sin or p a n e rea
.

tin if present is more likely to have an 1

e ffect sinc e it is active in neutra

, ,

, l and in alkaline solutions It .

is the product of t he pancreas and is largel y concerned in in

“

t es t in a Chemic a
,

l digestion l ly it much resembles pepsin but is

.
,
.

more resistant to heat retaining its power of digest ion after

a
,

heating to a temperature of 1 60 C in dry condition It s °

.

'
.

warmed solution di ssolves fibrin almo st instantly and in

.

large quant ity and peptonises gelatin so as to render it

,

soluble in water Wood found that a 1 per cent solution

. .

of p ancreatin acted far more rapi dl y than a solution o f pepsin

of equ a l strength A t 40 C in neutr a .l solution the skin fell
°
.

rapi dl y and the action continued even in the cold In fift e e n

'

.
,

hours the l iquid was swarming with minute bacteria A t the .

suggestion of the A uthor the experiment was therefore repeated ,

with the addition of 1 5 per cent of chloroform which prevente d .

,

the development of bacteria while it did not stop the action of ,

the pancreatin The skin fell as before but in neither case had
.
,

it the pecul iar touch of puered skin nor were t he characteristics

of the leather p roduced from it the sa
,

me Wood found later that . -

-

the unsatisfactory result of this experiment was du e to the

presence of excess of lime and the want of ammonia which is ,

necessary to activate t he p u r e pancreatic ferment In the body ‘

this is done by a special enzyme enterokinase which is secrete d

in the small intestine The practic a
, ,

l pancreatic bates such as

pa
.
,
”
n cre o l and o r o p o n c ontain ammonium chloride This , .

addition was due to Dr Rohm who patented o r o p o n in thi s ,

country but the principle was covered in A merica by a previous

,

patent of Wood s ’
.

It is certain however that fresh bird dung and probably that

, ,
-

of all animals contains ferments capable of liquefying gelatin

,
.

A n instance of this is found in the observation common in glue ,

manufacture that if the droppi ng of a sparrow falls on a cooler

,

ful l of solidified gelatin size it will liquefy a track quite down to .

,

the bottom of the cooler Trypsin or at least the secretion of .

,

the pancreas as well as the gall from the liver have great power
, ,

of wetting and emul sifying fats and this has possibly something ,

to do with t he action of the bate in enabling the skins to be

cleansed of fat .

1
Lo c . cit . ad B
n e i l s te i n , iii p . . 1 3 0 8, 2 n d e d it io n .
D E L I MI N G ,
B A TI N G P UE R I N G
, ,
D R EN C H I N G 22 1

afermentation and its products are

B acteri l however the main
factor in the action of puers and bates a
, ,

nd on this subj ect we ,

ow e most of our knowledge to the work of J T Wood since . .

, ,

though Popp and B ecker have worked over much of the same
ground they have not nearl y so freely published their res ults
, .

Wood showed that a fresh puer liquor even when boiled for
a
half an hour n d so f reed from living organisms and al buminoid
,

ferments has still considerable action on a limed skin though

,

, ,

much less than the unboil ed p uer H e found that this action was
princip a
.

l ly due to amines and their compounds with organic

acids which remo ved lime but did not remove the in t er fib r ill a
,
‘

,
ry

substance or give t he proper feel of q e r e d skin A very similar .

resul t was obtained with aniline hydrochloride in 1 per cent '

solution .

A considerable v ariety of bacteria from dung and other sources

were cultivated in v arious media and their puering power tested
but though greater than that of the unorganised chemic a
,

l com
p ounds such as amine s a l ts and o rganic acids it was in no case
a
-

equal to t hat of an ordinary puer or sufficient for practic l use

When however a sm a
.
,

,
l l quantity of the amine salts obtained
,

from the puer was added to a mixed bacterial culture the effect
on the skin was almost as rapid and considerable as with an
actu a l puer .

In order to determine whether the puering effect was due to

the direct action of t he bacteria or to their enzyme products the
'

latter were separated from a filtered puer solution by adding it

to a large volume of 9 8 per cent a l cohol in which the enzymes .
,

are insoluble When redissolved in water they had a decided

.

puering effect and a solution of 0 5 grm of the mixed enzymes

,
-
. .

and 0 5 grm of the mixed amine hydrochlorides in 1 00 c c of

. . .

water at 3 5 C brought down a piece of limed sheep —

°
. skin in
thirty minut es exactly like a puer The action is therefore
dependent on the mutu a
.
.

l action of the enzymes and amine

salts but as t h e s e p a ra
,

t io n of these woul d be too costly for

‘

practical use and the puering seemed effectual when they were
,

formed in contact with the skin by active bacteria Wood ,

adopted the method of preparing a suitable sterilised nutritive

liquid which wa s inoculated before use with a
i

,
m ix e d cul ture of
suitable bacteria Fo r laboratory purposes a suitable culture
.

medium was obt ained by digesting 1 0 grm of gelatin with 5 grm . .

o f lactic acid
( reckoned water free ) and 1 00 c c of water for -
. .

three hours in a closed vessel on the water bath Th e resultant

solution was neutra
-

l ised with sodium carbonate and diluted to

1 litre with addition of a sm a l l quantity of potassium phosphate .
222 P RI N C I P L ES OF L EA TH ER MA N UFA C T UR E

Thebacteria of fresh dog dung were not fou n d to pro duce a -

satisfactory puering e ffect but those fro m dung which had been
fermented a month ( as in practice) gave a resul t nearly equ a
,

l to
actual puer A still better resul t w s obtained by a mixed culture a
a
.

from the roots of wool loosened by sweating The bacteria Were

princip a
.

l ly of two species of which neither separately w s capable

of s a t is fa
,

t o r y puering but which together acted more rapidly

than an actu a
,

l puer These bacteria do not liquefy gelatin

. .

D uring the course o f his experiments Woo d found that fil tered

puer solutions were less active than turbid ones and that then ,

activity was increased even by the addition of inert substances

a
,

such as kaolin .

Wood ttributes the di fferences in action between dog—dung

.

and bird dung not o nl y to different bacteria but to the fact

t hat in the latter case t h e u r m a
-

r y products and esp ecially uric ’ “

acid are contained in the dung

,
.

From the resul ts of these and similar researches Wood in ,

England and P opp and B ecker in Germany succeeded in pro

'
‘

d u cin g a practical artificial puer which they manufactured in ,

.

”
conj unction under the name of B rodin consisting of a solid ,

nutrient medium and a liquid pur e c ulture of the bacteria

necessary to effect the re quire d bating or puering .

The preparation was quite successfu l and superseded dog dung

.
,
-

in many t anneries though for sheep ; and goat skins it never quite -

took its place but for c a

,

,
l f i t proved much safer and less liable
t o cause s t ains Details of its use are omitted as it has been
.
)
,

almost entirely replaced in its turn by pancreatic preparations ,

which are still safer and can be better modified to suit the ,

leathers which are being produced .

The pancreatic bates were suggested by Wood s work on th e

’

pancreatic fe rment which has a l ready been mentioned but thou gh

, ,

he included its use in an A merican patent he did not at the

-

time p ursue the idea thinking that the use of pure cultures of ,

bacteria o ffered better prospects of success His idea was how .

,

ever taken up by Dr R ohm in Germany who produced the

,
1
,
”
very Satisfactory bate o ro p o n and a similar preparation with
“

, ,

some improvement in detail is now being produced under the

name of P a
,

n c r eo l

The instructions for using P a

.

n cr e o l for calf and sheep skins -

intended for either vegetable or chrome tannage are as follows

Th e limed skins are partially delimed either by thorough washing
with soft water or by the use of weak organic acids The skins
are then warmed up and partly bated in a weak P a
.

n cre o l

1 ,
Ger P t . a . 1 9 08 .
2 24 P R I N C I P L ES OF L EA TH ER MA N UFA C TUR E

Seymour Jones has al so shown that in some cases it is su fficient

-

merely to paint the grai n with the enzyme bate without acting -

on the fibrous part of the corium which contains little or no ,

elastin
In addition to the artifici a
l bates which de pend on the p a
.

creatic enzyme a considerable number of preparations of a secret

,

FI G 4o
— But t of c a
l f ki
s n a a
b t ed w it h m m o n iu m c hl o ri d e o n ly El at i
s n

a a a
. . .

s t in e d w it h W e ig e r t s m g e n t
’
.

nature a re on the market most of which a re drenches or ,

deliming agents rather than true bates though for certain classes ,

of leather they may serve a usefu l pu rpose Many of them .

contain glucose or sugars and some lactic or butyric ferment

,
.

P erhaps an exception sho u ld be made to a patent by the late Dr

Eberle of Stuttgart 1 who employs gall and extracts of the
a
,

intestines in ddition t o the pancreatic ferments These contai n .

enzymes which activate the trypsin and steapsin and so render ,

1
En g P t
. a
. 1 9 09 .
DELI MI N C B A TI N G P UER I N G D R EN C H I N G
, , , 225

the addition of ammonium s a l ts unnecessary A good deal of

a
.

detail about this and the other advertised b tes will be found in
Wood s P u ering Ea’
tin g et c chapter viii .
,
.

A s the old fashioned puering method with dog du

, ,

-
ng is still in
considerable use s ome further details of its action are necessary
,
.

From the mul tiplicity of germs present and the adaptability ,

FI G 41
— But t a
o f c l f—s k in a
ft er s ix
’
a
h o u r s b t in g wit h t r yp s in a
S t in e d
a
. . .

s b e fo r e
.

of the dung 1 n fu sio n as a nutrient medium for any putrefactive

organisms which may gain access to it the bating and puering ,

process is necessarily a dangerous one for the goods always ,

leadi ng to loss of wei ght and if the process is carrie d on too

, ,

long to the more or less complete destruction of the skins Loss

, .

of weight however in greater or lesser degree is inevitable and

, , , ,

indeed necessary where a soft leather is to be produced I f the

skins are a
.

l lowed to lie in the bate or puer liquor m ud containing , ,

organisms and zoogl oea forms of bacteria settle in the folds and
,
-

f
1 5 .
226 P R I N C I P L E S OF LE A TH ER M A N UF A C T U R E

produce marbled markings streaks and lines by the destruction

of the grain surface (hya
, ,

l ine layer ) Black or bluish stains are

a a
.

l so often produced known as bate stains n d are either due to

,
-

bact erial pigments or in some cases to the action of evolved '

hydrogen sulphide on iron present from s a

, ,

l ting or ot her s ources .

Frequent chan ge of position is therefore necessary especially ,

FI G 4 2
.
— But t of c a
lf
-
s k in a
ft er t we n t y h o u r s b
’
a
t i gj
wit h t
n r yp sin a
S t in e d
ab
. .

s e fo r e

a
.

when the liquor is active from being used at high temperature ,

but it does not seem to be desirable to keep the skins in con

”
stant motion as weak grain may be produced by the
,
“

mechanical friction and if puering i s done in a paddle it

, ,

should only be run at intervals

T Pa
.

l mer
.
determined in experiments on pigeon dung bates
1 -

that there is considerable loss of nitrogen during the process ,

and recommended bating in pits from which the air was excluded
1
a a
L e the r Tr d e C ir cu l a r , 2 2 md Se p t . 1 89 1 1 887 , p . 66 7 ad Saf
n n ord,

jo u r n . S o c Che m I n d
. . 1 89 3 , p .
5 30 .
22 8 P R I N CI P LES OF L EA TH ER MA N UFA C T UR E

solution of glucose or treacle of about 1 0 per cent to which 3 per .

,

cent of pasty dog puer is added about a week before use was
tried m a
-
.
,

ny years since in a morocco factory at the suggestion

of the wri ter as at least a partial substitute for puer and rem a
,

,
i ned ,

lo ng in use there The mixture kept for some time in an active .

a
state and was added to the puer liquors in the same way and in
,

approxim tely the same proportions as the dung paste Similar .

in principle was t he solid bate supplied by an A merican firm in

which glucose was mixed with a sm a
,

ll amount of nitrogenous
matter and phosphates to gether with a lactic ferment and , ,

which only requires dissolving in warm water s ome little time

before use It s results were good for some purposes but rather
. -
,

res embled those of a drench than a bate In a similar way puer .

,

may be added to bran —drench liquors and induces in them a ,

fermentation which brings t h e skins down much lower than the

ordinary drench It is probable that a weak glucose solution with
.
,

traces of mineral constituents similar to Cohn s solution ( see ’

L I L B p 2 69 ) and t with sour milk or fermenting drench

. .

liquor rriight 1 n some cases b e used with advantage for drenching

. . .
,

with a savi ng of cost A writer in Hide a n d L ea

, ,

ther de scribes .

a bate in which 2 parts by weight of glucose are di ssolved in

about 2 5 parts of water and fermented for about three days , , ,

with about 1 part of old bran drench liquor or 0 I part of -

pressed yeast till a foam gathers on the top and then made up
, ,

with water to 1 00 0 parts the goods bated twenty four to thirty

six hours a
-

t a temperature of about 3 5 and the bate °

C .
,

streng t hened for a second pack w ith about one fi fth of t he original -

glucose a new bate being made at the end of a week and set with
,

one part per thousand of the old one A short bating of say ten .
, ,

hours produced very nice harness leather but the general tendency
was to make the goods looser and more spongy than a dung b te
It is obviously not a matter of indifference whether old drench
,

-
a .

or yeast is used to start the fermentation since in the latter ,

“

case only alcohol could be produced directly by the ferment

introduced though this might be fermented later by other acci
,

dental organisms into acetic acid These mixed bates containing .

glucose are however probably wrong in principle since the true

, , ,

puering and bating bacteria will not thrive in presence of acids ‘

and require nitrogenous nutriment and if such bates are service

able a
,

t all they act as drenches rather than as true bates

, .

A s regards the relative e ffect of dog and h en or pigeon dung -

bates the chief of the published experiments are those made by

W J Salomon at the Vienna Versuchsanst a
,

. . l t fur Lederindustrie ,
1

1
T ec h .
Qu a
rt ,
1 89 2 , v .
p . 81 .
D E L I MI N G ,
B A TI N G P UE RI N G D R EN C H I N G
, , 229

in which he determined the relative solvent power of equ a l

quantities as being for dog dung 2 1 for pigeon dung 2 and for
,
-

,
-

e n dung 1 t is obvious that these figures though interesting

h I
-
.
, ,

m ust be taken with som e reserve as the composition even of ,

pure dungs 1 5 by no means constant depending on the feeding ,

of the animals and adulteration is common Th e writer has

,
.

heard stories of a c ertain dealer who used to fabricate his product

’

from clay by the aid of a popgun though he does not vouch for ,

the statement " It is generally held that the action of bird

dung is more penetrating but less softening and loosening than
that of dog dung which is thus gener a
-
l ly used for descriptions
of leather where great softness a
,

n d st r e t c h are required It is to
”
.

be remembered in this connection that bird dung bates are

genera
-

l ly used cold and hence are much slower in their action

, ,

which allows them time to penetrate thicker hides more uniformly .

F e w analyses of the dungs used in leather manufacture have been

publi shed and these mostly with a View to manurial value
,
.

S ch ul ze 1
gives the result of forty analyses of pigeon dung as -

foll ows
Min Ma x . .

P e r cent P e r cent . .

Water 3 80 40 0 0
Nitrogen 1 47 5 04
-

Phosphoric acid 1 00 27 7 -

P otash o 7 1 2 57
-

On e sample contained 43 3 per cent of sand " 1

.

Wood quotes the following :

2

H e u du n g -
.

Water
Organic matter 3
Phosphates
Ca l cium carbonate and sulphate
A lkaline salts
Silica a n d sand

D og du n g -

Water
Ca
NaK , ,
Mg
’

P O4
CO2
Organic matter
Traces F e Cl Si , , ,
loss
1
D er La
n d wi r t 89 5 1 i p 3 0 1 1
j ourn S o c Che m In d 1 89 4 p 2 20

a a a
.

a
.
, , . . . . . .
, ,

3
Co n t in in g n it r o g e n e qu l t o 0 -

7 4 p er cent . of mm o ni .
230 P R I N C I P L E S OF L EA TH ER MA N UFA C T UR E

was apparently a sample from a dog fed on bones that

This
from the kennels which is more commo nl y used in leather manu
facture contains much less lime ; a sample an a
,

,
l ysed by Wood
gave 4 7 per cent mineral matter 9 7 p er cent organic and 85 6 .
,
-
'

.
,
-

per cent of water part of which was no doubt added

.
,
.

a
Th e quantity of hen or pigeon dung used in bating hides is -

very vari ble but may be stated at from 1 2 to 60 litres per

,

1 0 00 kilos of raw hide in at least 2 0 0 0 litres of wat er Th e bate

is genera l ly used cold t he hides rem a
. .

i ning in it four to eight days

with frequent handling ; but some tanners especi a
, ,

l l y in the ,

U nited States prefer bating in a pad dl e or drum at a temp erature

,

o f about 3 5 C in which case the time must be diminished to a

°
.
,

few hours The dung is best infused with warm water in a

.

separate vessel and all o wed to ferment for at least a week without
1

use when it will be found to swarm with micrococcus chains

,
-
.

Onl y the clear l iquor should be run into the bate pit the se di ment -

and dirt being thrown away or used as manure I n this way the .

danger of stains and flaking is much reduced B ates may be .

mended with fresh portions of dung infusion for several successive -

packs of hides but sho ul d not be used too long as they gain in
, ,

Solvent power by the dissolved hide — substance and the increased

fermentation and the method is not without risk
A fter bating the hides are usu a
.
,

,
l ly worked scudded ,

fin e haired -
on the beam to remove di rt and grease but in ,

A merica a wash in the wash Wheel is often consider ed su fficient .

-

Goods are occasionally stocked ( p 1 63 ) from the bates but .

,

this is not to be recommended as it is likely to drive o ut much ,

of the partially dissolved hide substance and produce undue -

looseness and loss of weight .

It is difficult to give any definite marks of su fficient bating

other than the soft and f a l len feel of the hides which is easily ,
,

recognised by a practised hand On e of the earliest signs of

commencing o ve rb a
.
.

t in g is the occurrence of bluish patches or a

bluish tinge somewhat similar to an iron stain which if slight
gener a
-

, , ,

l ly disappears in a few days after the hides are taken into

the liq uors He n and pigeon dung is probably best kept air
.
-

dried though if very wet or for convenience for immediate use

, , , ,

it may be kept in paste like dog—dung .

Do g dung shoul d never be all owed to l ie e xposed to the air

-

or it p u t re fi es and turns black the bating ingredients are ,

destroyed and it will not puer the goods which turn black and
, ,

putrid without softening Dung should therefore be mixed to .

, ,

Th is s e m s t oh av e b e fi r s t su g g e s t e d b y T P a lm E g Pa
1
e t e n . er, n . .

1 886 .
23 2 P RI N C I P L E S OF L EA TH ER MA N UF A C T UR E

point care being taken to avoid the intro duction of condensed

1

a
,

water containing iron; and the dung thoroughly mixed with a large
quantity ( say 1 0 0 g l lons) of water at 45 to 5 0 C allowed to ° °
.
,

settle and drawn o ff through a basket and strained into the p u er

, ,

ing paddle through a second basket lined with coarse open canvas
( such as is used by plasterers to cover wi ndows while the pla ster
is drying) A further quantity of warm water should b e poured
" ‘

on the residue in t he mixing tub a n d used for diluting that in

the paddle to the prop er vol ume The temperature of the liquor .

may reach 42 C before the skins are introduced The liquor

°
. .

should be of a light colour greenish to brownish yellow ; if ,

-

darker it indicates decomposition of the dung by improper storing

,

or too long fermentation and will be liable to cause staining and ,

i n j ury to the skins A bout 3 3 litres of dry dung is require d

per 1 00 kilos of wet skin prepare d for puering ( 3 3 g a
.

. l lons per
Dr y dung should be of yellow to brown colour dark
'

1 0 00
-

brown or black dung i s spoiled and unsuitable for use We t

'

dung is m ore di fficult to j udge but very dark brown or black ,

should be rej ected as well as that with a very s trong smell

indicat ing that it has already fermented Bo r gm a
, ,

n s directions
’

a
.

bear the stamp of experience and Comm on sense n d the book ,

as a whole repays study .

B orgman recommends that the skins should be warmed by

paddling for some time in water of about 40 C ; to which a
.
°
.

couple of pails of puer paste have been added before bringing .

-

them into the puer the temperature of which they should reduce ,

to perhaps 3 8 C The puered skins s ho uld fe el silky on the

° '

grain and even somewhat slippery and when pres sed between
, ,

the finger and thumb a dark impress should be left and the ,

flesh shoul d be tender and easily scraped o ff The requisite .

condition will however vary somewhat wit h the kind of skins

and t he purpose for which they a
, , ,

r e intended A fter puering

the skins may be pad dl ed for h a
.
,

.
l f an hour in wat er of about the
same temperature as the puer .

Th e only attempt of which the writer is aware to give an actual

mechanic a l and numerical value to the e ffect on the skin of
puering and deliming processes is that of Wood who in collabora
La
, ,

tion wit h Dr H Sand and w constructed an instrument

for measuring the exact c o m p re ssio n a
.
,

n d elasticity of the skin

under varying loads 2

Fo r full details the original papers .
“

must be consulted but the following brief description may be ,

1
Thi s s e em s ad ag n e r o u sl y a
h ig h t e m p e r t u r e , b o t h f o r en z ym es ad
n

b at ia
c er

a
.

2
Th e p u c ro m e t e r . P u er in g B tin g,
, etc .
, p 85 ;
. 1 9 1 3 p 39 8
, . .
 D EL I M I N G ,
B A TI N G P U ER I N G D R EN C H I N G , , 233

given here The apparatus consists of two discs of about 1

.

cm area the upper of which is attached to a long balanced

.
2
,

arm which is loaded by means of a sliding weight on the prin

,

c ip l e of the steelyard and of which the exact horizontality is

,

determi ned by means of an electric contact device The lower .

disc rests on a micrometer screw by which t h e thickness of the ,

skin can be determined when it is pressed against t h e upper disc

to such an extent as to exactly b a l ance the load With small
loads gelatin is perfectly elastic returning to its o r 1 g1 n a
. .

l thickness ,

when the load is released and this is also the case to a large ,

extent with s kin s t il l swollen with lime but in the delimed or

‘

puered skin this res iliency is greatly diminished while the com ,

p r essib il it y is increased Th e apparatus is of considerable value

as giving a numerical v a
.

l ue for the puering which can be referred ,

to and repeated at any time but the conditions are too complex ,

for it to be easy to draw theoretical conclusions from the results .

Th e skin consists of a mass of gelatinous fibres , much swollen

themselves in the limed condition but with some water between
'

t h e m whil e when puered the fibres are much less swollen but with
‘

, ,

a larg er proportion of water in the interstices The fibres them

selves especi a
.

l ly when swollen have also a certain degree of

and all j ellies like in dia
, ,

rigidity ru b b e r oppose an elastic, ,

resistance to change of shape Wh en a piece of skin is compressed

between two discs a
.

ll these fo rces come into play in varying

proportions but any re a ,
l compression of the water itself or of
the actual skin substance is qu it e n e gligib l e The first effect
-
-
.
,

especially on puered skin is to expel the water from the inter ,

s t ic es b e tween the fibres but if the pressure is su fficient to over ,

come the osmotic force which produces swelling ( see Chapter

it is also expelled from the fibres themselves and this required
'

pressure will be affected by temperature and by the degree of

a l ka l inity of the fibre I f j elly i s compressed between the discs
.

it will bulge round the edges and the degree to which this occurs ,

will of course depend on the relative size and thickness of the

compressed j elly Th e t im e element must a l so be considered -

especially as regards resilience a

. .
,

s most of these e ffects depend ,

on the flow of water through the skin where it meets wi th great

a
,

frictional resist nce and the comparatively small forces tending

,

to restore equilibrium must necessarily take t im e to act R apid .

resilience probably depends mostly on the mere deformation of

shape of the j elly fib r e s or of the mass of j el ly
-
.
 C HA PTER XV

P I CKL I N G A N D D E P I GK L I N G

TH E process of pickling though long used for the preservation of ,

untanned pelts has become of increased importan ce from its

extensive use as a preparation for chrome ta
,

nning and much ,

light has been thrown on its principles b y the researches of Procter

and Wilson so that it seems to demand a short chapter to itself
Th e gener a
, .

l process consists in the swelling of pelt with an acid ,

and then treating it with a strong solution of common salt in ,

which the swelling entirely disappears and the pelt becomes very ,

flat and thin and is in fact converted into a sort of white leather 1
, ,

which however at once swells again if placed in water The

, ,
.

prin c iples of the process are adequatel y explai ned in Chapter X .

,

and need not be here repeated but it is highly probable that in

addition to the disappearance of the swelling osmotic pressure
there described an actual s a l ting out ,
by the very strong
salt solution occurs which has not been compl etely explained
-

, ,

but which may be either due to the consumption of t he solvent

in hydrating the unionised salt or to the j elly b e c o m m g 1 m ,

p ermeable to the solution of the unionised salt and so ex

“

a
,

i h wh l instead of only a sm l l fraction of the outside

’

i t
‘

p e r e n c n g e o e

osmotic pressure There is littl e doubt that this is the explana

tion of the powerful effect of anhydrous a
.

l cohol mentioned on
p 5 86 and there are neutral salts especially ammonium sulphate
‘

which will s a l t out neutr a

.
, , ,

l gelatin and pickle skin with regard t o ,

which i onisation can hardly come in as an explanation .

Th e earlier m ode of pickling was to swell ( and incidental ly to

'

tuck up the skins in sulphuric acid much diluted and then

to bring them down in strong s a l t solution but it is now universal ,

to add some salt also to the rising solution itself to control

a
undue swelling A suitable strength for the rising solution is.

about 80 grm common s l t and . grm sul phuric acid per .

litre On e hundred c c of this solution will require abo ut 1 5

1

c c of N/I alk a l i to neutr a

-

. .

. . l ise it and it sho ul d be tested after ,

each lot of skins which sho uld weigh when wet about 660 grm ,
.

per l itre of solution and maintained at the same strength by ,

1 Th is is a
t th a
t e r e of 80 l b of s lt a
a d n 75 lb o f s u l p h u r ic aid c p er
a a
. .

1 00 g ll o n s ,
th m
or e s e n um b er o f o u n c e s p e r c u b ic f o o t ( Cp .
p .

234
236 P R I N C I P L E S OF L EA TH ER M A N UFA C T UR E

cal cul ated quantity of acid not exceeding about I grm — molecule ,
.

of sul phuric acid per kilo of dry hide substanc e but the method -

is not economic a
.
,

l in practice from the dilution of the b ath pro ,

du c e d by the water bro ught in by the skins and the necessity of

constant large additions of s a lt .

Pickl ed s kins must not be brought into contact with water ,

which b y diluting the brine they contain allows the excess of

, ,

acid to act upon and destroy the fibre Even drops of water .

accidentally sprinkl ed on the skins produce this effect and it is

said that it spreads to pa
,

rts which have not been wet Fo r .

similar reasons it is necessary in tanning pic kled skins at least

to begin the process in liquors to which sa
.

l t has been add ed the ,

quantity required bei ng dependent on the amount of acid used

in pic kling the skins and where this is reduced to a minimum it
“

, ,

is even possible to tan without further addition of salt than that

contained in the skins .

In place of mineral acids organic acids such as formic and ,

acetic might be substituted with great advantage as regards .

safety and easy subsequent tannage but would be much more ,

expensive but in some cases they certainly deserve attention

Formi c acid especi a l ly has itself strong germi cid a
.
,

l properties .

Some years ago Mr A Seymour Jones pickled sheep pelts with

formic acid and s a
-

l t and sent them in a light b o x up the A mazon ,

to Manaos and back and they arrived again in England in a ,

perfect condition , spite of the fact that the voyage was through .

on e of the most trying regions of the Tropi cs Th e Seymour 1

.

Jones process for sterilisation o f skins against anthrax is also a

formic acid pick ling and the addition of the sma l l percentage ,

of mercuric chloride practically guarantees not onl y against

anthrax but against moul ds and mildew To sterilise dried
,
.

hides they are soaked for twenty four hours in a solution of -

1 per cent of commercial 9 0 per c ent formic acid and o 000 2

. .

per cent o f mercuric chloride and for skins a less concentration

of formic acid has proved efficient Fo r pickling the act ua
.
,

l con .

centration is not so important as that the acid absorbed should

be about 4 5 per cent on the actu a l dry hide substance of the
-
.
-

skin A fter the acid treatment the skins or hides are treated
'

with saturated salt solution as usu a l or even s al ted with dry s a

.

lt ,
.

1
C o ll eg 3 9 p 1 04, 1 86 Se y m o u r Jo n es r eco m m e n d s fo r s k in s a
ft er

a at a a
-
. . .
, ,

d e lim in g n d d r e n c h in
g tm re ent f o r t w e n t y f o u r h o u r s in -
0 25
0

p er
cent s o l u t io n o f f o r m ic or a 1 or 2 p er cent s o l u t io n of
p yr o l ig n e o u s
at i ) aid f f ap a a
. .

ro m ir o n i n d dl w h ic h s h o u l d b e r u n f o r
( cru d e ce c c ree e

f w h
e at fi t Th y
o u rs rs e sh o u l d a
l ma
so i re n t w e n t y f o u r h o u r s in t h e
-

a a t d a
.

s t lt
ur l ti ? e s so u on
 P I CKL I N G A N D D E P I CKLI N G

The wri ter found by an a l ysis of skin treated in this way that ,

after the salting t he formic acid was practically entirely replaced

in the skin by hydrochloric It may seem rather strange at .

first sight that the weaker formic acid in the hide sho ul d have
been able to liberate and take up the hydrochloric from the salt ,

but the resul t follows from the mass law In treating with a
very large excess of s a
-
.

l t the Cl ions are in enormous excess and ,

the resul t is the formation of a very minute quantity of gelatin

formate and a comparatively large quantity of gelatin chloride ,

and a similar distribution of the sodium s alts It is therefore

'

1
.

probable that the process might be cheapened without dis

advantage by employing about 3 per cent of H Cl and o nl y
1 per cent of formic acid on the actu a
»
.
.

. l dry material of the skin .

This woul d correspond to say 2 per cent of ordinary commercial

, , .

hydrochloric acid on the wet weight of pelt and it might be

advisable to add say 0 2 per cent of formic acid to the final s a
,

, , lt .

solution rather than mix it with the H Cl of the rising solution

Sever a
.

l methods of pickling have been suggested which do not

involve the use of acids Meunier proposes to treat with a di lute
solution of bleaching powder and a
.

l so with saturated solution of

,

potassium carbonate ( Cp p but both of these methods have

a
disadvant ges which tell against their practic a
. .

l use It has also .

been mentioned that skins cou ld be dehydrated and preserved

by soaking in saturated solutions of ammonium sulphate but ,

the ordi nary commercial article co ntains phenolic or tarry im

purities which produce a
,
n actu a l tannage of the skin and prevent ,

its returning to pelt on soaking (Cp p “

Skins p ickl ed with acids and especi a

. .

l ly with the stronger acids

a
, ,

st ill retain enough to cause them to swell excessively if soaked in

water so as to remove the salt and if t nned in this state produce
ve g et a e ta e usu a
,

w ith bl n s a quite rotten leather T h l remedy is

to add s uffi cient s a
.

l t to the early liquors to prevent s welling until

a
the acid of the skins has been sufficiently displaced by tannin
n d in A merica it is not unusual not o nl y to add s a

sul phuric acid to sumach liquors in the first stages of tanning

l t but actu a l ly
,

a
,

which produces leather with a very much sm ller expenditure of

sumach than in the norm a l process Th e leather is apparently .

ful ly tanned and does not appear to contain free sul phuric acid
, ,

which is probably expelled by the tannin in the later stages of

the process
Wh en it is desired to give a norm a l tannage without s a
.

l t the
skin must be first de p ic kl e d that is the acid must be neutra
, l ised ,

or removed This may be done by any weak al kaline solution

.
,

1
C o ll eg .
, 1 1 ,
1 9 1 2, p . 68 7 .
238 P R I N C I P L E S OF L EA TH ER MA N U FA C TU R E ‘

but considerable care is required not to bring the skin into a

re a
l ly a l ka l ine condition Th e prettiest proces s theoretically is .
, ,

to dru m or paddl e with an insoluble alkaline carbonat e such as ,

”
whitening or with magnesia but it has the ev il in practice, ,

that some of the whitening is apt to adhere mechanically to the

skin and produce stains or bad colour Sodium bicarbonate or
borax a
.

r e suitable salts to use but excess must be avoi ded and

ordinary soda cryst a

, ,

a
l s may be used satisfactorily wit h sufficient
care No doubt St i sn y s neutralising mixture ( p 2 7 2 ) of soda ’

cryst a
. .

l s and ammonium s ul phate or chloride in about equal

quantities would also be safe and efficient On e of t he cheapest .

and most satisfact ory de p ic kl ers is sodium thiosulphate hypo

as recommended by Mr Seymour Jones as it is quite neutral and
1 -

, ,

cannot do inj ury by excess

When pickling is used as a p r el imm a
.

~
r
y to chrome tannage the ,

obj ect is qu it e di fferent from that of its use as a preservative

and is generally to introduce acid into the pelt Thus if he a a
,

vil y .

pickled p elt be introduced i nto a neutral bichromate solution it

will b e d e p ic kl e d by the a ction of the bichromate and su fficient
f

chromic acid wil l be liberated to chrome the skin and in any ,

case a much smaller amount of acid will b e needed in the chroming

1
Co ll eg 1 1 1 9 1 2, p 6 20 S ey m o u r — o n e s J u se s 4 t o 5 l b p er d o e n z
a aai t y f th a a
. . . .
, ,

p elt s l m ti He so en t ons v r e o o er u se s o w h ic h t h io s u l p h t e c n
b p t in l a m a fa ab i d i p l a
.

e u th e t Fi l y g er d h yp nu c ur e ne ro u n o c n e i se n ce

f a l t aa a ad ki It i a p w f l d h y d at
.

o s p s ti f h id r e s erv ve o es n s ns s o er u e r n

ad if p p ad p l t i a a ad t h t a t d wit h a w a
.
,

n re t ret d w it h h y p e s s ur k e o n en re e e

aid ab at if ul w h it l a
c e th
u lt pa t l y b y d h yd ae ti ad p at l y
e e r r e su s, r e r on, n r

ip it a , wh i h a b e f a d ad d y d
,

f m th fi ly p
ro e t d
ne lph re c t liq e su ur c c n uore n e

m i l a
-

a it a a t f ha
,

or, t t d w it h
re e bl il w il l p d su e th o s, ro u ce so r o c o s e er

f aa
-

I t a id a a lp h a ab
.

ns e d l m
o n l mi i m c t u d t d or m u n u su e c n e u se o eco

a a al mi a ta a ad if f ma
, ,

p o se t h h y p d e g i o n g ve l d hyd n b u n nn e, n or e e e

f th
ur a dd d aer g d b ff l a e th lt A oo i ad pla
u i d e er r e su s cur o u s n u n ex ne

f g a a d fa
-

a l a If g a
.
,

m t f m p lt
‘

ff t i t h l th
‘

e ec s e re ov o re
y se n ro e or e er re s

a d l im d b y a a ad t a t d w it h a
.

h id ki t t d h yp l ti
"

es or s ns re e e s ur e o so u on n re e

w a e k a id b a th c l a d ki a l igh t l y w l l wit h aid ad t h

or c e n se s ns re s s o en c n en

t ea a i ap a m t h g a ab
,

r t d wi t h h y pe i it h d dl
o, d
n e er c se n e or ru e re se c n e

th b a ma t th g a
,

w k d
or t e ou m th
on ki y be h m d wit h
e or e s ns e c ro e ou e re se

tly a pp a g
,

su b q se uen e rin

G a a ll i g m a a t
.

y b tt
re ft
s u y b
s p d d i
er ro
p n t; e su s en e n 1 0 o 20 er c en

l ti f h yp a t 4 Fa h f af w h
o wh1 th
0
g a wil l
°
r or e o urs , en e re

fl a
so u on o se

f a ad h a
.

o t t th o e ld b
sur k im m d ce, ff b f n th b tt s ou e s e o e o re e u s re

wit h d a w If r b q n t ly t a t d w it h asu w ea k a
se id p f a
u en b ly f mi re e c r e er or c,

d b t a g d d a l f t aw ill b
.
,

th l
e co o ur wil l b m h im p e uc t ip p d ro v e u oo e o n e s r e

ad if d f l th l a ta a aa
, ,

n u se th w il l
o r so e q i g eH yp e l b er re u re re nn e o c n so e

ch i g a ad if hid aé t a
-

d aa bl a t a
.

u se s g t f e t n en t d w it h f m or ex r c s, n es r re e ro

m a m —t a d w it h a t a
2 1 t op t
1 0 f h yp t
er ce nh y y b d o t o t i e e ru nn e ne ex r c n

a y h t t im
.

ver s or e .
 CHAPTER X VI

A L UM TA N N A G E OR TA WI N G

WE have now followed the raw materi a l up to the fin a l stage of

preparation for its actual c o n ve r s1 o n i nto leather and it remains
'

to consider the means by which that important chan ge is pro

du c e d . Though as yet the vegetable tanning p rocess is most
largely used and possesses the greatest commercial impo rtance
, ,

the use of mineral salts has long been known and through the , ,

advent of chrome tanning has placed the perman ent supremacy ,

of the vegetable tannins in considerable doubt No t onl y t he

importance o f minera l tanning p rocesses but their gre ater sim
.

p l ic it y from the scientific side j ustifies their consideration before ,

tho s e of vegetable origin .

In the previous chapters it has been shown that to produce a

permanent leather it is not only necessary to dry the fibres in a .

separate and non adher ent condition but so to coat them or alter
-

their chemical character that they are no longer capable of being

”

swelled and rendered sticky by water All salts ( see p 1 23 ) . .

which produce a contraction or dehydration of the fibre similar

to that caused by a l cohol are capable of the first e ffect in a greater
or less degree Many sulphates and particularly t ho s e o f sodium
.
,

and magnesiu m though they will not alone produce leather will
, ,

so far contract the fibres as to greatly hasten tanning by vegetable

tanni ng materials and they are therefore capable of useful
application in quick tanning processes especi a l ly where tough a
,

nd ,

light weighing leathers are aimed at which may b e s u b se qu e n t l y

'

weighted and solidi fied by further treatment Strong solutions .

of ammonium sul phate are almost as strongly dehydrating as

alcohol and will produce white leathers very similar to those
,

formed by pickling a fact which is certainly of considerable

commerci a None of these s a
,

l importance l ts however can form

.
, ,

a complete leather in themselves but re quire the assistance of

met a l lic s a
,

l ts which will permanently fix themselves in the fibre

, , ,

and diminish or destroy its attraction for water Many substances .

have this power in a greater or less degree but all those of com
m e r c ia l importance belong to the group of which a
,

l uminium ,

iron and chromium are representative and which are capable of

producing salt —formi ng oxides of the fo rmul a
, ,

Mz O3 ( e g alumina '

. .
,

2
40
 A L UM TA N N A G E OR TA WI N G
’

241

A1 20 3 ) Manganese of which the salts of this type are very

.
,

unstable has very slight tanning power while t itanium which

'

in many ways is a
, , ,

l lied to the group though it does not strictly ,

belong to it has recently been patented as a t anning agent

, .

Fo r the present however we may limit our attention to the three

metals first n a
, ,

in e d .

Al umina and its salts demand the fir st attention not only as ,

-

having been used for leather manufacture in very early times but
as being st ill important commerci a Th e metal a
,

l ly l uminium is .

now well known and its o x ide alumina A1 20 3 is abundant in

, , , ,

Nature combined with silica in the form of c lay and bauxite as

,

fluori de in combination with sodium fluoride in cryolite and

,
.

in some cases as a native sulphate Alum sh a

,

l e which was .
-

formerly the principal source of alum is a bituminous clay con ,

taining much iron sulphide and which when calcined yields

aluminium sul phate A s a
_ “

l uminium sulphate does not crystalli se

.

readily and was di fficult to free from iron potassium sul phate
was added t o the liquor obtain ed by leaching t h e c a
, ,

l cined shale ;
from which after concentration by boiling a double sulphat e of
potassium and a
, ,

l u minium potash alum

was easily crystallised out A lum is now usu a
-

, ,

a
l ly made by d e c o m
.

posing clay or bauxite with sulphuric acid n d ammonium ,

sulphate is generally substit uted for the potassium salt yielding

ammonia—a l um a double sulphate of a
_ ,

l uminium and ammonium

of similar constitution t o potash a A mmonium a
,

l um l um is
easily distinguished from the potassium s a
-
.

l t by the strong smell

of ammonia which it evolves on the add ition of caustic soda or
lime So far as is known there is no practical difference in
.

t anning effect between the two salts and ammoniu m alum is ,

cheaper and slightly Stronger its molecul ar weight being 9 06 as

against 9 48 for the potassium salt Either a
, , ,

l um dissolves readily .

in cold water to the extent of about 9 parts in 1 0 0 of water ,

and more easily and to a much larger extent in hot water from
which the excess cryst a
, , ,

l lises on cooling I t is said that for

purposes of leather manufacture a
-

l um solutions should not be

boiled and though it is improbable that this produces any
, ,

considerable change it must be remembered that chrome alum

on boiling re a
,

l ly does undergo decomposition to free acid and a

-

more basic salt indicated by change of colour from violet to

,

green from which it slowly returns to the violet form on cooling

,
.

A lum s are only valuable in leather manufacture in proportion

to the a
'

l uminium sul phate which they contain the potassium o r ,

ammoniu m sulphate taking no part in the reaction except as a

neutral s a lt ( p and since improved . m e thod s have

1 6
2 42 P R I N C IPLE S OF LEA TH E R M A N UFA C TUR E

rendered po ssible the production of aluminium sulphate p r a

-

ct i

cally free from iron it has largely tak en the pl ace of alum than
which it is both cheaper and stronger Cryst a l lised a
, ,

l uminium .

sulphate has a molecular weight of 666 and is

o f equal value to 9 0 6 of amm o nia a l um and 9 48 of potash a
, ,

l um
l ums a
- -

I ron is the most obj ectionable impurity in both a

.

nd
aluminiu m sulphate and may be detected by the addition of
, _

potassium thiocyanate which will produce a red colour or ,

.
,

potassiu m ferrocyanide yellow prussiate of potash which

will produce a blue A s the iron may be present in the ferrous
.

condition it is safer to add a little ferricyanide red prussiate

,

or first to boil the alum solution with a few drops of nitric acid
or bromine water Fo r more accurate determination of iron see
.

pp 20 1 3 6 .
,
.

No satisfactory leather can be produced with a solution of

alum or aluminium sul phate a l one the skin drying horny a
.

nd
'
'

, ,

i ncapable of softening by stretching In practice salt is always .

,

used in addition the proporti o n being very variable but averaging

about h a
a
, _ ,

l f the weight of alum or two thi rds the weight of sul

phate of lu mina employed Th e mode of action of the s a
-

l t has
a
.

long puzzled chemists and it h s been supposed that its use

was to convert the a l uminium sulphate into chloride a
,
'

reaction
'

which takes place to some extent but which fa i ls to expl a

.
,

in the
production of a soft leather since a
,

l uminium chloride though

f reely taken up by the skin produces a
, ,

l one no more satisfactory

leather than aluminium sul phate The re a
,

l explanation is found .

in Chapter X A lumina is a weak base which readily gi ves up

its acid to the pelt becoming c o n ve rt e d in t o a basic s a
.
,

,
l t ( see
below) The acid not o nl y swells the pelt and renders it in
.

capable o f producing a soft leather but the swollen pelt is less

ready to ab sorb the a l umina s al t and so remains u n d er t a
,

nned
-

.
,

Th e addition of salt prevents the swelling e ffect of the acid and

produces a parti a
,

l pickling of the skin ( p which in con ,

j un ction with the tanni ng e ffect of the basic alumina salt formed ,

yields a satisfactory leather though one which 1 s readily affect ed

by washing If instead of adding common s a l t to the a
,

l um
“

solution an a l ka
.

l i such as soda is added it combines with a

portion of the acid forming so di um sulphate while the a
, ,

l umina
remains in solution as a basic sa basic s a
, ,

l ti A s the term lt
’

must be frequently employed in con nection with miner a l tannage ,

it may here be explained B asic salts are compounds inter

mediate between the norm a
.

l salt in which the whole of the base ,

is combined with acid and the hydrated oxide in which the , ,

whole is combined with OH groups Thus aluminium chloride .

,
2 44 PR I N C IPLE S OF L EA TH ER MA N UFA C T URE
and have since been patented b y Hunt but the patent
“
'

1 85 8 1
,

( probably invalid ) has long lapsed A g ood stock solution for

practic a
.

l use i s mad e b y di ssolving I O lb of s ul phate of alumina

a a
.

in 1 0
g l lons of water and 4 lb of washing soda in 4 g l lons ,
.
,

and gradually mixing the latter with the former Salt can be
used in addi tion if desired and flour and egg yolk may a
.

l so be
added B asic a
-

. l umina solutions can also be used in considerable

quantities in conjunction with chrome without rendering the ,

leather incapabl e o f standing the boiling test or materiall y \

,

altering its colour

In curing sm a
.

l l skins where it is not desirable for the fur to , _

_

come in contact with the l iquid or in the tawing of wool rugs it , ,

a
is often convenient after freeing the skin as much as possible
from blood a
,

n d dirt and a dhe ring flesh to stretch it on a fr me

o r na il i t out on a board a n d apply a strong a l um and s a

, ,

lt ,
- -

solution as h o t as the hand wil l bear with a sponge repeating

, , ,

the operation till the skin is struck through 2 About I lb of

a lb of s a l t per g a
.
. .

l um and l lon is a suitable stre ngth I n p lace

of applyin g the solution powdered a l um and sa
. .
“

l t is sometimes
rubbed into the wet skin Al um e d goods shoul d genera
,

l ly be .

dried out rapi dl y and finally at a good t emperature as this tends

to fix the tannage which is a l so m a
, ,

d e more p ermanent and

,

resistant to water by keeping the skins for a month or m ore in

the a l u m e d condition an operation known as ageing When
first dried a
.
,

l u m e d goods are invariably sti ff and horny and to

, , ,

give them softness must first be damped back to a flexible ,

condition ( best by placing in slightly damp sawdust ) and then

gradua ll y softened by mechanic a
,

l means Staking and

perching are the usu a
.

l methods the first Consisting in draw ,

a
ing the goods vigorously over a bluntish blade fixed on the top
of a post and the second in fixing the skins on a horizont l
pole ( the perch and working them with the crutch stake
a tool formed somewhat like a sm a
,

l l shovel with a semicircular

blade in place of which a moon knife ( a round blade some
what like a
-

a
,

broad thin quoit ) is often fixed in a wooden crutch .

Th e tools n d mode of using them are sho wn in figs 44 and .

1
N tm a f
und We s e n d e wGe t/ be r e t B r a u n s c h w e ig , 1 85 8
am t h d a b g ba
, .

2
A s im il d w it h t
r e i ch m
o l ti c n e u se s ron s c ro e so u ons,

p d i g a l a th w h i h ab wa h d ad if t h l ti b a
t a t d
‘

ro uc n e er c c n e s e n e so u on e s ur e

l t ad a wa y tall i a
'

w it h a
,

s ll w d t d y nth ki b f o hi g t h
e o r on e s n e o re s n e cr s s

a k i at taki g a ay
, ,

ti
on o f th lt ft th
e s d
so s o lm t en s e s n s o r en er s n os u n n e c e ss r

t a t a
.

3
Th p e h w i fig 45 i
ro ce ss s ll y o p hi g b t
n g dn s no c u erc n u ro u n

i wh i h a k if wi t h ah a
.
,

i g
n n m c p t d dg i
oon d t d n e s r urn e e e s u se o re uce

h a m t im ait t t h
-

a
,

th e t hi k of t h
c ki n e ssth p t th e s n on e erc e s e e s s re c es

ad ft it b t t h at i i m h t h a
,

n so en s , um e c on s uc e s e .
 A L UM TA N N A G E OR TA WI N G

Machines described on p 2 48 are now gener a

, . l ly used for these
,

operations A fter the first staking or softening the skins are

.

all owed to become nearly dry and are then staked a second time
,

Some j udgment is required as to the precise degree of moistur e

in each case in the first instance the skins must be su fficiently
da m p t o yield without inj u ry to the mech nic a
m
l stretching but
in this state they retain su fficient moisture to enable the fib r c s
a ,

FI G .
44.
— St a
ki ng Wh it e L e a
t her .

again to adhere on drying and at the second staking or perch

ing they must be damp enough to a
_
l low these fibres to be
.
\

loosened without violence and dry enough to prevent their again

,
.

adhering Th e first stretching must n o t b e too severe

. .

Th e following slight sketch of the manufacture of calf — kid

will serve to illustrate the practic a l manufacture of t he finer
al u m e d or white leathers though little if any is now made
Th e raw materi a ca
.
,

l is in England mostly large market — l f though

sa
,

l ted and dri ed skins are sometimes employed A fter sufficient .

soaking or washing in water they are lim e d wit h o u t arsenic or '

other sulphides in limes which must not be a l lowed to grow stale

or putrid until the h a
,

,
ir can be easily removed A fter unhai ring .

and fle shin g in the usual way they receive a few days in a pretty
2 46 PR I N C IPLE S OF LEA TH E R MA N UFA C T UR E
fresh lime in order to plump them and are the n freed from lime
gradu a
,

l ly but as completely as possible b y successive st e e p in gs

,

and washings in water softened by a mixture of th t already

-
, _

FI G .
45 .
-
G r o u n d in g wit h t h e Mo o n —k n if e .

used on other goods and by working on the beam This acts as .

a partial subst itute for puering with dung which is no longer

used on calf kid Probably an o r o p o n or p a
,

. n c r e o l bate is now

employed The goods are next drenched in the ordinary way

.
,
2 48 P RI N CI P L E S OF L E A TH ER MA N U FA C T UR E
of flour and egg To replace these r é egging is necessary
.
-

and while some manufacturers give egg yolk or egg yolk and
-

,
-

flour only many add a propor t i o n of s a l t and sometimes a l so of

a
, ,

l um .This is done before dyeing if the skins are to be blacked

on the table but as t r ay dyein g ( see p 49 9 ) woul d again wash out
,
-
.
 A L UM TA N N A G E OR TA WI N G 2 49

'

the egg the r e egging is deferred till after dyeing if this p r o c e s s is

,
-

resorted to B efore dyeing the skins receive an alkaline mordant

.

to overcome greasiness and enable them better to take the

col our In former times this was usu a
. l ly st a l e urine but th is
'

has mostly been superseded by solutions of hydr o l e in e ( a

washing powder) or o f so a p rendered m ore or less a l ka l ine with
,
.

ammonia Eitner gives the following recipe viz 1 b Marseilles “

. .
.
,

( olive oil ) soap dissolve d in boili ng water 5 or 6 egg yolks add ed

and the whole made u p to 4 gall ons with water and 7 lb pot a
-

, ,

sh
1
.
,

bichromat e Th e colour used is infusion of logwood or its

.

extract or two thirds lo gwood and o n e—third fusti c which is 1

best e xtracted without alkali a sm a

-

, ,

l l quantity of soda or ammonia

a
,

b eing afterwards add e d Coal t r dyes are often add e d It is .

-

fixed and darkened by a wash of iron liquor or a solution of 1 of -

ferrous sulphate in 7 5 of cold water A fter being again dried .

the skins are sometimes grounded with the m o o n f kn ife softened ,

again by staking or perching for which a machine with inclined ,

or spiral blades attached to a drum and working on a sort of

leather apron is often preferred to machines of the Slocomb
type and rubbed over on the grain with a composition containing
oil wax etc and a r e fin a
,

,
ll y ironed wi th a heavy flat iron to
,
.
,
.

give them a fine and smooth surface Eitner gives a recipe for .

the gloss : 1 kilo gum arabic l kilo yellow wax kilo beef
ta
. . .
, ,

llow kilo Marseilles soap 1 litre strong logwood infusion

and 5 l it r e s wa
.
, , ,

t er The water is brought to a boil in an earthen

pot and then the soap wax gu m and t a
.

,
l low are added suc , , ,

c ess ive l y each being stirred till dissolved befor e adding the next
,

and lastl y the logwood After boiling for an h our it is al lowed .

to completely cool being incessantly stirred during the whole ,

process A fter ironing the goods are rubbed over with a final
'

gloss for which Eitner gives the following recipe 8 litres olive
,
.

oil 5 00 grm tallow 5 o o grm yellow wax 5o o grm rosin

, _
.
, .
,
.
,

5o o grm gum arabic ( previously soften ed in water )

. Th e .

mixture is cooked for two hours in an earthen pot till the water
is evaporated and all owed to cool with constant stirring The
skins are then rubbed with a flannel with a very sm a
, .

l l sprinkl ing
“

of French ch a l k and are ready for sale

kid has been a
.
,

The manufac ture of calf — l most entirely super

s e d e d by that of b o x —ca l f from the superior water resisting powers
of the latter a nd a
-

l so on account of the costly nature of the

‘

materi a
a
,

l s employed one Leeds manufacturer in former times ,

using not less than 50 tons of egg yolk annu l ly but the leather '

made a very smart and comfortable boot and a chrome c a

-

l f kid ,
-

1
Th e a
d d it i on of f u s t ic is t o co r r e c t t he b lu e b l -
'

ak c of t h e l o gw o o d .
2 50 P R I N C I P L ES OF L EA TH E R MA N UFA C T U R E

might very probably come into fashion again The difficulties

in its manufacture are however considerable as it is a
.

, l most , ,

impossible with basic chrome liquors to get the absolute smooth

ness of grain required and for this ca us e chrome leathers have
usu a
,

l ly a boarded grain It is possible that if the tawing were .

commenced with an al um tawing paste and a suitable basic

chrome liquor onl y added when the paste were a
,

l most ab sorbed ,

this difficulty mi ght be overcome Earlier substitutes for egg? .

yol k were unsuccess ful either because unsatisfactory in e ffe ct

or equ a
, k

l ly costly with t he genu i ne article but with our largely

“

increased knowledge of emulsions this di ffic ul ty might probably “

be overcome perhaps by the use of sulphonat ed oils The flour

, .
,

of which the gluten only and not the starch is absorbed and the
proteids o f the egg yolk which are importa
, , ,

'
-
nt as fillings mi ght , ,
‘

probably be replaced by o t her colloids of an organic nature or

by minera l s such as colloidal silica or a
,

l umina phosphate .

The manufacture of glove kid is quite similar in principle to -

that just described but varied i n detail to suit the softer and more
delicate skin s employed to give gre a t e r softness and especi a
,

l ly
' '

, ,

the quality of stretching in any directio n without springing back

which is so characteristic of the leather Lamb skins a
,

r e the

princip a l raw material though genuine kid is a

-
.

l so employed for
,

the best qualities The manufacture varies much with the

qu a
a
.

l ity and character of the goods Th e skins which are mostly .

,

dry are soaked in clean n d cool wat er for three to four days
according to age and thickness Common qu a
, ,

l ities ( small im .

ported slink lambs) are often unhaired by dipping in or painting

with a paste of gas lime lime and s ulphide Of sodium or lime
-

, ,

and red arsenic so as to dest roy the wool B etter skins are
,
.

sometimes unhaired by painting on the flesh with lime alone or

in mixture and in other cases ordinary lime pits are used with
limes which are most usu a
-

,
l ly strengthened with red arsenic ,

which is added to the lime while hot from slaking ( op p

The c a
. .

l cic sulphydrate ( and perhaps sul pharsenite ) thus formed

hastens the unhairing and preserves the gloss of the grain
a
.
,

Well conducted glove kid est blishments avoid as much as -

possible the use of old limes which produce a loose porous , ,

leather with a rough dull grain The liming lasts on t he average

, ,
.

ten days and is of the greatest importance It is essential that

the inter fib r ill a
.
,

r
y substance sho ul d be di ssolved that the leather
ma a
-

y have the quality kno w n in Germany as S t n d that is to say , ,

may be strongly stretched in either length or breadth without

spri nging back It a l so depends upon the liming ( and this is of
.

special importance in the case of lamb skins) whether the tissue -

2 52 PR I N C IPLE S O F L EA TH E R MA N UFA C T UR E

strain ed and the bran water onl y used to save t he trouble and -

cost of removing a
,

dheri n g particles of bran from the delicate

skins Sufficient of the liquid must be employed to well cover
the skins and the temperature ma
.

y range from 50 F ( 1 0 C )
° °

These conditions are favourable to bacteri a

.
, .

t o 68 F ( 2 0 C )
° °
.
-
. l
‘

activity which comes into play and on the one hand evolves
acetic and lactic acids which dissolve any remaining traces of
, , , ,

l ime and on t he o ther loosens and di fferentiates the hide tissue

, , , ,

so as to fit it to absorb the tawing solution Much care is required .

in the management of t h e bran drench especially in summ er , ,

a
since the lactic readily passes into some other fermentat ion ( see
lso p Th e tawing mixture is composed (like that em
a
.

ployed in the manufacture of calf—kid of alum s lt flour and , , ,

egg yolks in a quite thin paste A small quan t ity of olive oil is
a
-
.
,

l so generally used Th e ski ns are either tro dden in it wi th the .

feet o r more generally put into a t umbler drum with it Kath ;

r e in e f pointed o u t m a
- -

.
,

ny
y ears ago that a mixture of olive oil
,
'

,
1

and glycerine might be p artially subst ituted for the egg yolks .
-

in b o th t he tanning and dyeing of glove kid leather -

.

Th e t awed skins are now dri e d by hanging o n poles grain

a
,

inwards R pid drying in well ventilate d but only moderately

.

'
-

heated rooms is essential to the manufacture of a satisfactory

,

product .

The dry leather is rapidly passed through tepid water and ,

after being hung for a very short time to allow the wat e r to ,

drain o ff is trodden tightly into chests and allowed to remain in

them for about t welve hours so t h a
, ,

t t h e moist ure may be uni ,

forml y distributed It is then trodden on hurdl es ( German .

H or den ) composed of square bars of wood , j oined corner to corner ,

so as to make a floor of sharply angular ridges Th e next opera

tion is stretching with the moon knife after which t he -

leather is dried nearl y completely and staked again ,

.

This completes the tawing process Th e goods are now .

aged as in calf kid manufacture B efore dyeing they are

'

-
. .

washed with tepid water t o remove part of the tawing mixture

and especially superfluous alum and sa
,
lt a n d are re egged much
, ,
-

like calf kid before dyeing if the latter is done by brushing and
, ,

after if in the dye tray or paddle A niline colours are more -

.

used than formerly especially for topping and brightening the ,

natural colours but the dyewoods and oth er mordant colours ,

are still largely employed The leather is first prepared with

an a l kaline mordant ( st a
.

l e urine ammonia etc ) ( Cp p , ,

. . .

then repeate dly brushed with or dipped in the dyewood liquor ,

(1 (1 8 7 6 )
1
G e rb e r i , . 8 7 5) p . 1 7 0 ; ii .
p . 664 .
 A L UM TA NN A G E OR TA WI N G 2 53

and a mordant wash striker German Ue ber stmch) containing ’

some metallic s a l t is gener a

,

l ly applied with the obj ect either of ,

b ri nging out the special tone required or of making the colour ,

more li vely and permanent The striker is usually a solution of .

one of the so called vitriols white vitriol ( zinc sulphate )

-

blue vitriol ( copper sulphate) green vitriol ( iron sulphate ) , ,

a tin solution spirit or occasional ly other salts .

A ft er the dyeing the skins if dipped are wrung ou t and , ,

r e egged ;
-
if brush dyed sleeked out with a brass or ebonite
-

sleeker to get rid of superfluous water They are then dried in an .

airy room B efore staking ( stretching) the skins are laid or hung
.

in a damp cell ar or in moist sawdust They are staked twi ce .

once damp and once nearly dry ; and are finished by glassing
,

or ironing .

Skins which are much damaged on the grain or otherwise ,

faul ty are smoothed with lump pumice on the flesh side or

, ,

flu ffe d with fine emery on the fluffin g wheel They are then
dyed on the flesh side mostly by dipping but o ccasion a
.

l l y with
, ,

the brush in which case the method described is slightly modified

Tawing with a l um and sal t is frequently empl oyed for co m
.
,

_
moner
and stro nger leathers such as aprons ( of sheep skin ) leather for
,
-

whip lashes laces for belts and skivers for capping druggists
-

, ,
’

bottl es Th e process is practically the same as for calf kid

.
-

except that no egg and little flour is used Often flour is entirely
omitted and the goods may then be a
.

,
l u m e d in tubs in which ,

they are merely handled as the alum solution penet rates quickl y , .

Goods which are required white are frequently han dl ed or tumbled

”
with a milk of whitening both to improve the colour and to
neutralise any acid present and fix the a
,

l um by rendering it ,
,

more basic Al u m e d goods can be stuffed with greases either by

.
,

hand or in the drum after thorough softening by staking

Al u m and other salts of a
.
,

l umina are frequently used in com

bination tanni ng with vegetable materi a
-
l s ( see Chapter XX I I ) .

”
Green leather for laces dongola and dog skin glove , ,
-

leathers are made in this way Glazed kid for la di es shoes .

’

must be slightly vegetable tanned on the surface or it will not -

glaze but this is frequently accomplished by the use of materi als

,

in the dye l iquor c on taining tannins This was long considered

-

a French secret .
 CHA PTER XV II
CH R OM E A ND I R ON TA N N AGE S
B OTH chromium and=iron like aluminium form trivalent sal ts ‘

, ,

which have st rong tanning properties but in most other respects ,

“

they are very di fferent not only from it but f rom each other ,
.

While the atomic weight of aluminium is only 2 7 those of

'

_ ,

chromium and iron are 5 2 and 5 6 respectively— nearly double as

much Wh ile a
. l u minium so far as i s known only forms one oxide
, , ,

A1 2O3 i ron and chromium form quite a series chromiu m b eing

°

the more oxi di sable of the two and while a

, ,

l umina i s amphoteric
forming not onl y s a l ts with acids but a
.
, ,

l uminates with bases the

chrome and iron oxides are e ither acid or b a
,

sic b u t not both

'

The s a l t s o f Cr ( chromous s a
.
,
/

”
l ts ) are blue but so avid of oxygen
that they can hardl y be preserved while the ferrous s a
,

l ts are
green and only moderately oxidisable The triva l ent s a
,

l ts of
‘

.
,

chromium are green or violet while those of iron ( ferric salts) are , ,

yellow or orange and are stable in absence of reducing sub

stances 2 Wh ile iron has avery unstable higher oxide forming
,

red ferrate s a l ts the correspondi n g oxide of hexava

. ,
,

l ent Cr
a
“

, ,

chromic anhydride Cr O3 is deep or nge or red and forms very

, , ,

stable chromates and bichromates and there is yet another ,

oxide probably perchromic acid which when chromic acid is

, , ,

oxi dised with hydrogen peroxide can be shaken out with ether
as a bright blue solution B oth ferric s a
,

l ts and chromates are

.

reduced by light in presence of organic matter but not salts ,

of Cr 20 3 These differences are important in many ways with

.

regard to their tanning properties .

Metallic chromium i s a grey and very infusible metal derived

principally from chrome iron ore a miner a
, , ,

l which contains the ,

oxides both of chromium and iron This is furnaced with a .

mixture of lime and soda or potash when it absorbs oxygen ,

from the air the chromium becoming converted into chromic

,

acid which combines with the alkali present while the iron
remains u n disso l ve d a
, ,

s ferric oxide On lixiviating the mass and

'

1
So d iu m ad p t ai
n o ss u m a
h y d r t e s d is s o l v e sm ll q a
a t it i
u n e s o f c h r o m iu m

h y d r o x id e t o p in k o r gr e e n s o l u t io n s , p e r h p s o f s o d iu m c h r o m it e a
a aa
.

2
A c u r io u s e x c e p t io n in c o l o u r re t h e i ro n o x l t e s , o f w h ic h t h e

f e r r o u s is or ag
n e -
b r o w n w h il e t h e f e r r i c i s d e e p g r e e n
, .
2 56 P RI N C I P L E S OF L EA TH ER MA N UFA C T UR E

many m ordant colouri ng matters Fo r this purpose norm l or

a a
basic chromic s lts are sometimes used somet imes chromic a
.

cid ,

or dichro mates the latter acting not o nl y by yielding chrome ,

oxide on reduction but as oxidising agents to t he c o l o u rin g

'

matters Most of the colours produced with chrome mordants are

j

of dark shades that with logwood being deep violet or black , .

The mordanti ng p ower of chromium is important in the dyeing ‘

of chrome leather Bichromate of potash is often used in dilute .

solution for darkening the shade of leather dyed with other

materials but i s not to b e recommended on account of its
’

destructive action on the leather .

Numerous patents have been taken f o r processes of chrome

tannage Th e first practical method was described by Professor
.

Knapp in 1 8 58 ( see p though he did not recognis e its .

value Some of the patents have a historical interest t h ough no

practic a
.
,

l importan ce A mong thes e may be mentio ned that o i

Ca va
. .

llin a Swedish apothecary whose obj ect was dyeing rather

, ,

than tanning but who treated raw hide with a solution of ,

‘

bichromate which was afterwards reduced on the fibre by one ,

of ferro u s sul phate Th e leather produced is dark reddish brown 1

and tender from the amount of basic ferri c s a

-
.
,

l t formed at the same

time Mr J W Swan well known in connection with photo ‘

graphic processe s and electric l ighting a

. . .
,

a
l so patented a process of
chrome tannage ( a
,

s an ddendum to a patent on carbon printing) ,

in which the chromic aci d first fixe d in the pel t was reduced by ‘

o xalic or other suitable acid A lthough it is possible to pro

“

.
,

a
duce l e ather within the lines of the patent the strongly acid ,

reaction of the reducing agent renders it unsuit ble for practical

use The first chrome tanning process which made any show of
.
-

pract i cal succes s was that patented in 1 87 9 by H einzerling

which wa
,

s acquired in t his country by the Egli nton Tanning

Company and also worked under their license for a short time
'

, _

by the Y orkshire Tanning Company at Leeds Though t he .

process was not commercially successful on any considerable

sc al e it possesses points o f interest which make a brief description
,

desirable The hides or skins after preparation in the usual way

were treated in a mixed solution of s a l t alum ( or a
.
, ,

l uminiu m .
,

sulphate) and potassium bichromate but no systematic attempt

, ,

was made to reduce the chromic acid to a tanning form the pro
duct being a t first at least merely an a
,

l um tannage coloured
, , , ,

and perhaps somewhat hardened with chromic acid though on ,

1
B o t h Ch dw ic k in A m e r ic a a( U S A P at 56 44 8 9 6 ) ad G t t h a lk 1 0 1 n o sc

a 58 ha pa t d t h Caa
. .
,

228 ) se e m lh p w it h l ig h t
( Fr P t 2 to t ve re en e e v n ro c e ss s

d ifi a
-

. .

mo ti c ons .
 CH R OME A ND I R ON TA NNA G ES 257

keeping for a length of time reduction gradually t o ok place at

the expense of the hide fibre and of the fats employed in curry
ing so that the leather internally became greyish green and
re a
-

, ,

l ly chrome tanned Specimens of the early products of t he

.

process preserved in the museum of the Leather Indust rie sI

,

D epartment at Leeds have now all undergone this change but

, ,

are stil l tough and flexible showing that the rapid tendering of ,

the H einzerling leather which was one of the causes of its failure
, ,

must have been due to some error in manufacture , and was not
inherent in the process Interesting historicall y is the fact that
'

.
, ,

at an early st age in the life of the patent a specimen of the ‘

l eather was submitted to the late P rofessor Hummel l n order

that he should suggest some means of overcoming the di sagree
able yellow colour o i the product He reduced it with a b i .

sulphite and coloured it with an aniline dye and a piece is still

, ,

in the possession of Leeds University and in perfectly sound

condition If leg a
,

. l publication of this experiment coul d have

been proved it would have invalidated the important Schultz
patents under which most of the chrome kid of the United States
,

was manufact ured A s bearing on modern chrome tanning the

.
,

most important reaction in the process is that of the al um with

the bichromate It has been shown by H eal and Proct er 1 that
.

pelt absorbs practically no chromic acid from bichromate unless

it has been previously set free by acidification Wh en however .
, ,

alum or sulphate of alumina is added its sulphuric acid liberates

the chromic acid leaving a basic a
,

l umina salt in solution and

, ,

this fact has been utilised in some modern tanning p rocesses .

a
The first really impor tant advance in practical chrome tanning
'

was made b y A ugustus Schultz in 1 884 Schultz w s not a .

tanner but a chemist employed b y a Ne w Y ork firm of anilin e

,

colour merchants and his at tention was accidentally drawn to

,

leather by a friend who asked him if it were possible to produce

a leather for covering corset st eels which would not rust them
as ordinary a l u m e d leathers do Th e process which he adopted .

was probably suggested by a method then recently patented for

the mordanting of wool by chrome oxide and depended on the
power of the pelt to absorb free chromic acid ( as it does a
,

l l oth er
free acids) and the subsequent reduction of the latter on the
,

fibre to a basic chrom e salt which produced the tannage Th e , .

a
red ucing substance employed was the free sulphurous or thio
sul phuric acid of n acidified solution of sodium thiosul phate
( hypos ul phite ) and as it
,
was not certain which of the two acids
was the really active agent Schultz duplicated his patent so as ,

So c Che m I n d 89 5 , p
’
1
j ou rn . . . .
,
1 . 25 1 .
2 58 P R I N C I P L ES OF LEA TH ER
“

MA N UF A C T UR E

t o cover b oth he made no cl a im in his patent to having

. Though
discovered the best proportions of his ingredients those which ‘

he spe cified have proved practic a

-

l ly u seful aft er allowing for the

modifications required by di ffer ent skins a
.

n d slightly different

metho ds of working His fir st bath con sist e d of a sol ution of .

5 per cent of bichromate of potash and 2 1 per cent of con

cen t ra
. .

t e d hydrochloric acid ( or 1 2 5 per cent of concentrated

sulphuric aci d ) reckoned on the wet weight of the prepare d ,

pelt and dissolved in sufficient water for convenient use in the

,

paddle or drum which was to be use d in the process In this , .

bath the skins were worked till th ey took a uniform yellow

a
‘

colour throughout but without any t nning e ffect being p r o ,

du c e d They were now freed from superfluous chrome liquor by

.

draini ng or putting out ; and transferre d to the second bath ,

”
which consisted of 1 0 per cent of hypo and 5 per cent o f . .

hydrochloric acid similarly dissolved In this they rapi dl y took

a
.

du ck egg green colour from the re duction of the chromic acid

a n d wh e n t his wa
-

'

s un form throughout the s kin th e tannage was

'

-
.
.
,
’

complete The exact quan t ity of water is not of great importance

and good results c a n be obtained wit h a
.
,

n yt hin g varying from 2 0

‘

to 50 gallons per 1 0 0 lb of pelt ( 2 00 to 50 0 per c e nt ) if time b e «

a
- -

, . .

l lowed for the weaker solution to act Th e quantities of hypo .

and hydrochloric acid given for the second bath are often som e
what insu fficient and have to be slightly increase d t o complete
the reduction The r e a
,

c t io n which takes place in the first bath

.
i .

is repres e nted by the f e llowing equation in which the weigh t s ,

of the materials taking part in the reaction are also gi ven b elow
the symbols
,
.

P o t ssiu m a H y d r o c hl o r ic P o t ss iu ma '

Ch r o m ic
Wa
dic h r o m t e a .
aid c . c hl o r id e c id a .
t er .

r e e f 20 7
-

2 H Cl
-
z KCl 2 Cr O3 OH 2
1 8
'

294 73 1 49 20 0

ordinary concentrated hydrochloric acid does not contai n

As _

more than about 3 0 per cent of actual HCl about 2 5 parts

-

.
,
1

woul d be requi red to completely decompose 2 9 4 part s of di

chromat e while i n Schultz s formul a onl y 2 5 parts of hydro ’
-

chloric acid are used to 5 parts of dichro m

, G

ate thus leaving a ,

considerable part of the dich r omate undecompose d This excess .

has been found useful i n the production of a good leather both ,

to prevent accidents from an overdose of hydrochloric acid and ,

1
A c id o f sp gr 1 1 6
-

(3 2
°
Tw ) co nt a
i ns 3 1 5 p e r c e n t o f H Cl b y w e igh t
ad a a a
. . . .

or 3 6 6 gr m p e r l it r e n t h e r e fo r e is p r c t ic l l y 1 0 X n o r m l s t r e n g t h
a
. , .

Tw ) 4 6 9 g r m p e r l it r e
°
A c id o f s p g r . . 1 2
(4 0 . cont i ns 39
0
1 p er c en t .
, or . .
2 60 P R I N C I P L ES OF L EA TH ER M A N UFA C T UR E

still further addition of hydrochloric acid sulphu r is

On ,

separated according to the following equation and is deposited ,

partly in the skins and partly in the bath

( 3) 2 Cr 0 3 + 6H C1 + 3Na8 0 2 2 3
= 3N a80 2 4 + 3 5 + 2c r c1 , 3 OH , .

A ftercomplete reduction and consumption of the free hydro

chloric acid further reactions take place at the expense of the
,

excess o f thiosulphate which should be present resulting in the

production of basic chromic s a
,

l ts and the further deposition of ,

s u l p hu r m o s t l y within the skin as shown in the following

, , ,

equations
( 4) Cr , ( SO4 ) 3 o H , = 2Cr o H .
so , so , s +N aSO
,

( 5)
1

Th e thiosulphate bath therefore not o nl y reduces but p r ec ip i

tates sulphur l n the skin and reduces the chromic s a
, ,

, l t to a basic
state In boiling solution thiosulphate precipitates the whole of
.

the chromium as chromic oxide but inthe cold and in presen ce , ,

of free sulphurous acid it only reduces to a basic salt Eitner

, .

does not consider the possibility which certainly requi res investi
ga a
'

t io n that inste d of basic salts sulphite sulphates are forme d

at least in the first instance Such s a
-

, , ,

l ts of o ne base and two

.

acids are quite possible and it is known that the presence o f

,
'

acids even as weak as carbonic allows much mo r e alkal i to be

added without causing precipitation .

The free sulphur which is liberated is partially dep osit ed on

a n d among the fibres of the leat her and adds to its softness and

a
, ,
”
l so acts chemically on the oils used in fat liquoring, so that it -

is probably one of the main causes of difference between the

products of the Schultz or two bath method and the On e -

bath processes subsequently to b e described

It does not f a
.

l l within the scope of this book to describe in

detail the working methods for the production of t he diffe r e n t
kinds of chrome leather but a few precautions common to a , ll
forms of the process may be named ; It is not absolutely im
portant in a l l cases that goods should be completely freed from
lime before chrome tannage but i n this case a suffi ciency of acid
must be a
,

l lowed i n the first bat h to n eutralise the lime introduced

Fairly thorough liming is gener a
.

l ly advisable to plump and

1
p a a
O b v io u sl y t h e p r o o r t io n o f t h e s e r e c t io n s will v r y w it h t h e c o n
a
c e n t r t io n o f t h e s o l u t io n s a
n d t he r t e aa
t w h ic h c id i s d de d a a
St i s n y a
a a a a aa a
.

s t t e s t h t m o r e t e t r t h io n t e i s f o r m e d if e v e n t r c e o f r s e n ic is p r e s e n t
in t h e aid c u se d .
 C H R OM E A N D I R ON TA N N A GE S 26 1

separate the fibres but as a rul e the bating or puering of goods ,

for chroming sho ul d not be excessive } but shoul d be planned

not to remove more than is absol utely necessary of the hide
substance as the chrome tannage is in its nature soft and light
and does not lend itself to artifici a
, ,

l fil lings such as the flour and

egg yolk of the c a
,

-
l f kid process Skins are sometimes freed from -

and pickled skins may be chro med

.

lime by pickling ( p .

w ithout d e p ic kl in g as the acid will be removed by the dichromate , ,

but in this case the acid contained in the skins must be considered
l n the composition of the chroming bath Skins indeed which
are pickled with a sufficiency of acid may be chromed in a neutra
.
, ,
_

l
dichromate bath and this is sometimes a convenient mode of p r o ,

c e du r e To prevent drawin g of t he grain d u ring tanni ng skins

.
,

not unfrequently receive a preliminary tannage with alum or

'

sulphate of alumina and these materials together with salt may , , ,

be introduced into the chroming bath in which case they will ,

liberate a portion of the chromic acid as has been mentioned ,

in connection with the Heinzerling process Alum chrome

alu m and acid s a
.
, _

,
l ts such as sodium bisulphate may be sub , ,

stituted f o r the acid in the chrome bath but organic acids must ,

not be used as they would reduce the chromic acid ; The

a
,

quantity of free chromic cid in the chrome bath is of the most

vit al importance to success as it and not the dichromate ( which , ,

may be present in considerable excess) regul ates the amount

o f chrome taken up by the skin a
,

n d the subsequent d egree of

tannage It is very possible to inj ure leather by over chroming

rendering it rough harsh and even ten der If a
-
.
,

bath containing , ,
‘

.
-

excess of bichromate is to be r e —strengthened it may be as

sumed as a rule that a
,

l l the free chromic acid has been absorbed

‘

by the skins and whil e it is merely necessary to rest ore the

strength of the dichromate to its origi n a
,

l amount the full quantity , ,

of acid must be used which would be required in preparing a

new bath Where as in Eit n er s acid chrome bath ( p the ’

whole of the chromic acid is liberated the bath m a

. .
,

y be exh austed ,

by a second pack of skins Many tanners in order to avoid

complications of rema
.
,

king a bath run away their chrome liquors ,

a ki f gl aé kid d t h gh p i g t p d am t h
.

1
Go t s ns or c n ee o ro u u er n o ro uc e s oo

g a h w t ha id a
-

ir It ha n t ly b t s rec en bl lt f p i gi ee n s o n o n e co n s er e r e su o u er n s

t h la f la w hi h a p ia lly a d at i t h
.

t o m re y o ve t i fib e er b o e s c res c re s ec un n n e

g air f g a t k
n o i a d p ot t h fl a t t -
is g t f th g a
n, i n f a wh i h r eve n e en n o u o e r n su r
-
ce c

i q i d i gl a
s re z dg a
u re t ( p n I m p ime t ma d by M o se e 22 n so e ex er en s e r

ap a a ti ba ay f t h i
.

Wil tw ty f
so n , h i en t w our o urs n n cr e c e ere n e c e ss r or e r

w ld p b a p a
-

compl t l ti b t ah t
e e so u t im on, bly b ti a
u lly s or er e ou ro e r c c

suffi i t I t h ab
c en . a l i th St a t t p s am h a i t
e en u su n e es o
T
uer s uc s s x e en

h o u r s wit h d o g d u n g -
.
2 62 P RI N C I P L ES OF L EA TH ER MA N UFA C T UR E

after once using and containing a ll the excess of dichromate which

With proper chemic a
,

has been used l control this is not

'

a
necessary and is obj e ctionable not onl y from its wasteful ness
, , ,

b u t on cc ount of the very poisonous character of the unreduced

bichromate Even weak dichromate solutions especiall y if
warm a
.
,

r e liable to cause painful and obstinate eruptions on the

,

hands but t his rarely occurs to tanners as the poisonou s action

, ,

of the solution is removed or much lessened on reduction It is

a
.

well therefore to arrange that men who han dl e skins in the

, ,

chrome bath shoul d subsequently l so work l n the reducing bath

and to avoid as fa
,

r as possible c ontact of chrome li quors wi th

the skin Methods of an a

, ,

. l ysis o f used chrome liquors are gi ven

in pp 1 4 2 et s eq ; p 1 2 0 Those for the
. . . .

d etermination of acidity are not however easily applicable in the

presence of alum and s a lts of chromic oxide
The s kin s o n coming from the chroming bath may be a
.

'

l lowed
to lie for some time wit hout serious inj ury but should be carefull y ,

protecte d from the action of light which reduces the chrome ,

at t he expense of the skin and renders the subsequent tannage

l r re gul a It IS found th at skins if brought into a weak or neutra
,

r . l ,

reducing bath are apt to bleed or lose chromic acid which 1 s

, ,

reduced wastefully i n the bat h On the other hand a strong .

”
h yp o bath i s apt to draw the grain and contract the skins ,

owing to the tannage taking place too suddenly A somewhat

‘

strong hypo bath is therefore often employed as a preparatory

dip the skins being simply drawn through it to fix the chrome
,
”
on the surface piled on a h orse and subsequently reduced in
a
-

, ,

bath of ordinary strength The tendency to bl eed is lessened .

,

but at the expense of the pelt by the reduction which takes ,

plac e if the ski ns are allowed to lie overnight in the chromed

,

state Eitner states that skins chromed in an acid bath ( t e

. . .

wh e re the whole of the chromic acid is in a free state) sh ow little ‘

tendency to bleed and it is probable that the bleeding is mainly ,

of undecomposed di chromate A fter reduction t he skins are .

well washed with warm water and their later treatment is the ,

same as that of skins tanned b y the one bath process whi ch

l

is subsequently described ( see p

Naturally in practic a
.

'

l work the reduction cannot b e made to

'

proceed rigi dl y in the definite steps described by Eitner on p 2 59

but a
.
,

ll go on in di fferent proportions together though by supply

ing the acid in proper quantities and at proper interva
,

l s they ,

may be made in the main to foll ow in the given order B oth .

on this account and because neither the exact amount of chromic

,

acid in t he skins nor the sulphurous aci d lost by escape into the
,
2 64 P RI N C I P L E S OF L EA TH E R MA N UFA CT UR E

unt il the pelt is evenly chromed and yellow throughout A

'
. ,

solution of 1 5 1 b of thiosulphate hypo in 1 0 gallons of water. .

is now added to the liquor in the dru m and 5 lb of diluted

hydrochloric acid is gradu a l ly run in in sm a
.
,

l l portions Th e .

leather will first become brown from the deposition of chromium

chromate but as more acid is add ed will take the regular clear
,

blue green Th e s olution l eft in the drum should not be more

-
.

than tinged with gre en The goods should be well washed but .
,
.

neutralisation is probably not absolutely necessary unless the

goods are to be fat li quore d -

A s soon as the Schultz process proved s uccessful many

attempts were made to evade the patent by the use of other
r educing agents than t he hypo and other salts of sulphurous
acid which it covered and a l most every imagi nable reducing agent ,

was pat ente d A mong these the us e of h ydrogen sulphide and

acidified solutions of alkaline sul phides and especi a
.

l ly of poly
sulphides proved capable of practic a
,
,

,
1
l use though less convenient ,

than thiosulphate but were soon acquired by a combination

the P at ent Tanning Compan y together with Schultz s origin a
, ,
’
l ,

p atent s .

U nder these circumstances Martin D ennis either by fresh dis ,

c o v e ry or ot herwise r evived the original p rocess of Knapp p 2

(
which he patented 2 a
.
,

l most in Knapp s words and o ffered a basic

’

chrome tanning liquor for sale without further restrictions on ,

its use This liquor was made by di ssolving precipitated and

.

washed chromic hydrate ( easily prepared by precipitating chrome

al um solu tion with excess of a l kal i ) in hydrochl oric acid to
saturation and adding washing soda until the solut ion was
,

rendere d sufficiently basic Such a solution may be used on

. .

skins prepared in the ordinary way by diluting with water and

strengthened as the tannage proceeds l ike a vegetabl e tan liquo r
a
:

It is doubtful if the patent was a va

-

l id one s it was known that ,

the u se of such a solution was not new , and it was only grante d .

in A merica on the representation which has since been found to

be mistaken that chl orides a
,

l one were applicable fo r tanning

while Knapp had n ot restricted his st atement to th ese s a
, ,

l ts In
re a n d sulphat es seem e qu a a
l l y su it a
.

l ity chlorides b l e but to

'

produce similar results the former must be m ade more basic than
the latter In any case the patent could not cover the general
.

principle of basic tanning but only the particular liquor and , _

1
L iv e r o f su l p h u r o r s o l u t io n s , a
m d e b y b o il in g s o d iu m s u l p h i d e o r

so d awit h e x c e s s o f s ul p h u r

Ma ad
.

2
ti r n D e n n is 49 5 0 2 8 , 1 89 3 ; n 51 1 41 1 1 89 3 , 7 7 3 2,
aGa
ll a
, ,

1 89 3 . En g P t .
gh . er.
 C H R OM E AN D I R ON TA NN A G ES 2 65

mode of preparation specified It was soon afterwards shown .

by the writer 1 that a good chrome tanning liquor might be

prepared by direct reduction of dichromate with sugar or other
carbohydrates in presence of such a limited quantity of hydro
chloric acid as to produce a basic salt Suitable proportions are
5 mol H Cl to 1 mol potassium dichromate which p r o du c es a
.

. .
,

salt approximately Cr 2C1 3 ( OH) 3 The solution is easily made by .

dissolving 3 parts of dichromate of potash or soda in a con

“

ve n ie n t quantity of water adding 6 parts by weight of con

cent ra
,

t e d hydrochloric acid and then cane—sugar or glucose

gradu a
,

l ly till a green solution is obtained when the whole ,

‘

may be made up to 1 0 0 parts and will be approximately of

the same s trength as a 1 0 per cent solution of chrome a
,

l um A .
-
.

little heat may be needed to start the reaction but too much ,

should be avoided as considerable heat is evolved by the oxida ,

tion and as much carbonic anhydride is produced which causes

a
,

a
the solution to effervesce briskly the vessel used should be of ,

mple size In place of cane sugar a good qu lity of glucose

.
-

may be used b ut some samples contain some impurit y which

,

produces a violet solution which will not tan satisfactoril y

th ough it may be made to do so by sufficient addition of a
,

l kali .

This liquor is in regular use i n many tanneries producing a good

qu al ity of chrome c a
,

l f but is somewhat variable in its effects ,

according to the temperature employed in its preparation and it ,

appears to have no real advantage over a simple solution of

chro me alum rendered basic by soda A somewhat similar pre
ra
-

pa t io n is Eberle s chr o m a m which some organic ’

l in ,

substanc e probably crude glycerine is used to reduce the b i

, ,

chromate The organic matters and especially t he organic acids

which result from the oxidation of the sugar or gl yc e r in e a
.
,

r e not
'

without influence on the tanning properties of the liquor Of .

course t hese solutions may be rendered still more basic by the

ad di tion of sodium carbonate A good stock liquor of a p p ro x i .
-

mately the same strength as t hat above described is made by ,

dissolving I O parts of chrome alum in 80 parts of tepid but not -

hot water and adding with constant stirring a solution of 2 % to

,
3
,

1
Lea
t her Tr a
de s a 89 7 R e vie w J n 1 2, 1

C m p a Eb l G m a Pa 89 8 a
. .
,

3 67 8 89 9
’
2
o ret t 9 4 er e s d er n en s 1 1 0 2, 1 n 1 0 1

Th l a pp a t b a
a t i ip at d a t l a t a ga
, , .

t
e f th s o e se e d th
rs f o e n c e e s s re r s e u se o

g a ad t ah b y t h w it p b li a 89 7 a
,

gl ti i
’
u c o se , su r, n s rc b it d e r er s u c on n 1 o ve c e

La t ig a h a h w t ha a f t h wa
.
, ,

3
t i ti
er n ves t th t mp t
ons t i ve s o n e e er ure o e er s

t at if a l ka
li b a dd d b t h m a ia
_

un im p or n l m di t et m t t e u c ro e u ss o c es o so
'

e ex en

ad m p aa t ha h w
-

h t wa t ha
,

i
n t
o tier, p im n co t rl ti f ve e x er en s ve s o n so u ons o

th e norma l a lt ma d w it h t h aid f h a
s t a t k i aif m
e aid t h a e o e c on s n s o re c n

th ma
o se d i th ld e n e co .
2 66 P R I N C I P L E S OF LE A THE R M A N U F A C T UR E

a
3 5 parts of w shing soda in 1 0 p arts of water
dissolves s o m e wh a t sl o wl y witho ut the aid of heat
Th e chrome a l um
and the
,

.
.
-

n ,

solution is best made either in a small drum drive n b y power '

or by suspending t he cryst a
,

l s i n a basket near t he surface of the

liquor so that the satu r a
'

, ted solution can d escend .

Eit n er has pointed o ut the important e ffect that di fferences

"

of basicity have o n the tanning propert ies of chrome solutions

ea
.

Normal chrome s ul phate or chro m

.

l um colours t h e leather -

quickly and equally throughout and swells the pel t on account

th in a a
,

of its practically acid ch aracter but gi ves n d lightly ,

tanned leather from which much of the chrome washes o ut

, ,

u nl ess it is at once neutralised in alkaline solutions A s t he .

,

chrome s olution is made m o re basic t he tannage penetrat es ,

more slowly b ut i s heavi er and more th orough the colour is

a
, ,

d rker and bluer and m u ch :l ess o f the chromic s al t i s remove d

.
, _

by washing with water When th e basicity b eco mes e xcessive -

.

the solut i on becom es unstable and decomposes o n dilution wit h “

wat er or on cont a
-

ct with the skin i nto a very basic sal t which is

precipitated and a more a ,
ci d solution than that given by a ,

moderately basic sal t The effect of such solution s on the leather .

-

a
is very unsat isfactory producing the bad e ffects both of too acid ,

and too basic s l ts Th e pelt is apt to be swollen and lightly

coloured by the m o r e a c id s alt but at the same time the actu a
.

l ,

tannage proceeds very slowly and in extreme cases it is di fficult ,

to tan through while the surface becomes over tanned and di s

.

,
-

coloured and the g rain often tender and even brit tle from the
incrustation of precipitated basic s a
,

lt Eitner likens the e ffect of .

the more acid liquors to t he quickly pene trating and lightly tanning
vegetable tans such as gambier and that of the more basic to the
, ,
,

heavier tannages such as val onia ; and within limits advantage , ,

may be taken of these facts i n adj usting the liquors to the character
of the l e a t h er it is desired to produce In sul phate liquors he
considers the salt Cr OH SO4 as most suited to genera
.
,

l use and i n

a
.
,

the case of chrome—alum this is produced by the use of 2 86 parts of

so da c r yst a
_

~
l s or 1 0 6 parts of dry sodium c rbonate ( 1 molecul e ) to
9 9 8 ( or practic a
,

l ly 1 000 ) parts by weight ( 1 molecul e) of chrome

alum ( In using washing soda care must be taken to employ
r crystals of the s a
-

cl ea l t and not those w

.
,

hich have become white ,

by loss of water or to al low for th e greater strength ) In place of

,
.

soda Eitner makes a similar basic liquor by boiling 1 00 0 parts of

chrome a l um wi th 2 48 parts ( 1 molec ul e) of sodium hyposul phite
-

until the Whole of the liberated sulphurous acid is driven o ff

and the sulphur deposited In comparative experiments by the .

1
G erb e r , 1 901 , pp .
3 e t s eq
.
2 68 P R I N C I P L ES OF L EA TH E R MA N UF A C T UR E

the gas Th e finished liquor shoul d smell pretty strongly of

.

sulphurous acid and give a clear blue green on dilution ,

-

The effect of weak and especially of volatile acids in increasing , ,

the hydrion concentration of chrome liquors and so lowering ,

the precipitation point and rendering possible the use of solutions ,

extremely basic as regards their fixed acid deserves more attenti on ,

than it has hitherto received Burton has shown that even . .

1

carbonic acid has a not iceable effect of this sort '

.

Excellent chrome iqu o r s are also made under the patent of

i
“

J R Bloc key 2
in which the suitably acidified bichromate is
reduce d by spent t anning materi a
a
-

. .
.
,

l which is added in excess

t hat whic h is not oxidis ed n d dissolved b eing l eft in the va
, ,

t for
'

use on the next b a tch so that no residue remai ns to be removed ,

.

Eitner stated that he had made chrome sol utions of various

types containing organic compou nds in c o rr1 b in a t i0n with the
’‘
‘

chrome s a
,

l t ; which combine with the leather producing a fuller

and softer tannage , but he gave no details a
,

s to their prepar atio n ,

as they were made Commercially by the Erste Oest err e ichis che ‘

Soda Fabrik -
at Hruschau The writer has found that in some .

cases by t he addition of say three parts of sugar or still better of

glucose , to ten parts of the chrome a
, , ,

l um in making up the basic -

liquor a much fuller and plumper leather is produced which dries

, ,

perfectly soft even without staking or fat liqu oring and it is

,
-

probable that many other organic compounds may be found

which produce similar effects The addition of very sm a l l quanti
ties of neutra
.

l tartrates or lactates or of any other hydroxy

a
,

salts or acids have however a remarkable e ffect in lowering the

, , ,

apparent basicity o f the solution n d preventing tannage This is .

due to the property of hydroxy acids of forming complex ions with -

chromium which do not tan and it has been shown by Procter

and Wilson that solutions of R ochelle s a
, ,

3
l t ( sodium potassium

a
tartrate) will di ssolve all but traces of chrome from chrome
leather and leave it in a condition in which it c n be b o il e d fo r
,
'

glue making Th e R ochelle salt acts best for this purpose in a

neutra l or a l ka
-
.

l ine condition and may mostly be recovered by ,

suitabl e acidification when it is precipitated as the very sparingly , .

soluble potassium tartrate and may again be bro ught into solu ,

tion by the addition of s oda It is highly probable that the

'

unsatisfactory tanning liquors produced by direct reduction with

some samples of glucose are due to the presence of sm a l l quantities
of some such organic acid produced during the oxidation It has .

1
B ur t o n , 4 1 9 20, 205 B urt o n ad H n ey, i bid 27 2

a
.
, ,

7 83 A
2
Bl o c k e y , E n g P t 1 3 1 7 7 2 ; 191 9
a
. . .
,

3
P r o c t e r n d W il s o n , 1 9 1 6, p 1 56
. .
 C H R OME A ND I R ON TA N N A G E S 2 69

been found that these sol utions may be made to tan b y the liberal
addition of soda It is probable that more satisfactory results in
.

chrome tanning will be attained by the direct addition of known

organic substances to basic liquors of definite constitution than
by the somewhat uncertain products of organic oxidations
The quantity o i s a
.

l t to be added depends on the qualities

desired in the leather and u pon whether chloride or sulphate
,

liquors are employed salt in chloride liquors i ncreasing the soft

ness of the leather but in excess tending to flatness while in
s ul phate liquors it practic a
, ,

l ly diminishes their basicity by con

verting the chro mium sulphate into the equiva l ent chloride
which as Eitner points out behaves as a less basic s a
,

, ,
l t and ,

hence but little advantage is to be gained from its use It is .

best to begin with a very weak liquor to avoid drawn grain ,

and for the same purpose a preparatory tannage with alumina

sal ts or an addition of a
,
l um or sul phate of alumina and s a l t may ,

be made to the first l iquor as the attracti on of t he chrome salt

,

for the fibre is su ffi cient to produc e a chrome tannage even in

presence of excess of a l umina s a
, _

l ts Te n lb of chrome alum . .
-

will tan about 1 0 0 lb of wet pelt but more must be used for the
.
,

first parcel ; t o avoid loss of time the skins may be tanned ,

out in a pretty strong liquor The bath has a tendency to .

become acid by use and before strengthening it may be necessary

to add some more soda solution Little if any addition a l sa
,

l t is
required as it is only absorbed by the skins to a sm a
.
, ,

,
l l extent ,

probably as chromic chl oride A s the liquors graduall y become

.

charged with sulphates it is best to work them out like bark

'

liquors and not to go on strengthening the same liquor in

,

definitely I f old liquors are used for green goods it is not

necessary to neutr a
.
,

l ise them with soda before use as Eitner has

shown that less basic liquors colour more e ve nl y a
,

n d with less

tendency to produce drawn grain .

The cause of this increase of acidity in the liquors is that the

basic chrome salts hydrolys e on dilution and that the acid ,

di ffuses much more rapi dl y than the basic chrome so that at ,

first the liquor must be kept acid to prevent the precipitation

of the basic salt but as the process proceeds the hide be comes
_

saturated with acid which is not further absorbed while the

fixation of the chrome s a
, ,

l t still continues and t he excess of acid ,

tends to prevent a full tannage It is therefore necessary to .

maintain the basicity of the final liquors either by strengthening

with very basic solutions or by the addition of a
,

l kalies This .

is controll ed by determining the chrome by oxidation

and p 1 2 2 ) and titration with potassium iodide a
. nd ,
 27 0 P R I N C I P L E S OF L EA TH ER M A NUFA C T UR E

a
subsequentl y titr ting the acid with caustic soda in a boiling '
“

solution and calcul ating the b a T hi s nu m

,

,
s icit
y numb e r ber f
.

is the proportion Of sul phuric aci d to t he atom ( 5 2 ) of Cr Fo r

the norm a
.

l salt it is therefore 1 44 and diminishes as t he basicity

increases the practical va
,

l ues ranging about 9 6 corresponding to

It was suggested by St ia
, ,

SO4 Cr ( OH) . s n y when working on

chrome sulphates and of course was quite appropriate for his

,

purpose b ut is l ess conveni ent wh en worki ng with chlorides or .

other salts A much better way would be si mply to give the

,

proportion of ( OH ) to Cr 2 In thi s case the value of chro me

hydrate Cr , ( OI I) 6 would be 6 with less values for l ess basic
-

solutions It i s preferable to adopt Cr 2 rather t han Cr as it

.

gives a larger scale of w

.
,

hole numbers and fits better with 5 11 1

p ha
,

t es while chrome chloride i s very frequently written Cr z Cl G

, .
1

A practical way for the tanner o f determi ning t he basicity of

liquors i s that of Mc Ca n dl ish s precipitation point which h a s
’
-

a more direct relation to the t anning properties Of a liquor than

the exact acid determination which varies in its effect wi th
“

a
di fferent aci ds The chrome li quor i s fil tered perfectly clear with
.

the addition of a little k olin and 1 0 c c is titrated with constant ,

. .

stirring with a N/I O or N/2 O solution of sodium carbonate or of

whatever alk a l i ( e g borax) is u se d fo r neutr a
,
' '

l isation until a

a
. .
,

permanent turbidity is produced which does not disappear on

“

st irring or shaking This gives the largest quantity of l ka

‘

. li

a
"

which could be added H o w much the tanner should stop sho rt .

Of this in p ractice is questio n Of experience but a higher margin ,

must be left with green goods than with hides nearly tanned In
the early st a
.
,
'

ges t he absorption of acid by the skin is fr e qu e n t l y

so large that a portion of the basic ch rome salt is precipitated and “

the liquor becomes turbid

Chrome sole leather has become of some importanc e a
.

a
n d when

well m a n u fa
,

c t u i e d it is probably the most dur ble and water

proof leather known for the purpose though it is to be feare d

that a l l s upplied during t he wa
, .

r di d not merit this charact er

' '

It

a
.

is usually tanned by suspension in the ordinary basic chrom e

liquo rs n d should at l east be wel l washed and neutr a
,
l ised
slightly perhaps with thiosulphate dried to a sammed condition
and rolled or struck out a
, ,

n d then thoroughly dried often n ailed

(,

on boards for the sake of flatness) at a rather high temperature “

1
It h ab s e enp r o p o s e d in A m e r ic t o e x p r e s s t h e c i d it y a
o f chro m e a
liqu o r s in a aa
n n l o g o u s b u t in v e r s e w y Or z C1 6 n d C1 2 ( SO 4 ) 3 h v e n a a a a
a a a
.

6 Cr ( O H ) Cl 2 n d Cr ( O H ) 2Cl n d Cr ,
“
c i d it y

aid it y f C ( O H ) a
,

2, wh il st t h e c o r, is z ero Th e n umb er h e r e is t h t of

t aid a di a
6

a
.

t he m o n o v l en l mbi
c r c s co n ed w it h 2 Cr .
27 2 P R I N C I P L ES OF L EA TH ER MA N UFA C T U R E

seri ous i nconvenienc es in its subsequent treatment B efore pro

c e e din g further this excess of acid must be removed or neutr a
.

l
ised and it is not too much to say that most of the troubles
,

experi enced in fat liquoring arise from neglect or mistake in

the washing and neutra
-

l isation Th e di fficulty in the process

arises from the fact that while the acid should be reduced to a
.

mere trace it must not be entirely remov d as chromic oxide e 1

,

itself does not seem capable of tanning and at any rate the
effect of excess of strong a
,

l kalies is at once to render the leather

hard and pelty B o rax is On e of the safest neutralising materi a
. ls ,

about 3 per cent on the wet weight of the p elt being required
.

in not more than 5 per cent solution Eitner recommends the . .

use of silicate of s oda which sold as a solution o f sp gr 1 5 is , , . .

-

a
somewhat stronger and much cheaper than borax Hyposulphite
of soda and whitening together neutralise more r a
.

p idl y n d com
p l e t e l y than either alone O ther s al ts of weak acids may also . .

be used the acids exercising a regulating influence which pre

,

vents neutralisation goin g too far So di um carbonate or b i

carbonate o r ammonia may a
.

l so be used but with these it is

difficult to get even neutra
, , ,
”
l isation or to avoid the risk of
carryi ng the process too far St ia
,

s n y s mixture of 2 per cent ’

2
. .

of soda crystals and 2 per c ent of ammoni um chloride or sul .

phate to which 2 per cent more soda and 1 per cent more
ammonium salt may be added if the neutra
. .
,

l isation is n o t su fficient ,

is perfectly safe and effi cient and cannot Over neutralise and
.
,
-

statements about it s expense are unfounded since the mixture ,

can be used repeate dl y merely strengthening with soda and a ,

little ammonium salt as required since it is really the soda which

neutr a
,

l ises and the ammonia acts only as a

,
bu ffer to regulate
the hydroxyl concentration Even a thorough drumming with .

a milk of whitening ( calcium carbonate ) or magnesia is

'

effecti ve With the latter there is no danger o f overdoing t he

.

process but in some cases the adhering whitening and preci

a
,

p it t e d calcium sulphate are troublesome in later operations I n .

any case the neutralising sho ul d onl y be carried so far that the .

skins show no acid reaction to litmus paper and whatever means

of neutralising are employed the fat liquoring should take place -

without delay before the more acid l iquor in the centre of the
,
“

skin has time to diffuse again to the surface .

It is probable that one of the great causes of di fference between

one bath and two bath leathers i s the presence of fr ee
sulphur in the latter This may a
-
-

l so be introduced into . one

1
P r o ct e r ad G riff t h
n i , j o u rn . S OC C he m I n d
. .
,
1 9 00 , p . 2 23 .

2
C o ll eg . , 1 1 ,
1 9 1 2, p . 29 3 .
 C H R OME A N D I R ON TA N N A GE S 27 3

bath leather by treating it in the wet chromed state without

, ,

washing out the chrome liquor with excess of a solution of ,

hyposul phite or of an alkaline polysulphide which at the same

, ,

time will neutralise the skin The more acid the chrome liquor .
,

t h e greater the quantity of sulphur which will be introduced .

The simplest means of distinguishing two bath from one -

bath tannages is to test for the presence of sul phur by wrapping ,

up a silver coin with a piece of the leather in paper and leaving ,

the parcel for an hour in the water oven or some other warm -

place when the presence of sul phur will be shown by the blacken
,

ing of the coin Of course a sulphurised one — . bath leather

will give the same reacti on
The leather m ust now be dye d a
.

n d fat liquored Which of

'

-
.

these two Operations should be first undertaken will depend on

circumstances Most leathers dye more easily before fat liquor
. .

'
-

ing but if acid dyes which are soluble in the alkaline fat liquor
a
-

r e used a good deal of colour is Often lost This may be com ,

p en sa
.
,

t e d by dissolving a suitable aniline ( acid ) colour in the fat

liquor Bl u eb a
. c kin g is generally done before fat liquoring by -

drumming with methyl Violet or some other aniline colour ( with

or without logwood w hich gives alone a very dai k violet ) A n y,
.

shaving or Splitting required must of course be done before

b lu eb aki c ng .

Th e fat liquor is an emulsion of soap and Oil which for chrome

-

leather should be as neutral as possible if the neutralising has

been thorough but if any acid be left on the skins a neutral
.
,

fat liquor will be precipitated as a greasy mass This can some

-
.

times be remedied by the addi tion o i a little ammonia or borax ,

or by r e fat liquoring with soap solution only but if the washing

- -

of the skins has been incomplete and soluble chrome salts ,

remain the mischief is almost irretrievable as sticky chrome

, ,

soaps are formed often coloured with the aniline violet which
, ,

adhere to the skins and which can scarcely be removed by any ,

solvent which does not in jure t he leather As regards t h e soaps '

and oils used there is considerable latitude : 1 5

, 2
per cent of .

castor oil soap and 4 per cent of castor or olive Oil on the wet .

weight of the pelt has done good service in my hands but many ,

manufacturers employ soft soaps curd soaps etc with castor

olive cod Or n e a
, ,
.
, ,

, t s fo o t oil and sometimes sod oil or degras ,

-
.

Eitner considers olive oil and olive Oil potash soap the most
suitable and particularly warns against the use either of drying
oils or of Oils containing tallow ( such as n e a
,

t s fo o t ) which are ,

not o nl y apt to cause a white e ffi o r e s c e n c e but to give the leather ,

a disagreeable rancid smell Fish oils are unsuitable but mineral . ,

1 8
 27 4 P RI N C I P L ES OF L EA TH ER M A N UFA C T URE

oils a r e often useful Con stituents of fat liquors Wool fat a l so

a
- -

makes a good fat li quor but is unsuitable for goo ds Which r e -

to be glazed Turkey red oil ( which is sulphated castor) may

a
-

a
be used as fat liqu or simply mixed with warm water without
so p and has been recommended where d el ic a
-

t e c Ol o u r s are to
'

be dyed after fat liquoring ; but it is said to have an u n s a

,

-
t is

a
f actory after e ffect hardening and tendering the leather Some
1

s o aps m de from the s a a

.
,

—
a
ifi b l part of wo l grease such as
a
p o n e o

L n Oso a l so a
,

c t Well i n conj unction W ith olive castor or

'

p , , ,

Other oils Where l eather is t o be glazed t he amount of fat

liquo ri ng must b e kept very mod erat e Fa
.
,

t liquor s should be
a
'

-
.

thoroughl y emul sified n d are gen erally used warm They

penetrat e bet ter if the leather is p a r t ia
.
,
'

l l y dried by sleeking out

s mming b ut the leather mus t not a
,
”
or pressing or Cautious
b e complet ely dried ou t before f a t liquoring a
, , .

nd dyeing unless it -

has been previ ously treated with glyce rine glucose treacle or “

so me deliquescent s a l t which W
a
, , ,

ill enable it to be wet ba ck

'

Chro m
.
,

e leathers are not waterproof as has often been st ted ‘

a
, ,

unl ess rendered so by treatment with soaps and gre ses and are
ap parently e a
,

sily wetted but the fibre will no longer absorb water ,

after thorough drying and consequently wil l neither dye nor stu ff ,

satis factorily In order to e nable chrome leather to be k e pt in

.

an undyed condit ion glycerine or syrup is som etimes mixed With

the fat liquor but a s the watery portion of this is n ot gener a
a
-

,
l ly
completely bsorb ed the process is somewhat wasteful Mr M C
a
. . .
,

L mb avoids t h is diffi culty by applying a solution of glyceri ne

“

to the grain side with a sponge aft er fa t liquoring In this case

a
“

-
.
.

t h e leather m y b e dried su fficiently fo r s t aking or shaving

Without risk
a
.

Chrome leather can be dyed by many of the cid aniline colo urs
without a mordant B asic colours are o nly fixed when the .

l e ather has been first prepared wit h a vegetable tannin gambier

- -

o r a mi x ture of g a m b ier a
,

n d sumach being the most suitable

'

Considerable care must be emplo yed in the application o f t a

.

n n in s

to chrome leather as they have a tendency to harden it a

_ '

nd

aa a a
,

diminish its stretch or even to render it tender but traces of , ,

a
tannin in the dye probably f cilitate glazing B efore dyei ng
'

1
’

a
T h is i s
t d s o m e wh
b t f l if t h il ti f t il y p p d ad ou u e O s re s s c or re re n

f e f m
re f a
ro id a d i
ex c ess ay a l p h a o t d il t m c ly n n n c se su on e o s, no ere

at b t t h g ta ha m la ad a ch
,

c s or u bl ilo er g ly i t
ve e e o s, ve co e r e n o u se , n s su

fa t—
li q a t t ay g auors t ret t a l ka li
no ad m a y o b aid n re ex en n e, n e ve n e c

ad a t a ip it a t ali a
,

th y d e t t ip d y o no s r d il y p t d if t h
es, n re no so r e rec e e n eu r s

ti oni t q it mpl t
s no S lp h u at d fi h — il a l a
e co g ly d i th
e e u on e s o s re r e u se n o er

b ah f th t a d e ad h a g a
.

r nc es o t m l ify i g p w
e r b t t h w it n ve re e u s n o ers, u e r er

ha p i
s n o ex f th i h m l a
er e n c e o th
'

e r u se o n c ro e e er .
 R I N C I P L ES OF LEA TH E R M A N UF A C T UR E
‘

27 6 P

to caus e the r esin ific a t i o n of the Oil known as spueing by .

, ,

promoting its oxidation

Th e ferric s a
.

l ts are characterised by giving blue bla c k or green

black compounds with tannins a n d with many other a
-

l lied
bodies while the corresponding ferrous compounds are mostly
colourles s though they r a
,

,
pidly oxidise and darken on exposure .

Ferric iron like alumina forms an alu m a double sulphate

forming fine p a
, , ,

of iron and potassium , le

violet crystals b u t disso l vin g to a yellow brown solution ( It
,
'

x -
.

must be distinctly un derstood that iron alu m and chrome alum

contain no a
- -

l umina but are simply called alu ms because of their

similarity of c o nstitution iron or chrome taking t h e plac e of the
,

a
,

l uminium I ron alum in conj unction with salt can be used

.
-

,
.

for t anning giving a pale buff coloured leather very similar to

an ordinary alum leather ; Thus the presence of a sm a
-

l l quantity
of iron in a n a l um used for t awing is of no consequence except ,

as affecting the colour of the leather In impur e sulphate of

alumina such as a
.

,
l u m in O ferric it however ; generally exist s -

, ,

in th e green ferrous state and onl y acquires tanning properties

on oxidation Without common salt iron s a
,

. l ts are sti l l less -

satisfactory tanning agents than those of alumina under the same

conditions as the acid i s yet more loosely held and though basic
, ,

ferric salts are taken up i n considerable quantities by hide the ,

leather produced is thin and usually brittle P rofessor Knapp , .

devoted much study to the production of a commercial sole

leather by basic iron salts and took several patents which did
not prove practic a
-

, ,

l ly successful though the brittleness was to ,

some extent overcome by the incorporation of Compounds of iron

a
with organic materials such as blood and urine of iron soaps
"

Li ke most miner a
-

, ,

n d of rosin and paraffi n in the leather l .

tannages the process was far more rapid than that with vegetable
,

materials Knapp s basic tanning liquor was made by the

.
’

oxidation of ferrous sulphate with a small quantity of nitric acid

P atents have been taken for the oxidation of fe r r o u s s u l p h a
.

te
'

by peroxide of manganese in presence of sulphuric acid which ,

produces basic ferric sulphate in mixture with manganese sul

phate which has a l so some tanning properties A ttempts have
a
.
,

lso been made to tan by treatment of the hide with sol utions of
ferrous sulphate and subsequent e xposure to the air in order t o
oxidise the iron on the fibre and convert it into a basic ferric s a
,

lt ,

but have not proved of any commercial value

Owing to the scarcity of t anning materi a
.

l s in Germany during
the war and the great demand for leather considerable attention
‘

was paid to iron tanning and quite a number of patents were

-

,
 CH R O M E A ND I R ON TA NNA G E S 27 7

taken out and some of them claim to be successful in producing

,

merchantable leather Dr J Bystron treats first with ferrous .

1

sul phate and oxidises on the fibre with ferric nitrate The
,
.

Chemischen Fabriken Worms patent t he use of ferric for , ,

mates 2 Moos and Kut sis 3 of Stuttgart the use of iron salts in ,
-

conj unction wit h sul phite cellulose liquors and Dr Otto R ohm -

has taken a vari ety of patents for iron tannages in conj unction
4

with a l dehydes and other things Th e great di fficulty appears .

to b e to produce a leather which will not become brittle on

keeping More hopeful are the numerous patents which have
.

been taken for co mbinatio ns of chrome and iron tannages and

there is no doubt th a
,

t a merchantable leathe r can be made on

these lines Fo r details and a good general review of iron
.

tanning processes the reader may be referred to In g Josef

Je t t m a
.

r s little book D i e Ei s en er bu n published by chulze

’

g g S ,

and Co Leipzig 1 9 20 No attention appears to have been

.
, ,
.

paid to combined iron and aluminium tannage which would ,

seem worth experi ment as the combined salts would be very

'

cheap most natural clays containing both metals and their

, ,

properties being in some ways complementary It is said that .

iron tannages cannot be neutralised with alkalies without

destruction .

1
D R P 2553 24, 1 9 1 0
“

2
A u st P t a8 0067 1 9 1 8
a8 7 8
. . . . . .
, .

3
Swis s P t 1 1 1 9 1 8
Pa a 7 7 86 7
. .
,

4
Swis s t 7 4 84 9 .
,
1 9 1 6 ; 7 56 1 8, 1 9 1 6 ; A u st . P t .
,
1 9 1 9 .
 CHA PTER XV I I I
ANNI NG
'

VE G E TA B L E T M A TE R I A LS

As has been stated in the previ ous chapter our knowledg e of ,

a
t he chemistry of tanni ns i s no t su fficiently advanced to render
possible any strictly chemic a l classification while an dditional ,

complication arises from the fact that very different t anni ns may
coexist in the wood bark fruit galls e t c of the same plant I t , ,
_
,
.
,
.

t h e r e fo re rse e m s best to follow the example of Professor B ernardin

in his Cl a ss zfic ati 0n de 3 50 ma teer es ta
nna
.

n tes
l
and arrange the
'

a
-

_ ,

plants under t he orders of the natural system of bot ny as has

already been done by vo n Ho hn el 2 a
,

nd A de Lo f and con
a
.

sid e r b l e u se has been made not only of these books but of the
-

, ,

recent exhaustive work of D ekker on the vegetab le tanning

4

mat erials and of the various lists which have from time to t ime
'

appeared in the scientific press In the foll o wing pages onl y .

those material s which from their high p ercentage of tannin or

'

from some other cause seem of commercial interest o r value are ,

“

included as the tannin s are so widely dist r ib u t e d in t he vegetable

'

kingdom that a
,

n y exhaustive list w ould be quite out of the

question .

a
Tannins are not confined to any p articul ar part of t h e plant ,

though they are usually most abundant in b rks and fruits .

Insect galls are often very rich in tannin usually gallotannic

-

acid while in several cases woods are of comm ercial importance .

from their cheapness though the percentage of tannin they con ,

tain is not g enerally high Th e function o f tann i ns in the

’ '

vegetable economy i s not well understood In some cases they

a
.

are probably a w ste product of plant life and may help to -

a
,

ward o ff attacks of insects They u sually exist as cell contents

"

and as vegetable cells h ve frequently thick and 1 mp erm e a

-
.
,

ble
walls and the di ffusive power of tannins is low much time is
, _ ,

requ ired for extraction unl ess the cells have been previously ,

crushed or broken .

1
G ad n 1 8 80 2
D i e Ger be mn de n
'

B e r l in , 1 880
a at aa ai a
.
, , .

M d iz e res H ll e Cu ir s P 89 0 Se e
’

l Ag r i c u l t u r e;
‘
3 t n es , ux r s, 1
nn so

Ca tta
.
,

a
L e dg e r 1 9 0 2 N o 1
( G o v er n m e n t P r in t in g O ffi lce , cu by Mr
a a
l a f ma ad ai
.
, , , .

D H o o p e r wh i c h
.
,
co n t i ns much v bl u e in or ti on ,
n v r ous In di n

F o r e st r y R ep o rt s .
4
D e kk e r , D je Ge r bs t ofi e B e r l in , ,
1 9 1 3 .

27 8
2 80 P R I N C I P L E S OF L E A TH ER MA N UF A C T UR E

peeling or it may pro duce a thick layer of cork as in the cork

oak In many cases and especi a
,

. l ly in older t rees the oute r or , ,

pri mary layer of cork—cambium ultimately dies for want of

nourishment and a f e sh cork producing layer is developed in r

the still living parenchym A s cork is practic a

-

l ly air and .

water proof the new layer cuts o ff from its source of nourish
ment and kills a
-

l l the parenchym exterior to it I n some cases

"

l pl a
this peels o ff as in the Orient a ne ( P la
ia but usu a
.

r ms )
,
-
l ly it ,

FI G 4 7
— Se c t ion of a O k T w ig a
d r w n b y P r o f e s so r B s t in ; C , a c o r ky

a a f ad S t aa
.
.
,

l y e r ; t , t n n in c e l l s -
n st o n e —
c e ll s e t c C c m b iu m Mr m ed
a a
.
, , , ,

u ll r y r y ; P p it h , .

a
forms a constantly increasing coat of dead tissue forming t he
ross or cr p ( Ger B e r ke) which as it cannot increase in .
, ,

breadth becomes deeply fissu r e d as the tree becomes old In

, .

some cases the new growing layer or secondary cork cambium

forms a c om p l e t e coatin g par a
-

'

l lel with the fir st but more often ,

-

it consists of a series of arcs convex towards the tree and cutting

the primary cork cambium at various places so as to divide the -

tissue outside itself into scales Later on the process rep eats .

itself new arcs forming inside the first and cutting o ff further
, ,

portions of the parenchym 1

I n this way the cork forming layer
gradu a
-
.

l ly sinks deeper and deeper into the bark till it frequen tly ,

1
Th is st r u c t ur e is p at i l al y
r cu r o b vio u s in t h e o u t er b ak r of t he he m lo c k
ad A l
n ep p o p in e s .
 VE GE TA B L E TA NN I N G MA TER I A L S 281

passes even into the bast layer and very complicated arrange
-

a
,

ments of tissue result in which corky layers from the secondary

,

cork cambium r e interspersed with bast cells and sieve

- -

tubes .

A s a rul e the outer and dead part of the bark contains but
little t annin though to this there are exceptions as for instance
in the hemlock a
, , , ,

n d A leppo ines I t always contains a large

p
proportion of dark colouring matters ( reds p hl o b a
.

p he n e s p , , .

Cork consists of thin and often roughly cubical cells which

are fil led with air while tannin is usu a
, , ,

ll y contained in somewhat
si milar cel ls with thicker walls The wa
,

l ls of many vegetable
.

cells are perforated with fine holes and become thickened by ,

i nternal dep osits of hard ligneous matter which sometimes almost

fil l the entire cell stone cells B ark cells often contain
“

- -

starch — granules frequently of peculiar and characteristic forms

,

( which are easily recognise d by the bl u e colour produced on

treating the preparation under the microscope with a drop of a
sol ution of iodine in potassium iodide ) as well as cryst a l s of ,

oxal ate of lime and other matters These and the form and .
,

arrangement of the cells as seen in sections under the microscope ,

form useful marks of recognition of the various barks Tannin .

is most easily detected by staining before cutting sections with

a solution of ferric chloride in absolute a
, ,

l cohol .

A part from microscopic characteristics the external appear ,

ance of barks both to the naked eye and by the aid of a lens
a
, ,

forms a valuable me ns of recognition The arrangement of the

bast and corky layers the rem a
.

i ns o f epidermis or the form

'

, ,

and character of the fissures and of the lenticels or small corky ,

protuberance s which take the place of stomata in t he epidermis

'

sho ul d be observed .

Space does not permit of any detailed account of the structure

of fruits woods and leaves which are a
, ,
l so cellul a
,
r structures in
many respects resembling the bark The c u t icl e s of leaves and .
_ ,

especial ly the stomata or breat hing pores and the hairs are ,

often very characteristic ( Cp figs 5 9 —66 and p

V aluable hints may a l so be obtained from the chemic a
. . .
,

l reactions
which are described on pp 7 0 et s eq . .
 P RI N C I P L E S OF L EA TH ER MA N UFA C T UR E
i

2 82

BOTA N I CA L Lrs r o r TA N NI N G MATER I ALS 1

CONIF ER Z E , P i n e s , Cyp res s es , m ostly co n t a

i i n ng Ca
techol
a
.

t n s , y iel d i n g r e ds
A bies excel s aLa
m ( P in a
s A bi e s P in u s P ic e aP i a lga ce vu ri s ,

a a Ger Fi ht R tta
.
, , ,

Link ) Norway Spruce F r F u x s p iri ; m c e, o ie

a
. . . .
,

The source of the so —

c l led larch extract and a principal tanning
materi a
,

l of A ustria Contains 7 to 1 3 per cent o f a cat echol

tanni n and much ferment b le sugar n d on this account is use
ful for swelling and colouring but does not tan heavily English “
.

a ,
a .

.
,

and Scandinavian bark does not seem much utilised B c s t .

_

bark 2 to 8 mm : thick ; smooth yellow inside with red di sh , ,

brown ross outside Fo r detailed de scription of struct ure se e .

v o n H o hn el D i e Ger ber in den p 3 5

A bies p ectin a ta Silver Fir Sa Ger Edelta

. .
, ,

Fr p in r me ,

Sil ber ta Weissta

. . .
,

rm e mi e U sed to a limited extent but apt to

,
.
,

be confused with spruce Contains 6 to 1 5 per cent iron blueing -

tannin U sed in St yriaA u st r iaR ussia Witho ut 1 0 5 5 but

. .

. .
, _ , ,

silver grey and smooth outside ( Vo n H o hn el Die Ger berin den

-
.
, ,

p 40 Gerber 1 87 5 p 3 7 5 )
A bi es ( P in a s Ts uga) ca na
,

den sis Heml ock Fir ( fig Th e

‘

principal A merican tanni ng materia

.
, , .

l and source of hemlock ,

extract averages 8 to 1 0 p e r cent of a catechol tannin bu t .

-

variable ; 1 8 per cent reported possibly from a different species . .

A bundan
,

t in Canada and the No rt he irn and North west ern States -

of A merica Th e bark of old trees which is principally used for

tanning and extract making is 2 to 4 cm thick smooth a
.
,
”

nd
'

.
, ,

yellow within greyish and deeply fissu re d without The ross

a
.
, ,

whi ch is red and thick contains a considerable qu ntity of tannin

with much d ark red p hl o b a
, ,

p hen It does not di ffer in structure

-
.

from the inner living and yellow flesh Th e bark is easil y

'

recognisable by its well mark ed concave lamell a

. .

e of cork cutting -

,
.

o ff successive layers o f ross o f several millimetres 1 n t hickness ’ ’

a
.

n H ohn e l D i e Ger ber iri deri p ( p

C p
( V o

A bi es a l ba( P icea al ba
. . .
, ,

) White Spruce North A meric In , , .

character of tree and bark very similar to Norway spruce

La ea r op waD C a a
.

r ix ( A b i e s or P i n/ s L r ix ) Larch. Fr .
, .

a a
Th e p e r c e n t g e o f t n n in giv e n wh e r e t h e s o u r c e o f in f o r
1
t io n is n o t ma
a a a
s t t e d m u s t in m n y c s e s b e r e g r d e d s u n c e r t in m n y n l y s e s h v in
g a a a a aa a
a
,

b e e n m d e b e f o r e t h e in t r o d u c t io n o f m o d e r n m e t h o d s b t t h o s e qu o t e d u
ah am g b d i t h a a a a ad h a
,
’
s v e en one n e A u t ho r s l b o r t o ry r e o f r ec e n t d te n ve

ma
,

b d b y t h hid —p
een e e e o wd er m et ho d
Ba ad T im b l aC a aj a
.

A m e r ic A m er i c
’
ti 2
s n n r e s n o n if e r e n o u rn l f o

P hama
,

y r c .
2 84 P R I N C I P L ES OF L EA TH ER MA N UFA C T URE

surface The scorza rossa is dark red brown intern a ll y grey

'

and irregular outside frequently very thick a

-
.
,
.

n d di vided into

successive layers of I to 2 mm thickness by cork lamell a

, ,
,

e .

(p ( Vo n Ho hn el Die Ger beriri den p In appearance

“

.
, , .

the tree re sembles the Sco tch fir

P in a s ta e daA merica ; P La ma
.

r ici o A ustrian Pine ; P ri

timaMediterranean P C embr aA lps Tyrol 3 to 5 per cent

.
, , .

Ger Kief er Fr P in s a a
.
, , , , .

P syl ves tr is Scotch Fir i w g e 4 to 5 per

'

cent P l ongif olia

. . . .
, ,

R oxb I ndia 1 1 to 1 4 per cent

ju n ip eru s comma
. . .
, , .

m s Juniper B ark used in R ussia

P odo ca rp u s el ong a taand Thi mbergii Cape of Good H ope
.
, .

Geelho u t Y ello w woods

P hy ll ocl a du s tricho ma Ne w Z e a l and ; Ta n e kahi Ta
.
,

n oi de s rse

ka ki Kiri to a t oa Golden Tana U sed in dyeing glove leat her

, ,
”
- - -

, , .

Tannin 2 8 to 3 0 per cent gives green blacks with iron -

P a sp l eri if o li aTasmania
-
.
, .

Celery topped Pin e ; 2 3 per cent

P ky ll ocl a
-

da
.
, , .

s b elongs to Y e w family

P r homboi da
.

. lis Tasmania 2 0 6 per cent bark ( D ekker) and

, ,
-
.
,

red colouring matter

Ca llitr is ca l ca rata A ustralia bark 2 1 per cent tannin , . .

Most pine barks cont ain more or less tannin .

LILIA CEIZE

S cill amaitimaSquill r ,
. Tanni n st ated from 2 to 24 per cent .

More val uable for pharmacy .

PA LMZ E

A rec aa
t h c nut Pa l m of In di a
ec u , B etel
Yields a species o f -
.

cutch of no importance for tanning Fruits yiel d an extract

and contain 1 0 to 1 5 per cent tannin but n o c a
.

R ossa t e c hin
Sa ba ta
l s er r u l a Sa w Pa
. .
, , _

l metto of Florida ( Trimble) Dwarf

pal metto is S A da n s on i a ) Pa
.
,

l metto root has been much tal ked

of as a tanning materi a
. .

l and makes a light coloured leather

A n extract has been made from the roots of the Sa w Pa
-

.
,

l metto
which grows freely in the Southern Sta
,

tes of A merica and is ,

especially abundant on the east coast of Florida The plant is .

an evergreen the stem growing flat along the ground being held
in p l a
, ,

c e b y numerous roots each the size of a pipe stem

'

The -
.

leaves are fan shaped and ribbed and 2 to 3 feet in diameter I n

-

, .

its hardi hood the palmetto resembles a weed as the leaves may ,

be cut o ff quite close to the stem without damaging the plant ,

 VE GE TA B L E TA N N I N G MA TER I A L S 2 85

which will grow freely on poor sandy land which is worthless

for other purposes The average yield is stated to be about .

1 0 cwt to the acre but in good seasons and with rich land over
a ton per acre has been obt a
.
,

i ned
The a
.
-

ir dried leaves contain about 1 3 per cent of tannin but

-

.
,

the resul ts obtained by di fferent chemists vary from 5 to 2 0 per

cent P ossibly these variations are caused by the di fferent
.

amounts of moisture in the various samples Tri mble ( 1 89 6) .

foun d very little tannin and does not consider the plant of
'

importance .

The leaves must b e treated with a solution of caustic soda

to remove t he glo ssy siliceous shield which covers them and
prevents thei r being easily extracted A fter the tanning matter .

has been extracted the remaining fibre can be profitably disposed

of to paper and rope manufact urers
A s the supply of p a
.

lmetto is very large it was expected that it

would to a considerable extent substitute the employment of
, ,

gambier and in the United Stat es the extract met with a con
s id e ra
,

b l e sale but does not seem to have been sent to England

,

in any quantity Samples of the extract examined by the

A uthor an a
.

l ysed fro m 1 6 to 2 2 per cent of tanning matter and .

several per cent of mineral matter and produced a very Soft and
.
,

mellow leather of good colour The extract contains noticeable

a a
.

q u n t it ies o f common ‘

s l t and organic salts of soda which leave ,

so di um carbonate on ignition
C ocos n u cifer athe Cocoa nut P alm a
.

,
l so contains tannin in -

roots .

CA SUA R INZ E

C aai a qa
su r ri t if liaLa
i tif liaL ( l a m ) e Fil a
se o bark o er o

; Tja
ma al at Java ; Caa gh a
. .
,

m
R eu o n r u or Tinian
s Pine Ceylon , ,
.

Wid el y d ist rib ut e d in Southern A sia bark used for tanning and
dyeing Tannin gives blue blacks with iron Sever a
. l other -
.

species very similar in structure and properties ( Vo n Ho hn el ) . .

H ooper found 1 1 to 1 8 per cent of tannin . .

( W illo w s ) SA LI CA CEE

Most of the Willow tribe contain more or less iron blueing and

a
-

presumably pyrogall ol tannin in the bark and many have been

,
-

long used for t nning especially in R ussia The original su ede

leather was a combination tannage of the bark of S a l ix a
ren a
r ia
.
,

with alum and sal t and when this process was introduced in ,
2 86 P RI N C I P L ES OF L EA TH ER MA N UFA C T UR E

France the commo ner Sa pm a

l ix c a was substitut ed with a
'

ddi ,

tions of oak bark and madder to compensate its deficiency in

tannin and colour R ussia leath er owes p rt of its odour to
tannage with willow bark
. a
D ekker gives S a l ix a
lba
.

a
L bark 9 4 per cent tannin
Sa l ix c p rwabark 1 2 1 per cent tannin
. . .

Sa l ix f r a
gilis L 9 per cent tannin ; S R u ss eli a na
. .
,

.
, ( a variety) . .
,

1 2 per cent

Sa lix r ep en s or a
ren ar ia
.

L A strachan 1 3 p er cent
P oplars belong t o the same natur a
.
, , .

l order and t he l r bark

’ “

esp eciall y that of the A spen ( P op u lu s tr emn l aL ) has been used

, ,

for tanning but contains only bout 3 per cent t annin

,
a
_
.
,

MYR I CA CEZ E
Myr ica Ga l e Sweet G a l e or bog myrtle contains tannin
MyricaC omp ton iaor a s l en if o li aU S A
-

.
, , ,

p Sweet Fern , . . . .

Covers mil lions of acres in Michigan Yields 40 per cent of . .

extract Leaves 4 to 5 per cent roots 4 to 6 per cent t annin

according to season ( Trimble) H a
. . .
, ,

s been much talked of but .

,

in Professor Trimble s opinion is not likely to prove of much ’

importance
My ricana gi ( Hind Ka ipha
.

l ) India contains 1 3 to 2 7 per cent

of tanninin the bark and a colouring matter myricetin identic a
.
. .
, ,

,
l , ,

with that of sumach 1

Leather tanned with it is of a so m ewhat
reddish colour which is much brightened by su m a
.

chin g and con

verted into a p a l e yellow by treatment with a

, ,

l um It p r o m ises '

to be a val uable tanning materi a

.

l .

B ETU LA CEXE

A ln n s glu tin o s a Common Ger Er l e A lder Fr A u ln e ;

Cont a
. . . .
,

i ns 1 6 to 2 0 p e r cent iron green tannin with much red .

-

coLo u rin g matter old barks as low as 1 0 per cent Colour

, .

develops during and after tannage U sed alone it gi ves a red

hard and brittle leather but wit h g a l l s va
.
,

l o nia etc it produces

a satisfactory tannage It s princip a
.
, , , ,

l use is to furnish gunpowder .

charcoal and it is possible the bark might be obtained from

,

powder factories if the use of gunpowder is not superseded by

nitro compounds ( Vo n H ohn el ) The fruits have a
-

-
. l so been ,

used in tanning A n important fuel tree in high latitudes

A ln n s ma
-

r itimaH a Japan ; and A fir maMin iba

. .

n n o ki , ri , .
, .

1
P e r ki n ad Hn u m m el , Tr a ns . Che m S o c . .
,
1 89 6 , p . 1 287 .
2 88 P R I N C I P L E S OF L EA TH E R MA N UFA C T UR E

a
introduced as a tanning agent b y Aim é Koch The strength .

of extr ct is of course very variable even for the same density ,

( see Chapter XX IV ) but it usually contains from 2 8 to 3 2 per ,

cent of tannin The wo o d is a valuable timber and is now

grown in England for this purpose a
. .
,

s it is much q uicker in ,

growth than oak

a
.

The t nnin gives blue black with iron but is not identical -

with either oak—bark e r gall tannins but apparently a mixture , ,

or possibly a methylated derivative of the latter and identical ,

with oakwood tannin or so nearly so as to be indistinguishable

it may also be identic a
,

l with divi tannin De colorised chestnut

ext racts sometimes mixed with quebracho and other m teri a a
.

ls
are often sold as oakwood or oak bark extracts Th e -
f ’
.

extract gives a firm leather with a good deal of bloom if used ,

strong and a more reddish tint than valonia The extract often
,
.

contains dark colouring matters and the colour of leather tann ed ,

with it is readily darkene d b y traces of lime derived from cal

ca
-

r e o us waters or imperfectly delimed hides L ike all wood .

extracts it tans rapidl y the colour penetrating first and the tan , ,

following but according to Eitner it does not alone make full

or solid tannage perhaps from want of a
, , , _ , ,

c id a
fo r m in g matters but
, ,

answers particularly well in combination with spruce bark It is -

.

largely used in England for sole leather in combination with

va l onia myrobal ans and other materi a
,
ls ,
.

Th e higher the temperature of extraction and the more ,

colouring matter is contained in the extract in proportion

Much
'

to tannin mat ter the greater is its Viscosity ,

.

colouring matter remains undissolved if the extract is di s

solved in cold water but there is in ad dition a loss of
a
, , ,

tanning power the colouring matter being also cap ble of

a
,

combining with hide and it h s in fact been used for tanni n g ,

by dissolving it in solutions of b 0rax or alkaline salts By .

improved methods of manufacture the colou ring matter has

been much reduced .

Th e chestnut is an important food tree t he nuts forming a ,

considerable part o f the food of the inhabitants of Corsica and

Sardi nia and even of I taly
,
.

a
O ks

A lmost all speci es of oak contain useful quantities of tannin

in the bark and probably in the wood Most if not all oaks
yield catechol tannins with probably some m ixture of ell a
.
,

gi
-

, ,

tannic acid .
 VE G ETA B L E TA N N I N G M A TER I A L S 2 89

Qa
er cn s Common Oa k Fr Chen e ; Ger Ei che
r o bn r , It is . . . -
.

frequently separated into the two subspecies

eron s p edu n cu l aa Commonest oak of lowlands ngland
Q u t E
A corns in bunches or spikes on a st a
.
, ,

Ireland and Scotland lk

'

.
, .

1 ; inch long
1
hence G er name S tiel Eiche Leaves sessile or '

short stalked In favourable situation s s a

-
. .
, ,

-
id to yield about 2 per
cent more tannin than Q s essiliflor abut thi s is doub tful It is
.
,

. .
, .

the commonest oak in Slavoni a and the source of commercial

'

oakwood extract
s es s iliflor aGe r a
.

Q T b i h Common in hilly districts

'

. r u en e c e , .
_ .
,

and scattered throughout the country Acorns in bunch on the

branch or with very short st a
.

,
l k ; leaves on stalk to 1 inch
l 0n g
’

Of English barks Sussex and Hampshire are considered the ,

best and contain up to 1 2 to 1 4 per cent of tanning matter a

coppice bark from Wa st d a
.
,

l e Cumberland is however recorded , , , ,

to have yielded 1 9 p er cent tanning matter ( H el l o n ) . .

Probably each of the two varieties o f oak gives best bark

’

where it thrives best ( von H ohn el )

~

B elgian bark is sometimes equal to Engl ish and contains

“

Dutch bark a
,

I 0 to 1 2 per cent tanning matter s e x p o r t e d is

. .

general ly inferior and not cleaned ; Swe di sh is bright but very , ,

poor
Oa
.

k bark contains a tanning matter quercitannic acid giving

green blacks with iron s a
-

, ,

-
l ts and possibly containing both catechol -

and pyrogallol group s but its constitution is not full y under ,

stood ” It yields both r e d anhydrides and ellagic acid ; and

ga
_

l lic acid has been obtained by the action of hydro chloric acid

a
,

though not b y fermentation in the tannery The tannin is not a “

glucoside but th e fact that sugar l a

.

e vulose is al so present in
“

, , ,

the bark has led some observers to erroneous conclusions regard

ing the constitution of the tannin The un p u rifie d infusion of ’

the bark of Q r o ba
.

r gives a blue blac k with iron salts from the

.
- -

pres ence of a colouring matter ; but those of most other oaks

gi ve green blacks
-
.

Most tannin is contained in the living part of the bark The .

yield diminishes in trees over twenty five years and coppice

barks from absence of ross a
-

, re often strong and also contain , ,

less colouring matter and more fermentable sugar .

Warm and r ich soils seemto yield the best barks .

The brighter the colour of the fresh cut flesh the better -

, _

the bark D ark brown inner side shows that bark has been
.

exposed to rain which deteriorates strength and colour but a

,

very light colour is thought by some to indicate poorness in

I 9
2 90 P RI N C I P L ES OF L EA TH ER MA N UFA C T UR E

tannin Wh ite lichen is said to be a mark of poor bark and

. .
,

probably indicates a damp and unfavourable situation

Oaks are genera
.

l ly cut when the sap is rising ( 1 5t h A pril to

1 st h June ) when the buds open and new soft c e ll s begin to grow
, ,

for the bark 1 5 then more easily detached .

Experiments in France have shown that the bark of timber

felled at other seasons may be loosened by steaming and it is
said there is no practic a
,

l loss of tannin Superheated steam

produced In a sm a
.
,

l l boiler I n the woods is used , .

The bark is peeled with tools of various forms the branch

and knotted places being loosened by beating with a m a
,

l let .

The bark must be peeled immediately the tree has been felled .

Th e peeled bark in pieces up to 3 feet long is laid on hurdl es

, ,

sloped in such a way that the rain runs o ff as much as possible ,

and In this way it i s dried but l n wet seasons is much damaged , .

B ark so dried 1 n the woods often retains 40 to 50 per cent water

and must be stacked or stored so as to a
.
,

l low of further drying

a
.

English bark is s om e t im e s s o l d in long rind and sometimes

hatched or chopped in pieces a
,

bout 4 inches long B elgi n .

and Dutch barks are generally hatched B elgian t ree bark is .

cleaned ( and cleanings often mixed back with bul k) Dutch

bark is not cleaned Much sand and dirt is cont a
, ,

i ned in most
Cont inent a l bark : screenin gs of B elgia n b a
.

rk i l d d a black
'

y e e

liquor and contained so much san d that they would not even

a
,

burn
O k ba r k ex tra ct is occasion a l ly o ffered for s a l e but is not
usu a l ly genuine or of good qu a lity except that of t he A m eric a
-

a
,

chestnut oak Q prim is from which an excellent extract has been

m anufactured in the All e gh a
-
. /
, ,

n ie s F cti tious extracts often

contain myrob a
.

a
l ans and quebracho
Oa
.

kwo od contains only very small percentage ( from 2 to 4

p er cent ) of a tannin practic a ll y identic a
,

l with that of chestnut

a
.
,

but di fferent to that of o k bark It is stated b y de Lo t to reach -

.

9 to 1 4 per cent in old heart wood but this is doubtful Th e

-
. .
,

wood retains the tannin in it s i n t erio r for a long time Wood of .

_

a R oman bridge built at Mainz 55 is stated by d e Lo f to have

still contained 1 1 4 per cent tannin in A D 1 88 1 A good de a
\

-
. l . . .

of i mitated oakwood extract is undoubtedly made from ch estnut

wood and unfortunately no very s atisfactory way of distin
a
,

g u ishi n g it is known though oak bark, e x t r cft can be di stinguished

-

from oakwood by giving a precipitate at once even in dilute ,

solution with b romine water while the wood gi ves a brown

,
-

precipitate only after long standing Precipitation by bromine

water is a genera
.

l characteristic of catechol tannins and hence -

,
292 P RI N C I P L ES OF L EA TH ER MA N U F A C T U R E
'

the strength of the layer liquors Th e extract is al so used to

increase the weight of leather a
.

fter tannage by mopping on the

flesh side Al l the best oakwood extract manufact urers con
I
.

tract to sell on analysis and colour estimation and good Slavonian

oakwood extra ct generally contains 2 6 to 2 8 per cent of t a
,

n nIn g .

FI G .
5o .
— Co r k O k a( Q u erc u s s u b e r ) .

matter giving a tintometer measurement of 4 to 5 red and

,
° °

2 0 to 2 5 yellow when a solution containing per cent: o f tanning

° °

matter is measured in a I cm cell Fo r particulars of the manu . .

facture of concentrated extracts see p 49 3 et s eq

Q cerr is Turkey Oa
. .

.
,
k Ger Z err eiehe Common in Southern
. . .

Europe a fine tree but bark inferior to Q r o bn r ( fig

a
. .
,

Q p . u b e scen s Fr Cheri
. e ve l n Ger
. W e i ss or S chw r z eiche . .

In mount ain districts and scattered in Southern Europe about

equ a
,

l to Q r o bn r
a
. .

Q i
. l ex E vergreen
,
O k F r C hen e ver t Cheri e y eu s e ; Ger
. .
, .
 VE G E TA B L E TA N N I N G M A TE RI A L S 293

Gru n eiche , S tein eiche ; Span and It l En cin South Europe . a . a .

,

A lgeria . Said to be so mewhat stronger in tannin than common

oak yiel di ng 5 to 1 1 per cent of a rather darker coloured tannin
, .
-

but well adapted to sole leather Good bark is smooth outside .

,

without fissures short in fracture

O sa ber Cork Oa
.
,

k F Chen e l i ege Ital S ughero Sn oer o

‘
.
, . . .
,

( figs 50. The outer bark is cor k ; the interior bark contains
,

1 2 to 1 5 per cent of tannin which is redder than that of ordinary

.
,

FI G 5 1 . .
—Se c t io n of Co r k O k a , s h o w in g c o r k , in n er b ak r a
nd wo o d .

oak Trees at first produce an irregul ar cork sold as vi rgin

.
,

cork for ferneries etc A fter this is stripped later growths

“

are more uniform and fit for use t a nnin g b a

.
, ,

rk is only obtained
'

when the tree is cut down B ark is rough but pale coloured on “

.
-

both sides and about 1 cm thick ; interior l ike ordi nary oak
,
.
,

but more strongly furrowed P roduced chiefly on Mediterranean .

a
coasts and formerly largely used in Ireland
r A frican Oa n e fa
.
,

s eu dosn be— k F C h n x liege Al geria

Op
‘

. r ,
. . . .

No t stronger than English oak but with more co louring matter , ,

hence strikes quickly through leather B ark very thick . .

O M. ir be c ki F r C heri e Z een
. A lgeria R apid.growth . . .

B ark contains 8 per cent of tannin

r C hen e ta
. .

Q. T oz ee F n z in
. P.yrenees and S
‘
France B ark . . .

contains 1 4 per cent of tannin . .

2 94 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

Q .
f aKermes Oa
cocci er k Fr Kermes Ga
, r o u ill e
( fig . .
, .

South Europe and Algeria R oot bark is call ed rus u e

q or
ga
.

ro u ill e averages I O to 1 8 per cent tannin but trunk bark .

,

does not exceed 1 1 p er ce nt This tree is the food of the kermes

,
.

insect used for dyeing scarlet before the introduction of cochineal

, .

FI G .
52 .
-
a
K e r m e s O k ( Q u erc a f
s c o cc i e r a
) .

G a is principally used in the South of France giving a

ro u il l e

a
-

firm sole leather of a dis greeable odour and dark brown

colour
ca
Q ma cro l ep is gr a
.

E i l and probably other —

Q z g p (o s s p ec I e s

Ung er i co ccif er a) V alonia Fr Va l on e e ; Ger Va l on eaA cker

.
_ .
, ,
’

dopp en Or i en ta
.
, , . .
,

lische Kn opp ern B est Smyrna contains up to

a a
.
,

4 0 per cent Greek 1 9 to 3 0 per c ent C ndia v l onias up to 4 1

per cent and Ca rama n ia

. .
, ,

.
,
n ( probably not Q E gil op s ) 1 7 to 2 2 .

per cent of t annins which are at least principally pyrogallol

.
,

derivatives and which gi ve blue blacks with iron no precipitate

,
-

,
296 P RI N C I P L ES OF L EA TH ER M A N UFA C T U R E

the cups become dark coloured a n d damaged Th e acorn con

ta
.

i ns a considerable amount of fermentable sugar

Wh en ready for shipment the va
.

l onia is hand picked the -

largest and finest cups ( prima) going to Trieste the second ,

selection to England ( Inglese) and the remainder known as

natura a
, ,
”
l so coming largely to England I nglese
’

l The
a
,
.
,

l though inferior in appearance to the very large scl e c t e d cups

1 5 of course less costly and gives an equ a
,

l yield of tannin
,
.

In 1 88 7 Smyrna exported about tons to England

and tons elsewhere , p rinci pa l ly to A ustria Germany and , ,

Italy . The largest known crop i s stated at tons i n A sia

Minor and in Greece but the average yield is considerably ,

less than this .

The beard contains considerably more tannin than the cups ,

sometimes over 40 per cent It is often sold separately at the

same or a low er price a
.

n d in Smyrna is known b y t he Turkish

nam e tirn a c ( It a
,

l trill o )
In Greece the best va
. .

l onia is collected ( in A pril befo re the

cup is matured and whilst it still encloses the acorn and is known
as cha ma da( It ca ma taand c a ma tin a
,

.
) Th e colour of thes e .
’

kinds is excellent and t he percentage of t annin high Mai nl y .

a
used by dyers but often worth attention fo r tanning where
In c a ma
,

colour is important tin the acorn is completel y

covered in the cup while in ca ma ta
.

it is partly exposed
The next quality r ha
.
,

bdis to is beaten down by sticks in Se p

, ,

t ember to October (hence name ) while after the first rains the
fruit falls and turns black and is cal led cha l a It contains
rc a
,

.
,

but little tannin and is not generally collected

Sometimes va
.
,

l onia is attacked by a sort of honeydew prob ,

ably caused by an aphis which renders it very sticky and

.
, ,

perhaps more liable to heat but does not in itself damage it s ,

tanning properties .

The lighter the colour the heavier the weight and the thicker
the sc a
, ,

l es of t h e beard the better the quality usually proves

Ca rama n ia va
, ,

b ut analysis is the best guide n l onia is very .

inferior .

The tannin contained in valonia is especiall y valu able in the

manufacture of sole leather It deposits much bloom and if .
,

used as a dusting material has the characteristic of making the

leather solid and compact but leaves the grain somewhat rough
and hard to work In mixture with gambier and other materi a
,

. ls
it is an excellent tannage fo r dressing leather and with proper ,

management deposits little or no bloom ( 01 5 p

Q inf ect oria
.
. .

.
( fig 54) is the source of th e Turkish or Aleppo
.
 VE G E TA B L E TA NN I N G MA TE R I A L S 297

gal ls .Ga ll s are caused by insects princip al ly of the genus ,

Cynips or gall wasps which lay their eggs in di fferent parts of

a
pl nts a
-

, ,

n d in som e way cause an abnormal gr owth of the bud

, ,

leaf or other part The gall wasps affecting the different oaks
, .
-

are shown in the figures

A lepp o ga
.

lls are developed from the young shoot of the oak ,

FI G .
54 .
-
a a( Q
G 11 O k . i nf ec t or i a
) .

are best before the insect h as escaped and contain in this stage ,

up to 50 or 60 per cent of gallotannic acid When the insect . .

has developed and escaped the galls are o f course perforated

'

much lighter and more porous These gall s and those of

Rhu s s emialataare the principal sources of the tannin of
.
,

commerce
a
4

The Q inf ectoria

.

. l so bears a large gall like an apple A pples ,

of Sodom or rove caused by a di fferent insect This in a

crushed condition has been somewhat largely used a
.
, , ,

, s a tanning
material and contains 2 4 to 3 4 per cent gallotannic acid
, . .
29 8 P RI N C I P L ES OF L EA TH ER MA N U FA C T UR E

English oaks have severa l species of g a l ls and oa k apples -

but they do not seem to be of much value for tanning .

Kn opp ern are galls produced on the immature acorns of various

species of oaks principally Q c erris in Hungary and were
formerly largely used there for tanning as they cont i n up to
3 5 per c ent gall otannic cid
,

They are now less abundant and a

.

,
,

a
have been largely replaced by valonia sometimes called orien ta
. .
,

l
Like all purely gall otannic materi a
,

ische Kn opp ern . l s they ;

naturally give a soft and porous tann age ill adapted for sole ‘
,
-

leather purposes which has led to the A ustrian practice of ,

.

drying or rather stewing the leather in very hot and damp

, ,

stoves which make it hard and bri ttle

Chin ese and ja a a
, .

p n es e g l l s are the p roduct of the action of .

an aphis on a species of sumach and will be mentioned again ,

under sumachs ( Rhus)

Dja a a
.

f t de hif jj
t i i or jf r is a materi l apparently of E astern

a
, , ,

origin and said to be derived from an oak of Kurdistan D ark

, .

red scal es or fragments o ri gin uncertain very stringent and , ,

darkish tannage liquor when spilt dries whitish apparently from ,

crystallisation o f some sort It contains a large amount of .

tannin It appears very irregul arly in commerce and the writer

.
,

would be glad to obtain further samples and details of origin .

He once used 6 or 7 tons successfully in sole l eather tannage

It has a l so been attributed to a shrub allied to the Cee s a lp in i a
.

(p 3 27 )
The most important A merican oaks are : Q prin us ( ca s ta
n ea

mon ticol a ) the Chestnut or R oc k Oa A bout equ a

.
,

,
k ( fig l to .

our oak in strength bark very thick and infusio n strongly flu o r

especi a
, ,

es c e n t , lly in presence of ammonia . Source of chestnut “

oak extract The most import ant tanning oak bark of the
.
-

United States
Q a l ba
.

. or white oak is perhaps the most widel ydistributed

, ,

and abundant of any of the American oaks and very closely

'

resembles the European Q r o bn r

Q tin ctori aor n igraB lack or Q uercitron Oa
. .

k P oor as a
tanning materi a
. .
,

l but used for dyein g yellow and for mo difying

,

the colour of hemlock tannages The dyestu ff qu erc etin is

closely a l lied to that of fustic and gives yel lows with a l um a
.
, ,

nd ,

tin mordants .

A good deal of information is given by Trimble on A merican 1

“

oaks and other tanning materi a ls

Q pa chyphyll a A corn cups used very sim il a
.

. r in appearance
.
,

to Greek valonia Tree grows in hill y districts of N I ndia . . .

1
The T ai n n n s , vo l . ii . Lip p in c o t t , a
P h il d e l p h i a 89 4
,
1 .
300 P R I N C I P L ES OF L EA TH ER MA N U FA C T UR E

tannin ( Pilgrim dry material) The liquor has a: strong but

, .

not red colour

Other important Indian oaks are Q gl a uca and Q inca na
.

;
bark of last said to yield 2 2 per cent of ta
. .

nnin . .

In addi tion to these D ekker gives a large number of other oaks

'

cont a
,

i ning tannins but mostly in quite small quantities and

rarely so much as 1 2 per cent Q ru br a( common red oak of
, ,
"

N A merica) ha ga
. .

. s t wiga ll s in which Trimble found 3 48 per ,

cent tan nin but o nl y found 4 per cent in the bark though
.
, .
,

Eitner found 1 6 per cent .

P OLYG ONA CEZ E , Do c k s

Theroots of most members of this famil y contain tanni n often ,

a
in considerable quantity
ln m Ca
ex hy men o s ep a na
.

Gonagra ( Cana agria) R e d

'

Igr e , , ,

D ock wild pie plant ( fig

,
Common in sandy alluvial plains
-
.

of Mexico and Texas and considerably resembling rhubarb It s , .

tuberous roots resemble those of the dahlia and contain when , ,

air dried 2 5 to 3 0 pe r cent of a catechol tannin probably al lied

to that of mimosa but of a much p a
- -
.
, ,

l er and yellower colour

U ndried the roots c 0n t a in a
.
,

b o u t 6 8 p er cent of water and only

'
'

.
,

8 per cent of tannin When wel l harvested by slicing thin and

. .

rapidly drying it g1 ve s leather a bright orange colour and it is

"

said considerable weight and firmness and is thus specially

, ,

suitabl e for use in retanning and finishing light goods and harness .

leather B esid es tannin the root contains a yell ow colouring

.
,
.

matter and about 8 per cent of starch , of which t he granules

are very variable in form and size but mostly ova
.

l or elongated , ,

and do not stain readi ly with io di ne till they have been well
washed or treated wit h di lute sul phuric acid B oth the starch .

and tannin are contained in large and somewhat thin walled

cells , and the sliced materi a
-

l is easily extracted at low tempera

tures Greater heat gelatinises t he starch and extracts a darker
.

colour The best temperature for extraction is between 3 0 and °

Th e l a
.

'

5 0 C ( see p r ge c o n t en t of st arch and the cost of

°
. .

culture and harvesting has told against the use of this plant .

Fo r a drum tannage on Dr Turnbul l s principles however the

’
-

, ,

presence of starch woul d be no di sadvantage ( op p . .

Th e root is most readily grown from tubers or portions includ

ing the crown as the plant seeds sparingly Sandy soils subject
, .
,

to inundation or irrigation seem best suited to its cul ture In ,

.

California and A rizona the growth begins in October or November

with the winter rains blooming about the end of January while , ,
56 aa
C a a ad
ig ( R u m ex hy me n o s ep l n m
at
-
n re
) N e w Co m me rc i l D r u s
.

g n Pl n s, T . Ch r is t y
 P RI N C I P L E S OF L E A TH ER M A N U FA C T U R E
‘

302

the leaves die down in Ma y and the roots remain dormant during
the summ er It is not import a . nt at what time the root s are
harvested and they seem to improve in percent age of tannin up
,

to the second year after which they become darker and deteriorate
, .

The harvested crop sho ul d b e sliced in t o thin pieces and

rapidl y dried at a low temperature or still better converted at
once into extract This is a a
, , ,

l ready done on a consider ble scale

‘

at D eming Ne w Mexico Th e residue after extraction is used

in A merica as Cattl e food and might no doubt be a
-

.
,

-
l so applied
to the production of alcohol
Planting takes place in autumn in rows s a
.

y 3 0 inches apart , , ,

with 1 0 inches between each root R o ots for seed should be .

kept in the ground or stored in dry sand This should yield a

crop of 1 0 tons per acre in a
.

n average s e ason

a
.

R ef er en ces — R ep ort U S C o mmiss ion er of A gricu l tu re 1 87 8

pp 1 1 9 et seq Trimble A m eric n ]ou rn of P ha r ma
.
_
.
, ,

cy p 3 9 5

1 88 9 ; C a na
. . . .
, , ,

igr e B ull No 7 A rizona A gr Expt Station 1 8 9 3

Ca na igr e or Ta
. . . .
, , ,

nn er s D o ck B ull No 1 0 5 U niversity of Cali

’

fo rniaB erkeley Cal Ca na igr e Ta

. .
, ,

n n in Tr imble and P eacock

R ep or t t o the Germ a n Le a ther Tr a des A s s ocia
.
, , , ,

Philadelphia 1 8 9 3
ti on by v Schroeder 1 8 9 4 ; I l C a na
,

,
. igr e E A n d rie is Turin , ,
.
, ,

1 89 9
a a
.

R u mex m r i tim Central Europe England Ireland I f is

a
. .
,

said by de Lo f to be fou nd in C l ifornia where It is used by the ,

I ndi ans for tanning but he probably confounds it with canaigre .

De Lo f found it s roots wet to contain 6 per cent and after

a a
.
, , ,

drying 2 2 per cent of t annin together wit h st r ch n d an acid .

,
'

allied to malic .

Several English docks cont ain tannin the writer had a sample
of leather tanned with dock root ( very possibly R a qu aticu s) -
.
,

many years old but still s oft and close in texture and of excellen t
qu a
, ,

l ity
P olyg o n u m a
.

mphibiu m Said to grow on thousands of acres

R oots cont a
.

on the lower Missouri i n 2 2 per cent branches

P a
. .
,

1 7 per ce nt o f tannin mp hibium is a commo n English and

. . .

European plant with spikes of pink flowers g ro w mg I n marshes

a P robably this is t he P olyg on u m an a l ysed by Fr a a
, ,

nd ponds . s ,

who foun d 2 0 to 2 6 per cent tannin

m Bi st or ta Common in damp places in England
. .

P olygon u
Ea
. .

Bistort Snakeweed called

,
s t e r m er giants in Cumberland
, ,

where the young leaves are used for making herb puddin gs
Fr aa
-
.

s found 1 6 to 2 1 per cent tannin in the roots . .

Other species are known to contain much tannin P erkin

found a red colouring matter in P cusp ida
.
_

tu m a native of India .
,
304 P R I N C I P L E S OF L EA TH ER MA N UFA C T UR E

fiermu m
Leu c osj co n o e ap
r um . Kr upp el bo o m . Knotted Tree
'

Cape of Good H ope Said by de Lo f to contain 2 2 per cent of

a
. .

tannin ; but a specimen ex min ed by the A uthor yielded 1 0 9

per cent on analysis
P ro team ellif er a Sugarbush
. .

S u iker bos ch . Cape of Good . .

Hope Bark contains 2 5 per ce nt t annin accor di ng to de Lo f

but Pa
. .
,

l mer foun d 1 8 8 per cent D ekker only states 3 per cent

P r ot eagr a n difl o r a Wa a
. .

gen boom Cape Contains 2 5 per . . .

cent tannin ( de Lo f) 1 5 9 per cent ( Palmer) 1 5 6 per cent

.
1
.
-
.

( Procter )
P r o t ea sp eci os a Cape of Good Hope
.

U sed for tan ning

Leu ca den dr on a
. . .

r en t eu m Silver T ree , Si l ver bo om Wittebo om

g
Cape of Good H ope B ark said to cont a
, ,
.

in 1 6 p e r cent tannin
( de Lo f) ; a
. .

s p e c im e n exami ned by the A uthor i elded 2 per

y 9
1

cent
Bra biu m s tell a Wilde A ma
.

tif ol iu m n delboo m Wild Almond , ,

.

Cape of Good Hope A stringent . .

SANTA LA CEZ E

Osy ri s mp ress
co a( F a us nu s c om p”r essa
s C olp o on co mpressu m
P r u im B a
, ,

Thesiu m Colp oon ) Cape Sumach st leaves and

bark Cape of Good H ope Leaves cont a
, , ,

i n about 2 3 per cent

a
. .
,

( P erkin ) 1 7 per cent ( M i den ) of tannin and for m a useful

substitute for sumach but the tannin is not identic a
.
, ,

l and is ,

of the catechol cl ass resembling gambier

O a r bor e a Northern India
. .
,

. . Leaves rich in tanni n; 2 0 p er .

cent ; contains quercetin ( P erkin )

O a byss in ica Somaliland
. .

. Th e leaf contains 2 3 to 2 5 per

. .

cent tannin ( Watter )

Fu s a ac u m in atu s ( S a n talu m a cu min a Qu a
. .

nus tu m) n dony ,
.

A ustralia Eighteen to 1 9 per cent dark colou red tannin -

Ex oca
. . .

rp u s cup r e ss if o rm i s A ustralia B ark contains 1 5 p er

“

c en t t a
. .

n n 1 n ( Maiden )
'

. .

DA P HNOI DZ E , Sp ur g e L a
urels
a
D p hn e Cn idium L .
,
G a ro u . Algeria . U sed for dyeing and
tanning .

P LU MB A G I NZ E

P lu mb go Eu r op e Leadwort Fr a a ,
. . garden
D en t el ir e a . A
plant in England native in Franc e ; ,
contains much tannin ,

especially in the r oo t -
bark .
 VE G E TA B L E TA NN I N G MA TERI A L S 39 5

a
S l tice c o ri r i aaMarsh of R ussi
,

up to 3 metres long and 2 to 1 2 cm thick used b y Kalmucks

R oots R osemary .

.
South a .

for tanning sheep skins contain 2 2 per cent of t annin ( de Lo f)

-
. .

D ekker gi ves 2 0 to 22 per cent .

S gmeli n i W South R ussia U sed as above

S latif olia Caucasus and Mid dl e A sia
. . . .

Strongly astringent
S scop a ri a
. . . .

P all Siberia Strongly astringent

Se aLavender
. . . .

S limonum L Coasts and salt marshes

of Europe and A merica R icher in tannin than S coria r ia
. . .
,

; . .

a
used in France Spain and Portugal , , .

Several other species contain tannin Th ese pl nts are allied

to Thrift ( A r meria
.

) which is also astringent , .

MA LPIG H IA CEZ E
Byr s o n im ta
api a ( R ich )
s c . S A merica A ntilles
.
, ,
a
T m wo o d .

B ark contai ns up to 43 5 per cent tannin

aa Jamaica Golden Spoon
. .

”
B co ri ce
B chry sop hyll aetc
. .
,

B cr a s sif o li a
. .
,

. HEK Cuba Contains fn u c h tannin in bark

. . . .

and unripe fruit

cy don i a ef o l iavar
.

B . chiqu iten s is B olivia

,
Native . .

name m u r e c i B ark contains 20 per cent tannin

Ma lpighia a an g ru t t a
. . .

p u n i eif o li N icaragua Nancite M .

, .

B ark contains 2 0 to 3 0 per cent of light coloured tannin

a
-

M fa
. .
/

g i n e . M exico N ance B ark up to 2 6 per

-
cent , . .

a
“

P OLYGA LA CEE ,
Mil kwort F m il y

Kr meri a atriad iaR hatany n r , ,

P eru .

The root is used in medicine and is stated to con tain 40 per

-

cent of tannin . .

Wit t St e in found only 2 0 per cent of an iron greening catechol .

-

p hl o r o gl u co l tannin allied to tormentil tannin in the root bark

-

the only active part of root

EU P H OR B I A CEZ E

Cl eis l ath
n us c olli n u s , Ko d ai rs ,
D eccan . B ark stated to
contain per cent of tannin
33
P hyll a embl i c a ( A onla
. .

n thu s A mla ) India Twig bark .

,
. .
,

mature bark leaves and immature fruit ( em blic myrobalans)

, ,

20
39 6 P R I N C I P L ES OF L EA TH ER MA N U F A C TUR E

all contain considerable tannin A nalyses by P ilgrim and others

a
.

s follows

Twig B ark . Fruit without Stone ,

.

Per cent . P e r cent

1 9 to 24 2 6 to 3 5 ,

1 0 I 7 37 n 40

Twig bark gives smooth grain steady swelli ng of hides during , "

tannage R eddish colour when used alone

;
Very useful .

material
P dis tichu s and n ep a
.

. len sis both yield tannin g barks .

A NA CA R D IA CEZ E

S chin op s i s b l n s w aa
also named Qu ebr a chi a Lo r en l z ii
and Lox optery ngiu m Loren tz ii Span Qu ebr a cho co l or ado South . . .

A merica especially A rgentine R epublic

,
the highest proportion
of tannin occurring in the wood fro m Gran Chaco district Wood .

c ontains on an average about 2 5 to 2 8 per cent of a red diffic u l t l y

a
.
,

soluble tannin yielding reds and containing catechol and

, ,

p hl o r o gl u c o l The t nnin is not very soluble in water and hence

'

.
,

can only be used in weak or warm liquors but is very astringent

and gives a firm reddish leather The wood a l so c o n t ain s a
, ,
'

.
,

catechin and a colouring matter fustin identical with that of

1
, ,

young fustic It is imported int o England and more largely

.
,

to Havre and H amburg in logs which are th ere chipped like , ,

logwood and either u sed direct for tanning or made into extract
,
.

A very cheap t an With alum it gives a yellow col our The

. .

extract usually dissolves to a fawn coloured turbid solution -

.

Many quebracho extracts are now made completely soluble by

treatment with alkaline bisulphites ( op p o r b y t re a t m en t
'

with alkali which is afterwards neutra

. .

a
l ised Th e so calle d
insoluble m tter is really a sparingly soluble ta
-
.

“
nnin and if ,
.

agitated with hide will tan it comp letely .

Th e Spanish word quebracho means axe breaker and is

applied to many hard woods The wood of S ba la nsa
-

e has a . .

specific gravity of 1 27 to and is consequently much heavier

-

than water It is much used for railway sleepers for which it is

.
,

very durable The sapwood only contains 3 to 4 per cent and

'

. .

the bark 6 to 8 per cent of tannin . .

The annual cut is said to be much less than the annual growth .

It is common in Chili and P araguay as well as in the A rgentine ,

.

1
Se e P Ar t aa] o u rn Chem S oc 87 8, A, p 9 86 ; 1 1 88 1 A, p 1 1 52
ad P ad G a
. . . .
, , .
, .

n e r k in n u n n e ll , Tr ns . Chem S oc , 1 8 9 6 , 1 3 0 3
. . .
308 P RI N C I P L ES OF L EA TH ER MA N UFA C T UR E

contains iron Ma
a
lated sum ch Is w mn o we d to remove dust and sand which o ft en
sc o lin o
-

is the best sumach from P alermo

,
'

a
.

and district f e m i n ell consists of weaker sorts from other

parts and is genera
,
l ly used for mixing .

Th e di fferent varieties of sumach are classed as follows

R elative
Market V alue .

Su m ach for baling 2 5

for grinding 2 3 .
-

from yearling plants 1 5

from ends of branches collec ted I n
autumn

To prepare these d i fferent grades for ul timate consumption

they a
,
a
r e ground in mi l ls similar to those emplo yed for crushing

olives t h t is in which two large stone wheels follow each other

,

revolving upon a circular bed the whole construction being

'
,

simil ar to the Spanish or Mexican a rra

,

a
s tr e Th e sumach thus .

pulverised is passed through bolting screens to sep rate the -

finer from the coarser particles .

A fter the sumach leaf has been subj ected to the first process of
trituration the coarse remaining portions are re; ground and the
,

product added to that which h as been already obtained The .

still unpul verised residue known as pedu z z o is sift ed and the

, ,

coarser and ungrindable parts are used as fuel w

,

hile the finer

are mixed with the parti a l ly ground sm a
,

l l leaf bearing branches

a a a
-

zz a
-

, ,

(g m bu z z g m m u , ) and ground again ,

.

P alermo is the principal seat of the sumach t ra de Th e

materi a
.

l is general ly bought from the smal l growers by m iddle

men who hold it til l market conditions are favourable Th e
quot ations are a l ways in ta of 42 5 centimes per ca n ta
.
,
_

ri r of
'

7 9 3 42 kilos which are obsolete even in Sicily and have to be ,

reckoned into l ir e ( francs ) and kil os Consequently 1 t ari per

cantar equ a
.

l s 0 5 3 565 lira per 1 0 0 kilos

°
.

I n 1 8 9 4 the prices delivered at the mill s were about 4 1 to 42

tari for mascolin o 3 7 to 3 8 tari for fe m in ell a1 4 to 1 8 tari for
,

, ,

brusca and 1 0 tarl for stinco per cantar the lira being worth
,
'

about 9 d 1

Sumach has been introduce d into A ustra

.

l ia and is said to ,
,

thrive well in the dry plains of the Wimm era district .

Sumach often contains much sand and sometimes particles ,

of magnetic iron ore which cause black stains and may be , ,

coll ected by a magnet and which dissolve in dilute hydrochloric

,

1
Cf Ke w B u l l e ti n , No 1 07 29 —6
.
, pp .
3 .
 VE GE TA B L E TA NN I N G . MA TERI A L S 30 9

acid without evolution of hydrogen to a yell ow solution : Metallic

iron which is a,
l so attracted by the magnet dissolves in hydro ,

chloric acid with effervescence to a colourless or green solution

Good sumach cont a
.

i ns at least 2 5 to 2 7 per cent of tannin Th e

Author has an a
. .

l ysed samples of undoubted genuineness contain

ing as much a s 3 2 per cent of a tannin alli ed to gallotannic
with some el l a git a
.
, ,

n ni c acid and a colouring matter ( myricetin ) ‘

identical With that of Myrica na

,

i
g ( p which gives ye l lows
with a
.

l umina and tin mordants and is fu gi tive to light

Sumach is the best tanning materi a r pa
.
,

l kno wn fo_ l e colo ur

and soft tannage and is hence used for moroccos roans skivers
etc and a
, , , ,

l so for brightening leathers of darker tannages such

'

.
, ,

as mimosa gambier the colou ring matters of which warm sumach

, ,

l iquors seem able to dissolve .

In the r eport of the Society of A rts Committee on bookbinding

leathers it is stated on abundant evi dence that sumach tanned
1
,
-

leathers are less affected by light and gas fumes and less liable to -

decay than those of any other kn own tannage

, .

Sumach is frequently adu lterated with the ground l eaves and

twigs of P ista c ia sc hin ia or C oria ri a

a
l en tis cu s skens
2

my r tif oli stinco Ta ma r ix a f r ic ana brusca Ai l a n tu s

g l an d u l o s a Vi ti s v in i f er a ( leaf of the common grape vine ) C i s tu s

sa
, ,

lvif oliu s and som e other species of the Rhus family but
P ista cia
-

l en tis cu s is used to a much larger extent than any of the

ci a c or i a r iaand t a ma r ix al l cont a
others P is ta
quanti t ies of tannin though less tha
.

di fferent chemical constitution

,
in considerable
n genui ne sum ch and of a
,
,

a ,

The m ost s a t is fa
.

c t o r y m e t ho d of detecting these ad ul terants

is by microscopic examination none of the chemic a l methods ,

proposed being very satisfactory though as many of the added ,

matters contain catechol t annins while those of sumach are purely

pyro ga
-

l lol d erivatives the method proposed by Hughes for the ,

detection of quebracho in oakwood by the reaction of c o n c en

t ra t ed s ul phu ric acid might render good service and any suma ch ,

infusion which was rendered turbid by bromine water wo ul d at -

least be open to grave suspi ci on .

The most important work on the microscopic structure of the

tissues of sumach and its adulterants was done by An dre a sch ,

when during the later stages of his last ill ness he was obl iged to
winter in Sicily 3
His work will well repay study but u n fo r t u
.
,

1
S oc A r ts ]o u r n 1 901 p 1 4
a aa a ab ail y d
. . . .
, ,

2
A d u l t e r t io n h s g o o d d e l l e ss e n e d , sin c e it h s een e s et ec t e d

b y t h e m ic r o s c o p e
ai ah a
.

3
S icili n s c her Sum c u n d s ein e Ve rf l sc hu ng , Wi e n ,
1 89 8 .
31 0 P RI N C I P L E S OF L EA TH ER MA N UFA C T UR E
n a
t l y does not
e admit of useful abstraction here A very useful .

investigation was also made in the Author s laboratory by Messrs ’

M C Lamb a nd W H H arrison as r egards the treatment and

1

a
. . . .

examination of the leaf cuticles which renders the detection of

mi xture compar tively easy Fo r details the ori gi n a
-

l memoir .
,

must be consulted but if the suspected sumach be gently warmed,

for a few minutes with strong

nitri c acid its more delic a te ,

leaf structure is entirely de

stroyed and after washing and ,

neutralising with sod ium car

bonate the strong cuticles of
a
'

the l e ves of the more common

adulterants s chin ia ( P ista ci a

( C o r iari a
,

l en ti scu s ) stinco
my r tif o li a a a
.
,

) brusca ( T m r ix

a fr ic a na ) and A il a gl a
,

n tu s n

du l o s a
,

are uninju red and easily ,

-

recognised Examination i s .

rendered easier by dyeing the

cuticles safranine adid green ,
’

, ,

Bismarck brown and naphthol ,

yellow bein g suitable for the

purpose Mr Lamb s photo .
’

graphs of the cuticles are r e

produced in figs 5 9 —6 6 but if .
, ,

possible it is most satisfactory

F I G 5 8 —A m ic a n Su m a
,

ch to compare the suspected sample

er

( R i m gl abm l
direct with known specimen s of
s “

the adulterants
R gl a br aSo uthern States U S A ( fig :
a
.

Very largely
’

. .
, ,

used in the St ates to take the place of Sicili n sumach A .

sample collected by the late Professor Trimble and analysed in ,

the Leather Industries Laboratory contained 2 5 per cent of

tannin and produced a leather of very much d a
.
,

,
r ker c o l o u r than

Sicilian but this may be largely due to carelessness in its

,

harvesting
R typ hin a staghorn
.

. or Virginia sumach contains 1 0 to 1 8

. ,

per cent of tannin A sample from same source as above

. .

contained 1 3 per cent .

R col on oides U S A
. Th e analysis of a sample of this material
,
.

1
Su m ah ad t h Mi
c pi D n e c ro s c o c e t e c t io n o f it s A d u l t e r at n s, ]o u r n
ad C l i t Mah 8 9 9 a Lea
.

S oc . Dyer s n o or s s , rc 1 . Cp . l so t he r Che m i s ts
’
P o c ke t
B o o k, p . 20 2 .
31 2 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

gave 2 1 p er cent of tanning matter and leather tanned with it

was a l most equal in c o l o u r to that from R g l a br a
.
,

Other sorts found in States R semia la

ta
. .

( 5 per cent tannin)

'

R a r o ma tic a
. .

( 1 3 per cent tannin) R mel op ium ( 8 per cent )

R cop a ll in aR p umilaR ca na
. .
. .

'

den sis ; R toxicoden dr on is the

'

. . . .
,
”
well known poison ivy a climbing plant which causes a severe
-

and irri tating eruption if touched

R gl a br a and R cop a llin a
.

. .are chiefly recommended for extended

Cultivation I n the U nited States
a
In Virgini t he leaves a
.

re collected and cured by the country _

people and sold and d elivered to owners of mills for grinding

_
'

.
,

Their particul ar obj ect being to secure the largest possibl e quan
tity of product at the lowest cost li ttle attention is given to the ,

qual ity obtained or the manner of colle cting The most in t ell i
‘

gent dealers in the r w materi a a

a
.

l urge upon coll ectors to observe

“

the following particul ars — To ensure maximum va l ue for

tanning purposes the leaf shoul d be taken when ful l of sap
, ,

before it has turned red has begun to wither or has been affected
, ,

by frost Eit her t he leaf bearing stems may be Stripped o ff or

.
-

the entire stalk may be cut away and the leaves Upon it allowed ,

to wither before being carried to the drying shed ; but care must -

be observed that they are neither scorched nor bleache d by the

Sun . Wh en wil ted they are carri ed to a covered place and
, ,

spread upon Open shelving or racks to dry avoiding the deposit ,

in any on e place of a quantity so great as to endang e r the quality

of the product by overheating and fermentation Sumach should
be a l lowed to remain in the dryin g ho use for at le a
.

s t o ne month -

before sending to t he market in case of bad weather a longer ,

period may be required When ready for packing for shipment.

it should be perfectly dry and very brittle otherwise it is likel y ,

to su ffer inj ury in wareho uses from heating and fermentation

B uyers of SII m a
.

ch leaves for grinding depe nd largely upon

’

colour for the determination of the value ; the leaves should ,

therefore when ready for market present a bright green colour

, ,
-
'

which is evidence that they have su ffered neither from rain after
being gathered nor from heating during the process of drying
,
.

Leaves having a mo ul dy odour or appearance are rej ected The .

Virginian crop reaches 7 00 0 to 8000 tons and I s collected at any ,

time between I st J ul y and the appearance of frost

There is an important di fference in the va
.

l ue of the European
and A merican products The proportion of tannic acid in the
latter is genera
.

l ly lower than that found in the f orm e r which ,

is much preferred by tanners and dyers By using Sicilian .

sumach it is possible to make the finest white l eathers while by ,

 VEGE TA B L E TA N N I N G M A TER I A L S 31 3

FI G . 63 .
-
P i st ai al
c e n ti s c u s . FI G . 64 — Rh u s m e t o i u m
p .

FI G 6 5 . .
-
R hu s c or i aia
r . FI G 6 6 5
.
—Ta
ma f r ica
r ix a na .
 P R I N CI P LE S OF LEA THER MA N UFA C T UR E
I

31 4

the employment of the A merican product the leather has a

'
‘

di sagreeable yellow or dark colour apparently due to a colour ,

ing matter which exists in larger quantity in the A meri can

variety than I n the Sicilian .

Experiments upon the presence of colouring matters made

by treating an infusion of sumach with a so l ut io n o f gelati ne
'

gave the following results

Virgi n i a m1 x e d collected in June gave A nearly white pre
a
, , ,

c ip it t e .

A d e c id e dl y yell o w
'

ish white p reci

-

pitate .

A ugu s t A dirt y yellow pre

c ip it a
t e .

A very dirty white -

precipitate .

Fredericksburg mixed ,
A dirty yel low
precipitate .

Sicilian A slightly yellow

ish white pre
c ip it a
t e .

Fo r the purpose of tanning white and del icately coloured

leathers therefore the collection should be made in June while
for tanning dark coloured leathers and for dye in g a
, ,

-
n d calico , f

printing in dark col o urs where the slightly yellow shade will
,

have no injurious e ffect the coll ecti on may be made in July It

appears that for a
.
,

l l purposes the sumach colle cted after the I s t

, ,

o f A ugust is inferior in quality .

Experimental results as regards percentage of tannin obtained

by collecting sumach at di fferent seasons showed

Virginia ,
mixed collected in June gave
, ,

July
R gl a
br a
I :

A ugust
a a
.

R co p lli n

a ia ia
.

SI c Il i n, R
. cor r

It is evident therefore that in order to secure the maximum

, ,

amount of tannic acid the sumach should be collected in July ,

but the colouring matter of the leaves has an import ant influence
upon the value of the product The leaves of the upper ex .

t r e m it ie s of the stalks are always richer in tannic acid than those

 MA N UFA C T UR E
, .

31 6 P R I N C I P L E S OF L E A TH ER

Pistacia 1
pass their as exual stage inside the g a
The ap hid
s ll es

which is large and thin wall ed A similar aphis g a

.
,

l l is found on -
.
-

the A merican sumach A specimen of the leaves examined at

Leeds University yielded only 5 per cent of t a nni n
R s u cceda n ea
. .

. I ndia Leaves said to contain 2 0 per cent . .

tannin .
n

R Mysor en s is
. S I ndia B ark gives pink colour to chromed
. . .

hide powder and is a pyrogallol tannin A nalysis ( Pilgrim dry

, .
,

m aterial) tannin 1 9 5 per cent non tannin 1 1 4 per cent on

,
-

.
,
-
-

dry material
Ma ng if er a in di caMango widely distribu t ed in the Tropics
.

Ba
.
, ,

rk and leaves rich in tannin which gives green blacks with

'

I ron .

COR IA R IACEAE

C o ria
ria my rtif oliaFrench sumach (o f which there are four
a
kinds— f u vis don z er e r edou l or r edon a
,

n d p u di s)
,
A poisono us , , .

shrub of South of France ; leaves used for t anning and as a ,

sumach adul terant under the name of stinc o contain about

1 5 per cent tannin C p
(p
C r u scif olia ba
. . .

. r k the l u l u of Ne w Z ealand contains 1 6 to 1 7

, ,

per cent of tannin

C n ep a l ens is ( Wa l l ) En g India Leaves 20 per cent a
. .

. l l parts , . . .
,

rich in tannin .

Other Coriarias merit examination and are known to contain ,

much tanni n .

R U B IA CEZ E

R u bi aMadder a
,
to G a
l lied l iums which a re a l most the only
, ,

English representatives of the family Th e c o ffee and cincho na .

plants are foreign representatives

Na u cl ea( or Un ca
r ia ga
.

) m bi r E ast I n d ies ( fig A . .

climbing shrub so urce o f gambier o r Terra Japonica

also called Catechu in common with sever a
, ,

l other solid ,

extracts Gambier is first described by the Dutch trader

.

Couperus in 1 7 80 plant introduced in Malacca 1 7 58 planta ,

tions established in Singapore in 1 8 1 9 .

Culture is mainly by Chinamen and is very rude it yi elds ,

'

rapid return but under the tre atment to which it is subj ect ed a
,

plant ation is worn out in ten to fifteen years Cropping com .

m e n c es three years after planting and is continued two to four ,

times annually with little regard to fitness of shrubs the plant ,

1
Se e Fl uc k ig e r
'

ad H ab
n n u r y, Ph amag a
rp hi a co r
'

.
 VE GE TA B L E TA N N I N G M TER I A L S
A 31 7

being cropped till it has barely leaves left to support existence

‘

.
.

It is found advantageous to combine p epper cul ture with that of -

gambier the spent leaves form a good protection f o r the pepper

plant roo t s but they have little actual manurial va l ue
Cropping is done with a knife c a l led a pa
, .

l m rig While a larger

/
,

FI G . . a
6 8 — G m b ie r Sh r u b (Na
u ol e aga
m bi r ) .

knife is used for chopping the leaves and twigs before they are
put in a boiler in which they are heated with water till the liquid
, ,

which is constantly stirred during the operation with a wooden

five pronged stirrer becomes syrupy The leaves are then
a
-
.
, .

brought out with a wooden fork and allowed to drain on a tr y

, ,

so that the liquor runs back into the boiler The coarser matter .

still remaining in the boiler is removed with a strainer like a

racquet and the finer by straining the liquor through a perforated
,

cocoanut shell into smal l shallow tubs Where it is allowed to

-

cool wi th constant stirring with a cylindrical wooden bar which ,

31 8 P RI N C I P L E S OF L EA TH ER A
M A N UF A C T U R E

is worked up and do wn with a rotary motion until the catechin

crystallises When quite cool the pasty mass is turn ed out of
.

the tub cut into cubes with sid es 1 inch long with a hoop iron
”
-

knife and dried on bamboo trays in racks u n der sheds or some

, ,

times smoke dried with wood fires

Good cube gambier is a
-
.

n earthy looking substance and is

dark out side but p a
-
,
,

l e wit hin from cryst allisation of catechin

'

.
,

Catech in is not itself a tanning material but is apparently con ,

verted into a tannin b y dryin g at 1 1 0 to 1 2 6 0 when it parts ‘

f
0 °
,

with a molecule of water It is very probable that a similar .

change occurs in the tannery The tannin is a catechol p hl o ro .

-

gl u co l derivative less astringent than most of t his series and of

, ,

pale colour ( see p .

A commoner quality called block gambier instead of being ,

-

cut into cubes is run into large oblong blocks of about 2 50 lb

, .

weight which are wrappe d in matting and exported in a pasty

condition These cont ain 3 5 to 40 per cent of tannin a
,

s esti
”

mated b y t he hide p o wder m et ho d while the best cubes reach

. .
,

,
.
_

5 0 to 65 p e r rc e n t B esides the forms named various others are

made princip a
.
,

,
lly for native use in chewing with betel nut in -

the form of small biscuits or in thin d_iscs wafer gamb ier ,

by running the pasty mass into bamboos and cutting the cylinder
so formed into thin slices These forms are us ually light in .

colour and very rich in catechin

,
.

Fo r details of the chemistry of gambier see 1 57

Un ca ri a
.

Moluccas Java
U B em a
.
,

y s ii ( F v Ne w Guinea
'

U da s on e m a
. . . .

.
y ( Thwaites ) Ceylon A r e said also to yield
/
. . .

gambier

A P OCYNA CEZ E

C ai a pi a
r ssmm s n and N; I ndia B ush ( Karund ) aC
. . . .

Le aves used in mixture A nalysis ( B rumwell ) tannin 8 0 to .

,
-

1 1 5 per cent
-
non tannins 1 3 5 to 1 5 0 per cent
.
, No t very
- -

easily absorbed by hide Infusion pale in colour and of extreme

A ccording to Fr a
.

swelling power ym o n t h and P ilgrim pro

. .

duces very tough leather

A spi dosp erma m qu e br a Qu ebr a bl a
.

c ho Sp cho n co B razi l
B ark contains a
. . . .
_

sp id o s p e r m in an alkaloid used in medicine but ‘

both bark a
, ,

n d wood are poor in tannin

a
c ho c a a
.

Q u e br l m do see A N ACA R D IA CEZ E p /

3 06 , , . .
3 20 P R I N C I P L E S OF L EA TH ER MA N UF A CT UR E
>

COMB R ETA CEZ E

Several families of this genus cont a

in trees rich in tannin ,

but most important are the Myrobalans ( often but incorrectly , ,

FI G . 69 —
. Myr o b a
la
n Tr e e ( Te r ra li a
iu a Che b u l a
‘

) .

written Myr a b olam s or Myr a b ola n s ) the unripe fruit 0f various

species of In di an Termin a lia

,

Termin a li a Chebu la(fig

.

a tre e 40 to 50 feet high and

.
,

y ielding good timber is the source

,
of all the
_
ordinary varieties ,

which di ffer only in the district from which they are obtained and
the state of maturity of the f ruit The nuts contain from 3 0 to 40
.

per cent of tannin Of t h e various sorts probably those known

. .
,

as Bombays are least unripe while lean greens are the most so
, .

The unripe fruit is the richest in tannin B ombays have a

.

smooth skin in coarse wrinkles and when out are porous and
J s ( ]ub b a o rl a
,

light coloured . l p o re s) and

’
V s ( Vin g s )
’
 VE G E TA B L E TA N NI N G MA TER I A LS 32 1

have finer a n d shallower wri nkles a n d are harder; solider and , ,

consequently darker looking but do not gi ve a darker liquor ; ,

while lean gr eens are greener have less yellow colouring

“

matter and consequently more nearly approach in character

'
,

to sumach which the tanni n in many respects resembles though ’

probably cont a ining more ell a gi t a

, ,

n n ic acid in proportion to
ga ll otannic acid than the latter .

Th e nuts shoul d be bright in colour not worm eaten nor ,

-

waxy or soft If kept in a damp place they rapi dl y absorb

moisture and fa
.

ll into the waxy con dition in which they are ,

ery difficul t to gri nd sticking to and choking the cutters o r

,
-

beaters of the mil l .

Neither the large hard stones nor their kernels contain tannin ,

but the latter have an o il which gi ves a peculiar odour to leather .

The tannin exists in large and rather thickly wall ed cells and is -

not very easily extracted ; the skin is wrinkled but the u n ,

crushed nuts swell up to their original plum like form when

placed in water for some time The bark is a
-

l most as rich as
the fruit and the tree a
.

l so yields galls
T B eler ica
.
,

yi elds B eleri e or B edda nuts which are downy

rounder a n d larg er than or di nary myrob a
.
, ,

l ans and cont ain about ,

1 2 per cent of tannin used as adulterant of ground myrobalans

A sample of solid extract made fro m the bark of T B el cri ca

. .
,

cont a
.

i ned 7 0 per cent of tannin

T t oméu tos a
. .

has down y nuts contai ni ng about 1 0 per cent

of tannin bark stated by de Lo f to cont a
. .
,

i n 3 6 per cent of tannin

a
. .

A sample of soli d extract contained 5 6 per cent of tannin Th e

‘

b rk cont a
. .

i ns about 1 1 per cent

There are severa
.

l other Indian species

T Ca ta pp a B a da
.

. mi e r bark
,
of Mauritius contains 1 2 per ,

cent of tannin
T rri a u r itia u a Ja mro s a bark s a i d to cont a
. .

.
,
i n 3 0 per cent ,
.

of tannin .

T Oliver i Mal ay A rchipelago yields

.
,
Thann leaves from , ,

which an extract is made as a cutch substitute A sample of the .

extract from B urmah examin e d recently in the A uthor s labora ’

tory contained 62 per cent of tannin The tannin is a catechol

derivative differing from that of A ca cia ca
. .

,
techu in containing no
p hl o r o gl u c o l ( p
A sa mple of bark from Manda
.

l ay contained 3 1 per cent of .

tannin while the leaves from the same tree contained 1 4 per cent
T a u ri a ( Kahua )
.
,

. rj . C India B ark gives 1 8 to 24 per cent

. . . .

tannin ( P ilgrim ) Light fawn coloured leather B ark suitable

’

. .

for harness and sole leather tannage Apparently mixed tannin

-
. .

Z I
3 22 . P R I N C I P L E S OF L EA TH ER MA N UFA C T UR E

T br aili i z for tanning

en s s B razil U sed
a(Wright )
. . .

T u cer s B A ntil les U sed for tanni ng

A number of other species of Termin a li a
. . . .

are rich in tannin

La ria
a ra cemo s a( Gartu ) on oc arp u s r a
.

u n cu l ( C c emos u s
g .

West Indies B razil Jamaica West A frica White mangrove

Pa
aa
, , , , ,
”
l e t u vie r gris V ery rich in tannin 1

A n ogei s su s l a t if o l ia ( Dhawa
. .

Dh ur ) C and S I ndia .
, . . . .

B ark and leaves rich in tann in Dhawa twig bark sh ows ( Pilgr im )
'

1 3 5 p er cent tanni s and 1 3 7 per cent non tann i ns the mature

n
' - -

. .

bark 1 5 5 per cent tann ins and 8 8 p er cent non tannins U sed
-

. .
-

in mixture Leaves show ( P ilgrim B rumw ell and others) 1 0 to

.
, ,

1 8 p er cent tannin and 1 2 to 2 3 p e r cent non tannin

. Immature .
-

leaves or shoots ( Dhawa sumach ) yield 2 0 to 3 0 per cent tannin .

and 1 2 to 1 6 per cent non tannin R e d tips of immature shoots .

-

.
,

separately collected in S I ndia showed 54 p er cent tannins and .

, .

1 4 5 per cent
-
non tannins Mixture of bark and leaves tans .
-

quickly giving p ale greenish leather Good bleacher like

, , .

Eur o p ean sumach U sed as a dye Gives little swelli ng . . .

The tree grows like a true mangrove in th e water on marshy

coasts and the borders of large rivers Th e bark is often mixed .

with other rhizophore barks in extracti ng but would give a very ,

superior tanning extract if it could be extracted separately .

R HIZ OP HORA CEZ E, Ma

n gl e s or Ma
n g rov e s

R hiz ophor other aaMagl and

ll ied spe01 es Mangrove or n e,

Ca s ca
l ote grows on tropic a
Magli P a
,

Mangle u er e u v er
,
l t i l coasts , , ,
‘

all round the world The barks vary much in strength from 1 5 .
,

up to 40 per cent in different species ( see C eri op s) Leaves

a
. .
, ,

used in H avana are said to contain 2 2 per cent ; tannin A ccord , .

ing to Eitner the younger pl nts contain the highest proport ion
R Ma
,

of tannin ngl e see m s to yield a bark inferior to several -

. .

other species From their mode of growt h most mangro ve .

barks contain sal t .

All trees growing in swamp and of the same character of ,

growth as mangrove are called B akau in the East In di es

a
,

l i e mangrove ) and various species of C er i op s yield the be st

( g
n c

tanning bark A tida

a
, ,

l mangrove swamp at low water is a tangle

“

of rched roots like inverted branches on which the trees are

supported .

The catechol tannin which i s easily extracted is of deep red -

, ,

colour and al lied to that o f the mimosas In admixture with .

1
N ie r e n s t e i n ad W b t n e s er, Qu a
r t J o u rn o f Co rn R e s e ah rc i n Tr op i c s ,
3 5 ad C ll g
. . .

i p
. .
7 0 ,
v .
p .
, n o e iu m 7,,
1 9 0 8, p . 1 61 .
3 24 P R I N C I P L ES OF L EA TH E R MA N UFA C T UR E

LECYTHIDA CEZ E

C ou ra
tar i do mesti c aor estrell eri sis B razil
C l ega Jigu it ib a
. .

lis B razil rose large forest tree B ark

“

. . .
,

contains tannin
C gu ia Guiana B ark de mahot c o u r a
.

u eu s is
. t o ri ;
. .

for tanni ng
sa p uc a
ra
.

Lecy this pisou is ( Cambes ) B razil used by .

,

natives
Many other species of R hizophora Ceriops and Br u gu ie r a
.

, ,

yield barks containing good percentages of tan nin .

ONA GR A CEZ E , the ( En o t he r aFa

m ily

Fu chsiaexcortica tathe only deciduous tree of Ne w Z eal and , .

Contains 5 per cent tannin

Fu chsi ama cros t emm a Chili
.

Y ields Til c o o r Chilco b rk

Churco bark has b een incorrectly attributed to thi s plant but it
.
.

.
-

a .

is certainly derived from an ox a lis as stated by the Ke w a

,

u t h o ri ,

ties ( Cp Vo n H ohn e l D ie Ger ber iu de p

Lu dwigi aca a a a ar o s s a B razil
. .
.
,

p ross C p B ark 20 to 2 5 per , , .

cent tannin A bundant in Minas Geraes and Goyaz

. .
-
.

G U NNER A CEZ E

Gu n n er b a( P a
aa g sc r n ue P ak
u e, Chili . U sed occasionally
in the tanning of goat skins -
.

MYR TA CFJ E
a
Eu c lyptu s gl o bu lu s and other species of Eu c lyptu s common a
a
, ,

in Austr l ia and introduced into Algeria and Southern Europe

.
,
‘

( gum trees ) are more or l ess rich in catechol tannins their sap
a a
-
-

, ,

being the source of Botany B y or A ustr l i an kinos which contain

a
,

up to 7 9 per cent tanni n Several species of Eu c lyp tus afford

a
a
. .

” ”
stringent extracts ; those from the red whit or flooded e,
t ata ymb a
,

gum ( E ) the blood wood (E

r os r ) d E -
c or os n

it i d abeing quite suitable for replacing the ffi i a

. .
.
, ,

l kind
‘

c r o or ,
o c n .

The gu m is chiefly obtained by woodcutters being found in a ,

viscid state in flattened cavities in the wood and soon becoming ,

inspissated hard and brittle Minor quantities are procured by

,
.

i ncising the bark of living trees a treacly fluid yi elding 3 5 per

cent of solid kino on evaporation is thus obtained The gum
. .
 VE G E TA B L E TA NN IN G MA T ER I A L S 325

is imported from A ustralia but there are no st a tistics to show ,

in what quantit y 1

Eu ca lyptus l ongif oliabark the

.

woolly butt of Australia ;

cont a
-

i ns 8 3 per cent of t annic acid and 2 8 of gal l ic The

peppermint tree cont a
.
, .

i ns 2 0 p er cent of tannic acid in its

bark The stringy bark ( E obliqu a
.

) gi ves 1 3 % per cent of

'

-
. . .

kinotannic acid The Vict orian f iron bark ( E l eu c oxy l o n )

‘

cont a
-
. .

i ns 2 2 per cent of ki notannic acid but is available only .

,

for inferior leather

E Occiden ta Ma
.

lis ll et Flat topp ed Y ate yi elds the

va
-
.
, , ,

l uable mall et bark containing up to 44 per cent of a yellow , .

brown tannin free from the red of the mimosas Tannin 3 9 9

a
.

per cent non tannin 8 1 per cent ( P oll ak C oll 1 7 1 9 1 8 p

U sed a
-

It is most bundant in Western A ustra

-
.
, .
, .
, , , .

li a l one it gives .

a leather somewhat hard and inclined to brittleness but is quite

satisfactory in mixture with milder materi a
, ~

ls
Myr tu s commun is and severa
.

l other myrtle species Contain , ,

a considerable amount of tannin in the b ark and leaves

Eugen ia br a
.

z ili eri si s P araguay B ark stated to con .

tain 43 4 per cent t annin ; leaves dry 1 6 6 per cent wood

-
’

.
, ,
.
, ,

1 1 6 per cent ( St o c kb e r ge r
-

E or Sizygium ja mjol au a I ndia and cultivated in A ntilles

.
,

Fruit ja
. . .

mo o n or Java plum B ark 1 9 per cent tannin . .

( Hooper) .

E michellii
. P araguay B ark 2 8 5 per cent tannin .
-
.

( St ockb er ger )
S terrno l ep s i s gu mmif er
C ledonia Yields resinous aN w . e a .

matter with 80 per cent tannin accordi ng to Heckel and Schlag

d e n ha Thu a
.

u ( 1 9 0 8 ) found 4 2 7 per cent in resin and

’

u ffe n .
,

1 7 4 per cent in bark

-
. .

SA PINDA CFJ E

Mostly climbing shrubs usually rich in saponin and often , ,

containing tannin
Cup a n ia ur a
.

g u e ri s i s P araguay B ark 1 7 5 p e r cent tannin . .

-
.

( St o c kb erger ,

C spec P araguay ce drill o

. . 1 5 8 per cent tannin ( Stock ,
.
-
.

berger)
Pa u l l in ia or cup a u a B razil and Columbia ; fruit
.

s or bil is .

Guara possibly identical with cascalote is very rich in

, ,

tannin ; said to contain up to 5 5 per cent T Call an found .

4 3 to 48 per cent tannin 2 3 per cent non tannins (

. See , .
-
.

1
Co m p a] re ou r u . S oc . Che m I n d . .
,
1 9 02, p . 1 59 .
3 26 P R I N C I P L ES OF L EA TH ER MA N UF A C T UR E

pp 2 41 A ppears to be a m ellow
1
9 5,1 .
,

pyrogallol tannin ; develops acidity in liquors and gives crimson

-

colour with concentrated H z SO4

P mu ltiflor a P araguay
.

. I s also rich in tannin

. . .

R HA MNA CEZ E

Z iz yphu s X yl op yr C India Fruit in a ( Gothar

.
, Gh o u t ) . . .
,

appearance like a small plum contains a hard stone Flesh and

“

a
.
,
\
stone about equal in weight Tannin contained in fruit which
a
.
,

l so yie l d much glutinous or st rchy matter rendering filtration ,

difficult Said to give cracky leather if used in large prop ortion

. .

P enetrates quickly Liquor ferments rap idly and then ac t s as .

a bate Very abundant and Cheap A nalyses ( B rumwell) of

.
‘
.

flesh 2 3 per cent tannin and 4 1 5 per cent non tannins -

C ea ve l u tin a
-
. . .
,

n o thu s s Colorado California Snow B ush

Leaves contain 1 7 per cent of a
-

c a
. .
, ,

t e ch o l tannin and 7 per cent .

-

,
.

of a brittle wax soluble in petroleum spirit 1 91 6 ,

p 3 1 9)
.

G R A NATA CEAE
( P U NI CA CEZ E)
P u n i caGr anatu m P omegranate Rind of fruit used in
An a
. .

Spain and t h e East Substitute for sumach l yses ( B rum . .

well) show 2 7 to 3 0 per cent tannin and 1 8 to 20 per c ent non . .

tannin on dry material B ark of tree said to contain 22 p er cent

of tannin B a la
. .

u s ti n es wild pomegranates E I ndies up to 4 6

.
, , .
,

per cent tannin in fruit . .

R 0 SA GEE

Tormen till a variously

er ect aP ,
o ten till at orm en til l a R oot .
"

stated to contain 20 to 46 per cent tannin R e d coloured leather

a
-
. .
,

formerly used in Orkneys Shetl nd , and Faroe I slands and in , ,

some parts of Germany

S or bu s or Pyru s A u cup a
r iaMountain A sh
.

B ark said to be , .

stronger than oak .

Many other plants of the family co ntain tannin among others '

the strawberry .

PA PILIONA CEE

B u te af ron cto s a.
1
This ( with P ter oc fur ap
r us m a pirsu um ) 2

nishes East Indian kino . The flowers are used in India as a

1
D i c ti o n a
ry of E c o n o mi c P r o d u c ts I B ,
. .
, p .
9 44 ; H u m m el ad Caa
n ll v o,

P r oc Che m S o c 1 89 4 , p ii
a a
. . . .

2
A gr i c u l t L e dg er , . 1 901 , No . 1 1 , G o v e r n m e n t P r in t in g O f fice ,
C lcut t .
328 P R I N C I P L E S OF L EA TH ER MA N UF A C T UR E

somet imes under the name of Algarobill a which is simply a ,

diminutive of Algaroba the carob or locust bean derived from

, ,
-

FI G .
7 o .
—Al g a
r o b il l a( Cws a
lpin i abr e vif o l i a
) .

a
A rabicl Kha baand appl ied to several smal l pods
r ro
(S ee

Ba m a
l a
.
,

s
p and P
oc r pi ) on r oso s

C ( or B a
l a
m a p ) b if liaChili ordinary Algarobilla
.

. s oc r on rev o , ,

( fig
. of the strongest
On e tanning materials known con ,

t aining an average of 45 per cent of a tanni n very like that of .

divi but less prone to discoloration The tannin lies l o o se in a

,
.
'

N w C mme i al D ug a d P l at N o 5 T Ch r is ty
'

1 s n s,
e o rc r n .
, . .
 VE G E TA B L E TA N N I N G MA TER I A L S 32 9

very open skeleton of fibre and is easily so l u b l e in cold water ,

the seeds contain no tannin If not allowed to ferment it pro .

duces a very bright coloured leather -

A lgarobilla has been att ributed to P r o s op is p a llidabut this

.

appears i ncorrect Severa

,

l species of P rosopis are known to yield

tanning pods those o f P S tepha n ia na
.

of the desert of Kaschan

in P ersia are cl schigh dschighe perhaps identic a
.
,

l with dchif t or
a a
, ,

j f t ( S e e p B ark of P sp i c ig e r n se d in P unj ab “

C ( or Hwma toxy l on ) ca mp echia n u m Logwood Centr a

. . . .

. l A merica , . .

I n ad di tion to colouring matter and a glucoside which it yields

on oxidation thi s wood cont a
,

i ns about 3 per cent tannin It s

princip a
.
, .

l use is in dyeing blacks wi th iron or Ch rome mordants .

( Se e p . Trees B astard Logwood occur apparently of ,

the same species but devoid of colou ri ng matter

C tin ctoria Ce velin a or Cel a vin a
.
,

Central A merica
and western South A merica P o d very rich in a
. .

lmost white
pyroga
.

ll ol tannin gives no bloom

C echin a ta
-
.

yields B razil Wood ( S e e p

C Sa pp a
-
. . .

n Sappan wood I ndia

"

Ca ssi a a ta
u r icu l a Tur wa d A va m or Ta ngha
-

ra
. .
, ,

cli bark Southern

U se d for tanning s o c a
, , , ,

India . l led P ersian sheep and goat -

-

skins contains about 1 7 per cent of a catechol tannin Leather .

-
.

tanned with it is of a pal e yell ow Colour but rapidly reddens in

The bark is sm a
.
,

sunlight (cp p . . l l and thin and curls up ,

like cinnamon hence its name cassia It is one of the most

important materi a
.
,

l s of India but somewhat costly as compared ,

to babul
Ca ss ia fistu l a( Amaltas Sonari Ko n n a
.

r i) S I ndia B ark , , . . .

contains up t o 1 4 5 per cent tannin 1 6 0 p er cent n o n tannins-

.
,
-
.
-

( B rumwell ) Gives smooth

,
grained almost white l eather
U sually employed in mixture with t u rwa
-

d or babul H usk of .

pod contains 1 7 per cent o f tannin Pulp of p o d used as an .

-

aperient
C el onga ta and l a ta Senna leaves
n c eo l a
.

U pper Egyp t
C S ophor a B a li ba bil a
. . . .

. n ,
-
.

P el top horiu m du biu m P araguay B ark 3 1 2 per cent tannin . .

-
. .

MIMOSEZ E , aT ib r e of Le g u m in o s a
Ac aiaaa
bi ac r garad
c or ,
B abool ,
B ab ul ,
India ,

Sunt pods Sudan Gambier pods ( fig ,

B ark contains ,
.

about 1 2 to 2 0 per cent of catechol tannin ; o n e of the principal .

-

Indian tanning materials used for kips and heavier leathers ,

.

P ods used in India for bating contain about same amount of

, ,
3 30 P R I N C I P L ES OF L E A TH E R M A N UFA C T UR E

t annin as bark but of a di fferent ki nd that of the bark being a

, ,
-

catechol tannin with a good deal of red colouring matter while

the pods contain a p a
-

, ,

l er t annin allied to divi which is not preci

p it a In Egypt the pods are call ed ba bl a
,

t e d by lime water h a
name which is a
-

l so applied to pods of A cin er a r iaand A ver a

.
,

. .

and others They are used for dye ing glove leathers
.
-

FI G .
7 I .
— Ba
b o o l (A ca
ciaa
ra
bi c a
) .

n i l iti c aEgypt called n eb n eb or ba bl a

h Pods -

ca
. .
,

techu India The wood yields cutch or dark catechu

A lighter coloured variety called ka
. .
,

th containing much crystal ,

l ise d catechin is als o made in India and principally used for

chewing with bete l A ca
, ,

techu is a i ree 3 0 to 40 feet high com

mon in Indi a and Burm a h a nd a l so in tropic a
. .
,

l East A frica where

however it is not utilised In Southern In di a A su ma
, , ,

,
is also .
, .

used for the same purpose .

Trees of about 1 foot di ameter are cut down and the wood ,

( some state the heart wood only ) is re duced to chips

-
and boiled ,
332 P RI N C I P L ES OF L EA TH ER MA N UFA C T UR E

A ustr aabo unds in acaci a

lia s ( mimosas ) many o f which a re ,

used in tanning but vary greatly in strength not only according

to species but probably a
, ,

l so by situation and growt h Probabl y

the best information is to be found in a pamphlet o n Wa
.
,

ttl es
an d Wa ttl e B a
.
i

rk b y J H Maiden published by the

His an a
-
. .
, ,

Depart ment of Public Instruction at Sydney 1 8 9 0 l yses , .

were mad e by the Lowenthal p rocess and can only be roughly

compared with those by the hide p o wder method The an a
,

l yses -

gi ven are by t h e method and mostly on samples ,

furnished by Mr Maiden .

A pecul iarity largely developed in the mimosa family is the

tendency for the true leaves to be suppressed and their place ,

taken by t he flattened and expanded midrib ( phyllode) Thus .

leaves of two very distinct forms are common in the genus and
some acacias as A heter ophyll amay have both forms on the
,

same branch Compare A pycn a n tha

.
, ,

and A decu r ren s

Th e A ustralian mi mosas have been natur a l ised in India a
. . .

nd ,

grow freely In the Nilgiri Hills but t he bark does not appear to ,

be utilised .

Th e most impo rtant species are as foll ows

A pyc n a
. n tha ( fig B road leaved or Golden Wattle
.
-

South Austral ia On e of the strongest tanning barks known

“

speci a
. .

A sample marked l analysed in the Y orkshire College

cont a
a
, ,

i ned 50 per cent of tannin another sample marked

ordi n ry cont a
.

i ned 4o per cent

A l ongif oli athe Golden Wattle of Ne w South Wales only
.

cont a i ns h a lf a s much tannin as A pycn a n tha

.
, ,

A mol lissima a
. .

with its two v rieties A decu rren s ( fig 7 4) and

a
'
’

A dea lba taare among the most import nt of the Wattle family
. . .
,

.
,

commercially Two samples of the former marked

. Green
Wattle showed 3 6 to 3 9 per cent of tanning matter ; another .

sample marked Sydn ey Green Wat tle contained 41 per cent

”
.

A sample of A decur r en s the secon d variety was much weaker

sho wing only 1 2 per cent on an a
.
, , ,

l ysis . .

A p en n in er vi s ( Hickory bark ) 1 5 said to be partic ul arly hardy

.
,

but its strength seems to vary A sample from B ateman 3 ’

Ba
.

y contained 3 8 per cent of tanning matter

A bin erva taanother
. .

Black Wattle contains up to 3 0 per

cent tanning matter as does a
.
, ,

l so the Weeping Willow A

sa lign a Th e latter is poisonous and is said to be used for
.
, ,
'

.
,

kill ing fish .

A p romin en s the bark of which resembles that of the Golden

Wattle A l ongif oliain appearance contains only 1 4 per cent
.
,

. .
, ,

tannin .
 VE G E TA B L E TA NN I N G M A TER I A LS 333

The cultivation of wattles in Australia has been somewhat

neglected b ut woul d render possible the utilisation of many
,

acres of land lying waste or which have already been exh austed ,

and ren dered unfit for the growt h of cereals It requires so .

li ttle attention as to make it very profitable and wattle growing ,

-

and sheep grazing can be combined satisfactor ily after the first
-

year when the young trees in the plant ation have reach ed the
,

FI G 73
— B ro d l e a a d Wa
t tl ve
"

e FIG 74
-
Gr e e n Wa
t tle
aiapy atha
-

ai ad
. . . .

(A c c ) cn n .
(A c c ecu r ren s )

height of feet In Nat al the A ustralian wattles especi a

3 to 4 ll y
molliss imahave been acclimatised and cultivated with
.
,

A .
,

success and large quantities of excellent bark are now exported “

to England A frican wattle barks usuall y cont a

,

. i n about 3 0 per -

cent of tannin
. .

Wattles grow in almost any soil even the poorest but their , ,

growth is most rapid on loose sandy patches o r where the sur , ,

face has been broken for agricul tur al purposes Wh en the soil .

is hard and firm plough furrows sho ul d be made at a regular

,
-

distance of 6 to 8 feet apart and the seeds dropped into these

The seed should be sown in Ma
.
,

y having been pr eviously soaked ,

in hot water a little below boiling temperature in which they

a
, ,

may be allowed to remain for a few hours It should be dropped

'

at an aver ge distance of 1 foot apart along the furrow in which _

,

case about 7 2 0 0 seeds would su ffice for one acre of land Th e .

334 P R I N C I PL E S OF L EA TH ER MA N UF A C T UR E

seed sh ould not be covered with more than about i inch of

soil
On loose s a
.

ndy soil it might even be unnecessary to break'

up the ground in any way the furrows may be dispensed with ,

and the seed sown broadcast after the land has be en harrowed .

A fter the plants have come up they sho ul d be thinned so that ,

they stand 6 to 8 feet apart Wh en the young trees have attained

3
.

the height of 3 to 4 feet the lower branches sho ul d be pruned o ff ,

and every e ffort afterwards made to keep the stem straight and
clear in order to fa cil it a
b

,
t e the stripping and induce an increased ,

yield of bark It is advisable that the black and broad leaved

kinds should be grown separately a
-

s the black watt l e , being ,

of much larger and quicker growt h woul d oppress the slower ,

i broad leaved one Care should be taken to replace

'

g ro vv n g
-

a
.

every tree stripped by r e sowing in order that there shoul d be -

as little v riation in the yield as possible In Victoria the

months of Sept ember to D ecember are those in which the sap
.
,

a
rises without intermission and the bark is charged with tannin
A n lysis proves that the bark from trees growing on limestone
is greatly inferior in tannin to that obt ined from other forma a
.

tions di ffering 1 0 to 2 5 per cent

The following are South A merican mi m
.
,

osas
A ca ven ia Espinillo B ark contains 6 per cent pods 1 8 to “

. .
.
, ,

2 1 per cent or more of tanni n

B ark cont a
. .

A cebil R e d Cebil
.
,
i ns 1 0 to 1 5 per cent leaves
.
,
.
,

6 to 7 per c e nt tannin A rgentine R epublic

A Gu a
. .
.

ren s is Algarobil la of A rgentine R ep ublic B ark pods

and flowers s a
.
.
, , ,

i d to be used for tanning

A tim bo or P ip ta cl en ia B uenos A yres
.

. . .

A cu rupi Cu r u p y bark
.
,
Wichmann fo und 1 8 3 per cent . .

tannin
A a ngico or P ip t a cl en ia ma croca rp a a
.

a
( or r ig i d ) B razil yields
a n gic a
.
, , ,
'

bark a s mple of which contained 2 0 per cent o i

a
.
,

tanning matter when an lysed in the A uthor s laboratory Said ’

to cont a
.

i n 2 0 to 2 5 per cent .

Wh ite B ark South A merica probably an acacia ; bark

internall y very similar to a n gic a if not i dentica
, ,

l
A horr i da D oor n bosch
.
,
”
.
,
Cape of Good Hope bark contains
'

, ,

8 per cent of tannin . .

The follo wing are other leguminous plants containing tannin

I ng a B ark 2 5 8 per cent tannin P araguay -

I ng a a a
. . .

f eu i l l ei P yp y P eru P ods said to contain 1 2 to 1 5

per cent of tannin ( doubtful ) Several other species of I nga

.
,
,
,

. .

known to contai n tannin .

3 36 P R I N C I P L E S OF L EA TH ER M A N UF A C T UR E

LYTH R A CEZ E

Woo df or diafloribu n da ( I tcha Thawai) India B ark and

.
, . .

leaves contain tannin Form er used for sole leather ; gives good
.

colour but cracky grain when used alone Leaves contain 1 5 4

per cent t a
.

n m n and 1 7 2 per cent non tannin ; bark 2 6 6 per

- -
-

, .
,

cent and 1 3 per cent ( B rumwell)

. . .

The followingthe writer has n ot been able to place botanically :

Eu co upiacor dif oli aSantiago Ulmo bark

m king .
, , A considerable
quantity was imported into Germany prob bly for extract
a
,
a
.
 CHAPTER X IX

TH E CH E M I S TR Y OF TH E TA N N I N S

THE essenti a l constituents of tanning materi a l s are members of

a large group of organic compounds known as tannins or
”
tannic acids which are widely di stributed throughout the
,

vegetable kingdom and said to have at least one representative

,

among animals in the body of t he c o rn weevil Their use in

,
~ .
-
.

vegetable physiology is as yet uncertain and indeed they appear ,

in some cases to be waste products of organi c change The

tannins though varying considerably in their chemic a
.

l consti
t ut io n are all marked by the power of p r ec ip it a t in g g e l a
,

t m and
ot her proteins from solution of converting ani m a
,

l skin into
im putrescible leather and of form
,

ing dark coloured compounds

‘

with ferric s a They are a

-

l ts which are often used as in ks

, l so .

precipitated by lead and copper acetates stannous chloride etc

and fo rm insoluble compounds with many organic bases p a
, , .
,

r t ic u

la rl y the a
,

l kaloids such as qu inine and strychnine and with basic ,

aniline colours They have a feebl y acid character Finall y

'

. .

what is perhaps the most important fact must be mentioned ,

namely that they are in aqueous s olution negatively charged

,
“

colloids .

With regard to less characteristic properties it may be said

that tannins are a ll soluble in water but like other coll oids have
no definite solubilities They are a
,

l so soluble in part at least

.
, ,

in alcohol ethyl and amyl acetates aqu eous et her acetone etc
, , , , .
,

but not soluble in the fat solvents including dry ether Since ,
.

tannins are un crystallisable and without definite melting points ,

their preparation in a state of purity is a matter of the greatest

difficulty Indeed gal lotannin is perhaps the o nl y member of
t he cl a
.

s s that has been prepared pure Metho ds used for other .

tannins are very empirical and tedious and their description is

outside the scope of a genera
_ ,

l account
A classification of tannins accor di ng to chemic a
.

l constitution
is di ffic ult sin ce so little is known of them in this respect P erhaps
,
.

the most useful classification is the early one based on the colour
reaction with ferri c s a l ts i e the di vision into the two classes
,
. .

pyrogallol ( iron — blueing) and catechol ( iron greening) tannins It -

.

3 37
338 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

has been found that tannins giving a blue colour with ferric salts
yi eld pyrogallol on dry di stillation or so di um gallate on fusion
with a l kali whilst those giving a green col our yield catechol or
the sodium s a
-

l t of protocat echuic acid These bodies are phenols .

or phenolic acids The ph enols are a class of derivatives of

.

benzene CGH G in which one or more of the hydrogen atoms are

replaced by h ydroxyl — OH) groups Common phenol or c a
,

r .

b o lic acid is t he simp l e st representative :

‘

HO OH
‘

Phe no l . a
C t e c ho l . a
Pyro g l l o l .

Ben z en e .

In the phenolic acids a further hydrogen atom in the ring or

nucleus is replaced by the carboxyl —GOOH) group and th u s
a
_ ,

a true ci d is formed :
'

GOO H

a
S l icyl ic aid c
CO O H
a aid
.

Pro t o c t e c huic c .

Ho w these bodi es are linked together in the tannin molecule is

not known with certainty exc ept in the case of g a ll otannin nor ,

how they are combined With glucose as oft en appears to be the ,

case A G P erkin suggests the subdivision of the pyr ogallol

class into two others namely ga ll o t a
n n in s and ell a git a
. . .

n n in s or
'

better into depside tannins and e ll a git a

, , , ,

,
n n in s Th e last .

named class co ntains an ell agic acid nucleus and yields this acid ,

bloom on fermentation or hydrolysis with mineral acid

This treatment with ga l lot a
.
,

n n in s gives rise to gall ic acid From .

the point of View of leather technology howev er this further “

classification is of little moment as it a

, ,

l most amounts to pro

vi di n g a separate class fOr ga
,

l lotannin
The two classes pyrog a l lol a
.

n d catechol tannins
,
are fairly ,

clearly distingui shable by other reactions B oiling with dilute

sul phuric acid gi ves a precipitate of reds or p hl o b a
.

p h e n es
with catechol tannins The behaviour of t he pyrogall ol group .

has been mentioned above Bromine water added till the solu .

tion smells strongly of it gives a yell ow or brown occasionally ,

3 40 P RI N C I P L ES OF LEA TH ER
’

MA N UF A CT UR E

of Schiff was adopted namely that g a

l lotannin was , ,
m
-
diga
l l ic
acid :
O 0 11 _ _
ou
HO
n
<o: > < “
co o
_

co o n

There were difficul ties however in this view even though p r a ct i

ca ll y a
, , ,

l l of the reactions of tannin co ul d be explained by it In

a
.

the first place the molecul ar weigh t determin tions carried out
,

on t annin though in very poor agreement were without e x c e p

, ,

tion very much higher than that of a digallic acid Secon dl y

tannin is always optic a a
.
,
-

a
l ly ctive there sho ul d be therefore at
le st one asymmetric carbon atom in the molecul e i e a carbon , . .

atom with each of its four bonds attached to different atoms or

groups This is not provided for in Schiff s formul a A nother
.
’
.

difficul ty was that glucose was summarily rul ed out as a con

s t it u e n t of the molecule The subsequent work of Fischer and
a
.

a
his coll aborators has led to a much more s atisfactory formul
At the outset they a
.

do p t e d method of purification previously

'
'

used b y P erki n and St ia sn y whi ch implied a disbelief in the

presence of a carboxyl group This method was to neutralise .

a
a tannin solution to litmus with di lut e alkal i and extract the
t nnin with a solvent T his was to leave behind ga
.

l lic acid
as so dium salt but woul d obviously do the s a
.

m e with any
di ga
,

l lic acid present Phenols other than phenolic acids would

n ot b e neutr a
.
, ,

l is ed under the circum stances Tannin thus purified .

was found to yield 7 to 8 per cent of glucos e on hydrolysis . .

The details of Fischer s subsequent work are too c omplex for

’

description here He had however before 1 9 1 3 brought

.
, , ,

forward the strongest evidence that gallotannin was an ester of

one molecule of glucose and five molecules of diga l lic acid i e
diga
. .
,

penta— l l o yl glucose
-

‘ Hz O R
j OH HO OH
‘

c rro n ) 4
( whe re R = — OC C
< :> 0
0H ( > OH

CH O

The synth e sis of this body in the laboratory was hindered by

many difficulties but fin a l ly Fischer prepared a substance
,

identical with the tannin of Chinese gal ls save i n one respect ,

the specific optical rotation in aqueous solution In organi c .

solvents the optical activity presents no difficulty There can be .

no reasonable doubt that Fischer has produced at least an

isomer of natural tannin Dr Freudenberg who was associated .
,
 TH E C H EMI S TR Y OF TH E TA NN I N S 341

with Fischer in much of this work is continuing investigations

on tannins particularly chebulinic acid from myrob a
,

l ans and
ha ma m el i tannin from H a ma melis virgin ia
n a This latter body
,

is exceptio nal in being cryst a

.

l line .

It has been mentioned above that solutions of pyrogallol

tannins deposit bloom on standing This is particul arly the .

case with valonia divi di vi and myrobalans A similar preci

pitate is obtained on boiling with dilute acid especi a
-
.
, ,

l ly in the ,

presence of an oxidising agent such as hydrogen peroxide .

Bloom is ellagic acid and has been shown to have the con
,

st it u t io n

O— OC

Po ssiblythe ellagic acid is formed as fol lows hydrolysis of t he

tannin either by fermentation or the action of acid results in the
formation of ga
, ,

l lic acid ; two molecul es of gallic acid then unite

‘

partly by oxidation a nd p ar t l y by loss of w

,

ater to form ellagic ,

acid :
co o n H0 011 0 0 —0

< 231O <

"
1 10 +0 0 11 HO
_

HO OH H O C H
O

To understand the above it m ust be remembered that at the

corn ers of the hexagon r ep r e se n t ifig b en z en e a E CH group is ‘

al ways pr esent except when a substitutin g group has been intro

duced such a group replaces the H of the E CH group Two .
.

hydrogen atoms have been written in the left hand side of the -

equation to in di cate where the oxidation takes place .

Numerous methods have been devised for the synthesis of

ellagic acid but they can all be represented by the equation given
, ,

since they only di ffer with regard to the particular oxidising agent
used Lowe oxidised gallic acid with arsenic acid Ernst and
.
,

Z we n ge r boiled ethyl gallate with sodium carbonate solutio n in

presence of a i r Gr ie ss m a
yer oxidi sed with water and iodine ;
,

the best methods are those of Perkin in which potassium per ,

sulphate and acid are used and of Rupe in which acid and sodium
.
, ,

nitrite are used .

P repared synthetically or otherwise ell agic acid is a more or

less yellow sandy or cryst a
,

,
l line substance of remarkable stability
, .

It does not melt below 3 60 C but sublimes with co n siderable

°
.
,

decomposition at higher t emperatures It s al most complete in .

3 42 P RI N C I P L ES OF LEA TH ER
‘

M A N UF A C T UR E

solubili ty in the usu a l organic solvents Wa s a great obstacle to its

purification until Perkin found that it dissolved easily in pyridi ne ,

from which it could be crystal lised in prismatic nee dl es These

cryst a l s cont a
.

i n pyridine which may be removed by washing

with a l cohol a
,

n d drying at 1 60 C Ellagic acid may perhaps °

.

di ssolve in other basic liqui ds such as quinoline or solutions of

urea Solutions of ell agic acid in a l kali are yell ow and give a
cryst a l line precipitate when di luted with hot a
. -

l cohol and aci di fied

Th e most im p o rt a n t c o l o u r t est for ella ic acid is Gries sm a
.

g ye r s
test carried out by adding ni tric acid containing nitrous acid and
,

subsequently dil uting A blood red coloration is given once

.
-

thought characteristic of ell agic acid b ut shown by P erkin to be

al so given by an a l lie d substance fla vell a
,

gic acid which contains

a
, ,

five hydr o xyl groups

Leather tanned with b loom yiel i ng materi a l s n tura l ly cont a
.

i ns
d
-

el lagic acid the presence of Which I s often desir ed as it gi ves some

, ,

weight and solidity to the product In order to extract it the

”

leather sho ul d be thoroughl y freed from fats and water soluble

matter in the usu a
-

l way th e residue then well dried and fin al ly

“

, ,

extracted with hot pyr idine Ell agic acid so obtained was found
by Nierenstein to be identic a l with the synthetic a
.

l product .

Most solutions of catechol tannins are decomposed by long

boiling particul arly with acids or by heating under pressure
, , .

A reddi sh precipitate is obtained totally different from bloom

and t o which t he name of p hl o b a or reds is usu a
,

p hen e s l ly
given These p hl o b a
.
p h e n es appear to be present to some extent
ready formed in the solutions capable of yiel di ng them If ,
.

alcoholic or very concentrated aqueous t annin extracts are

a
poured into cold water a red precipitate is sometimes formed
Which wil l not redi ssolve Phl o b a p h e n es appe r to be produc e d
.

from the catechol tannins by condensation of molecul es through

an h ydris a t io n or oxidation or bot h Nothing exact can how
,
.
,

ever be said o u this point since t he constitutions of cat ech ol

tannins and p hl o b a
, ,

p he n es are ali ke unknown Alcohol dilute

alk al ies sulphites and borax di ssolve p hl o b a
.
,

have been made on th ese li nes to render p hl o b a

p h e n e s and attempts
p hen es ava a
.
, , ,

i l ble
for t anning On e of t he most successful of these efforts has been
.

the sul p hit in g process of Lep et it D ollfus and Gausser who heat
with bisul phite under pressure Some p hl o b a p he n es a
, , ,

. re in
soluble in water even at boiling temperatures though they ,

dissolve to some extent in the presence of sugars tannins etc

This is probably a case of the well known colloida
.
, ,

l phenomenon -

of peptisatio n Other p hl o b a .
p h e n es are more soluble in water ,

probably because they are more hydrated Such substances are .

3 44 P RI N C I P L E S OF L EA TH ER MA N UF A C T UR E

a
Ne r do l N and Ne r dol ND a
are similar products prepared from
a
naphth l ene sulphonic acid s Or d o va
l G is prepared from higher
‘

hydrocarbons princip a ,
l ly retene Al l these bodies must be .

neutralised to a suitable degree with alkali before they are ready

fo r use
Ne r a
.

d o l D is a substance of brown colour similar in appear

anc e to o rdinary tanning extracts and has a c haracteristic smell ,

of phenol It is c ompletely soluble in water and the organic part

but not the sodium sal ts produced by n e ut r a l is a
,
.
,

t io n in alcohol and ,

in ether The ordinary fat solvents with the exception of ether

.
“

, ,

exert no solvent action The aqueous solution is usually acid to

methyl orange a accordi ng to Gr a
.

'

n d gi ves ,
sse r t h e following
, ,
.

reaction s : with barium chloride a white precipitat e insoluble in , .

nitric acid a deep blue colour with fe rr1 c salts no precipitate

‘

with bromine or with formaldehyde and hydrochloric acid

,

complete precipitation with gelatin a di stinct precipitate with

a
aniline n d hydrochloric acid It s b ehavi our 1 5 thus very much .

like that of a pyrogallol tanni n It wil l be noticed that it b ehaves

a
.

with reg rd to aniline in the same way as sulphite cellulose

'

Ner a
' -

extract d o l D in acid aqueous solution is electricall y

negatively charge d The practical use of Ner a
.

,
do l D cannot be
described here but attention may be drawn t o it s power of
solubilising p hl o b a
,

p h en e s and its probably consequent property

,

of lightening the colour of leather tanned with quebrach o and

similar materials
‘

The react ions of Ner a do l N and Or do va

.

l G are summarised in
the following tabl e due to Grasser : ,

a
Ne r do l N . Or d o v l aG .

Gelatin somewhat sol Moderate pptn in

Pp t .
,
.

ubl e in excess of fine flocks .

tannin .

Ferric chloride No colour Slight darkening . .

B arium chloride White ppt insol Turbidity .

,
.

uble in H NO3
B romin e water No reaction N0 reaction .

Silver nitrate No reaction Opalescence . .

A niline and HCl Pp t soluble on B rownish black

.
,
-

heating ppt . .

Formaldehyde and
H Cl No . ppt .

The failure of the iron reaction is probably due to the absence of

hydroxyl groups .
 CHA PTER XX
TH E SA M P L I N G A N D A N A L Y S I S OF TA N N I N G M A TE R I A L S

ALTHOUG H the an al ysis of tann i ng materials fal ls more properly

within the scope of a book for ch emists than one intended
primarily for tanners a n d though it has been treated at con

b l e length in the Lea

sid e r a bor a
ther I n du str ies La
.
,

tory B oo k and
more recently in Lea
,

ther C hemists P o cket B o o le a slight sketch

’
1
, ,

must now be given of the methods in general use since it is of ,

great importance that at least the principles on which they are

based sho ul d be un d erstood by a l l to whom they are of pract ical
interest but the method h a s become too complex and detailed
“

to be within the scope of the ordinary tanner ; and those who

wish t o pursu e it will find full details in the books quoted and in ,

the Journals of t he respective A ssociations of which it is open ,

to anyone to become an A ssociat e who is interested .

It must specially be insisted on that absolute adherence in ,

every detail to the methods given is essential to obt aining con

cordant results and little points of manipulation which appear
,

in themselves unimportant are frequently the result of long

experience and careful discussion The members of t he Society
of Le a
.

ther Trades Chemists especially are bound by their rules

’

to make note in their an a l yt ical reports of any deviation however ,

small from the prescribed process

The first step i n the a
.
,

nalysis of any material is to draw a

sample trul y representing the bulk which usually depends on

a
,

the tanner himself or his agent and which is often by no means

,

easy while f ilure to accomplish it is probably the cause of more

,

errors and di sputes than any inaccuracy of the method of analysis

itself In very many cases chemists are blamed for discrepancies
.

which really exist in the samples supplied to them and they ,

can o nl y hold themselves responsible for the accuracy of their

an a l yses when t h e sampling has been done strictly accor di ng to
the rul es prescribed by their A ssociations On this account a ll .
,

important samples sho ul d be drawn in the presence of a principal

or some other responsible person
I n liqu id extr a
.

ct s the thorough m ix m g of the liquid is of the

,

greatest importance Most extracts contain a portion of diffi

“

1
E . F N Sp o n ,
. . 1 9 1 9 .

34 5
3 46 P RI N C I P L E S OF L EA TH ER MA N UFA C T UR E

soluble tanni ns ( see p

c ul t l y which slowly settle to the .

bottom or adh ere to the sides of the cask from which such
"

e xpedients as merely rolli ng a full cask are quite inefficient to

dislodge them In fact nothing but taking the heads out of a
su fficient number of cas ks and actu a
.

l ly stir ring them with a ,

suitable p lunger which should be specially applied to the sides

,

and bott om or empty ing the entire contents of the casks into a “ ”

tank i n which the whole can be adequately mixed is really ,

FI G 75
— Ka
t hr e in e r
’
s a
S m p l in g To o l s A s t r o n g c r o ss h n dl e ; B g u a ad r ~

a a a
-

a
. . .
, ,

t u b é sh r p e n e d t C D , b r s s o r Wo o d e n p l u n g er
’
CC
'

’
d is c , br ss .

thoroughly reliable though at times it is necessary to be content

,

with less satisfactory methods In any case w hen it is probabl e .

,

that samples must b e submitted to more than one chemi st the ,

whole shoul d be drawn at once thoroughl y mixed and divided , ,

and sealed in separate bottles and in dividing a sample the ,

same care must be taken to ensure complete mixture as in

drawing the origin a l sample
n d pa
S ol i d a cts s u c h a
s ty ex tr a
.

s quebracho cutch and gambier

are still more di fficult to sample fairly as the outside is a

, , , ,

l most
invariably much drier than the interi or Genera
,

ll y the only .

way is to select such portions as are thought fairly to represent

the bul k to chop them into moderatel y smal l pieces mix and
, ,

seal in an air tight tin leaving it to the chemist to draw from

-

,
3 48 P R I N C I P L E S OF L EA TH ER MA N U FA C T UR E

describes more than eighty but of these only two have kept their
,

place as of pract ical value— the hide powder method for all
commerci a
-

l analyses and the Lowenthal volumetric method for

,

some purposes of tannery control The earliest attempt at

‘

quantitative analysis of t anning materials see ms to have been

made by Biggin in 1 80 0 and improved by D avy i n 1 80 3 or 1 80 4
,
.

Th e tanning infusion was precipitated with gelatin and the ,

FI G 6 — K e n ri ck
’
D r u g m ill
7 s -
. . .

precipitate dried and weighed after more or less washing and the
t annin re ckoned as h a
,

l f the w ei ght of the precipitate Com .

- z

p l e t e washing was di ffi cult or impossible and it was found that ,

di fferent prop ortions of t annin were carried down in the preci

’

pitate by di fferent concentrations of the solutions Almost

innumerable met a
.

l lic salts will precipitate tannin especially

those of the heavy met a
,

l s and many methods have been founded

,

a
on this fact but the precipit ates are of inconstant composition
and as the tannins are a cl ss di ffering rather widely in chemical
constitution and not a single chemic a
,

l individual as was at one

,

, ,

time supposed it foll ows that even if an actual tannin salt could
'

b e obt a
a
-

i ned it would be of di fferent proportions for di fferent

tannins In fact sever a
,

l of the methods with met l lic salts will

a
.

give fair results if only one species of tannin is to be determined .

A more serious trouble perhaps is that all n tural tanning materials

 A N A L YSI S OF TA NN I N G M A TE R I A L S 349

contain not merely the tannins themselves but their phenolic

derivatives such as ga
,

l lic acid which are incapable of tanning

but which are mostly precipitated b y the metallic s a
, , ,

l ts Th e _
.

a
necessity therefore arises of removing these bo di es by a separate
oper tion which is not generally possible
,
.

M1 1 ch more useful and rapid methods are those dependent on

the oxidation of the t annin by a volumetric solution of potassium
permanganate or so me other oxi di sing agent an d the best of
these stil l se ems to be the original Lowenth a
,

l method invented
in 1 860 and subsequently improved by Lowenth a
,
l and others .

This depends on the oxidation of the tannin in very weak solution

in presence of a known quantity of sulphindigotic acid till the
deep blue of the solution is changed to a clear yellow The .

sulphin di gotic acid serves not only as an indicator but as a ,

regulator of the oxidati on o nl y those substances being attacked

,

which are more readily oxidisable than the indigo itself A s

however these include ga lli c a
.
,

c id and other phenolic derivatives

‘

generally present it is necessary t o r e m o ve the tannin by hide

a
'

powder or by precipitation with gelatin a

,
.

,
nd make second ,

a
determination of the r emaining
obt in the permanganate va
non tannins and thus -

l ue of the tannin by di fference

-

that of the indigo being deducted in each case Th e process .

sounds complicated but where a number of determinations are

, .

to be made it is the quickest known as each titration onl y takes

a few minutes and the end point is quite sharp while the remova
,

a
,
-
l ,

of the tannin especially with gelatin solution in presence of

,

salt and sulphuric acid is also very rapid It has the ad v an t age
,
.
-

that it can be done in extremely dilute solution and is thus

especiall y adapted to the control of weak liquors but like a
-

ll .
,

other purely chemical methods it gives di fferent results with ,

di fferent t annins The permanganate value of the di fferent

.
-

tannins may be determined by comparison with the hide powder -

gravimet ric process and the permanganate solution is now

genera
,

l ly standardised by a comparison with a solution of pure

ga l lic acid under the Same conditions as the tannin test but the
chief use of the method is for the relative determination of a
series of liquors made from the same materi a
.

l s as in the control ,

of suspender liquors or of the e xhaustion of spent tanning

materi a
,

ls Ful l details of the precautions required in its e x e cu

tion may be obtained from the text books a
.

l ready named and if -

the st andard solutions are provided it s houl d not be beyond the ,

ability of an intell igent foreman to carr y out the actual deter

min a t io n s for the purposes j ust suggested .

The hide powder gravimetric process is of a quite di fferent

-
3 50 P RI N C I P L ES OF L EA TH ER MA N UFA C T UR E
character and is really of the nature of a miniature tannage
,

carri e d out on a laboratory scale and in a very limited time It .

is therefore applicable to all tannins and determi nes the actual ,

quantity of matter present which is absorbable by hide but of ,

course does not give the relative value as affected by colour or

b y the qu a l ity of the leather produced B eing an empiric a l .

process it is necessary to carry out the experiments with absolut e

,
-

uniformity to ensure comparable resul ts and though it has now ,

been perfected so that very concordant resul ts are obtained

there are still severa
,

l sources of error which have not been c om

p l e t e l y eli minated On e of which is the di fference of absorptive
,

power of di fferent batches of hide powder e ven when the

greatest care is taken to ensure auniform product Fo r t hi s
-

reason the powder of a single maker is employed by a

_ .

ll the
chemists of the Society and no batch is all owed t o come into
use till it has been practica
,

ll y tested and passed by a committe e

appointed for the purpo se .

The princi p le of the method is that a weak solution is made

from a kno wn weight of the t anning material in a gi ven volume
,

of water and after fil tration the dissolved matter it c ontains is

‘

, , ,

determined by evaporating 50 c c of it to dryness and weighing . .

in a tared basin A s this includes all soluble matters present it

.
,

is necessary to remove the t annin from a portion of the solution

by shaking with a known weight of a carefull y wa s hed a
n d lightly

chromed hide powder which can be proved to give no appreciable

-

soluble matter when shaken with pure water and to determine ,

the non tannins by evaporation of a second 50 c c under

-
. .

similar con di tions The moist ure in the original sample is

.

now determined by drying a weighed portion ( generally at

C in va or a
_

cu o) l ternativel y in the case of extracts the

°
1 00

tot a
. , , ,

l solid matter by evaporating 50 c c of the well mixe d

and from these da ta
-
. .
,

unfilter ed solution the following resul ts are

obtained by c a l culation

Tanning matters absorbed by hide ( = tot a l soluble less

non tanni ns -

No n tannins -

( y
b di rect weigh ing of the dried d e t a
n n is e d
solution )
Moisture ( by loss on drying the origi n a
.

l substance or by ,

deduction of total solids from total weight used or from ,

1 00 per

Insolubles ( by deduction of the above from 1 00 per

It is curi ous that the greatest discrepancies between different
analysts have often occurred in those points which seem most
 PR I N C I P L ES OF L EA TH ER MA N U FA C T U R E

during which it has been cooling and it is almost i mpossible for ,

two chemists to obtain identical resul ts while solutions which

‘

are transparent to trans mitted light may contain 1 0 p er cent of .

ma t ter which may be removed by closer fil tration It was .

hoped that these di fficulties woul d be largely overcome by the

use of the B erkefeld can dl e fil t e r which consists of a hollow
‘

cylinder of finely divided silica cemented by some adhesive ,

and through which the liquid is forced b y atmospheric pressure .

This did not by any means wholly overcome the difficul ty and
"

during the war it W a

,

s impossible to o btain candles _ of

the same cons tant texture and recourse had again to b e made ,

to fil t er paper with the assistance of powdered kaolin This

a
'
-
.

introduces a fresh difficulty since some paper its elf bsorbs a ,

small amount of tannin which mus t be allowed for It is n ow

stated that satisfact ory can dl es can b e obt a R ea
.
,

i ned l ly
a
“

insoluble m t ter such a a

.

s s wdust and fragments of vegetabl e

,

tissue are rare in wel l manufactured extracts and are easily

,
-

removed while the so cal led insolubles are mo stly completely

,
-

soluble at a higher temperature or b y the addi tion of a little

ether and it has been suggested that a fil tration should take
,

place under these con di tions when in most cases no insoluble ,

would be reported As however many ext racts are rendered

.
, ,

wholly soluble by additions of bisulphite and in other ways it is

a
,

necessary that these should be distinguished though perh ps a ,

measurement or statement of the turbi di ty at l aboratory tem

p e rat u r e might be su fficient Clear soluble extract s are largely
a
-
.

used for ble ching purposes but as tanning agent s they give ,

porous and light weighing leat her while the difficul t l y soluble
-

tannins greatly contribute to weight and soli di ty .

a
Al though for many purposes the colo ur of leather is quite un
important light colour has become a f shion with a money va
,
l ue
and where leather is to be dyed a clear shade it is essential ,
.

Th e e ffect of a tanning material in this respect is best determined

by t anning small pieces of prepared calf or sheep Skin for a -

determined time in a solution of determined strength Details .

of the execution of such experiments are gi ven in the laboratory

text books They do not however give n umerica
-
. l results which
, ,

can be inserted in a contract and neither samples of ext ract

nor of leather can be kept unchanged for a length of tim e so ,

that a direct optical measurement of the colour of the solution

’

which will give defin ite figures has become very customary as , ,

although the colour of the liquid bears no very definite relation

to that of the leather which will be produced it serves as a mode
of comparison of the bulk delivered with the origin a
,

l sample on
 A N A L YSI S TA N N I N G M A TER I A L S
"

OF 3 53

which it was bought Th e method usually adopt ed is to com

pare the colo ur of t h e fil tered analyt ic a l solution in a h a
.

"

l f inch
( now 1 cm ) gl a
-

.ss sided c ell with that of the graded glasses of the

-

Lo vib o n d tintometer t il l a match is obtained A s the anal ytical .

solution varies somewhat in strength of tannin the result is ,

usually calculated to that which should be given by a solution

containing 0 5 per cent of tanning matter as sho wn by the
-

an a
.

l ysi s. This method is i mperfect in many respects since the ,

colour of the glasses though visually the same as that of the

,

liquor is really di fferently constituted as will be seen at once

, ,

on comparing the two by a spectroscope Whi le the spectrum

'

of the liquid shows a regul ar gr adation from the blue end of

the spectrum which is most absorbed to the red that of the
, , ,

g lasses is irregul arly banded especially in the green which is

speci a
, ,

l ly absorbed by the red glass If the two colours were

really identic a l their match would not be affected by the qu a
.

,
l ity
of the light which would influence both in the same way A s it
,
.

is however if both be looked at through a colo ured glass they

will u sually cease to match a
, ,

n d s imilarly on a clear day with a

,

blue sky the match will not be the same as on a dull day o r
'

with a yellow fog or by artifici a

,
.

l light,
I t was found that even .

using the ident ical set of Lo vib o n d glasses a di fferent match

was required in Londo n to that obtained under the clearer sky
of P aris Fo r the same reas o n a double thickness or strength
.

a
of the liquid is not matched by doubling the glasses and the ,

c l culation from the approximately 0 4 per Cent analytical .

solution does not give the same result as one obtained direct
from a O 5 per cent solution speci a
f
l ly made after the analysis is
.

completed A furth er di fficulty arises from the fact that the

. .

colour of soluti ons usually darkens on stan di ng A ttempts have .

been made to get over the di fferences in daylight by the use of

artificial light either of the Welsbach burner or from a tungsten
,

or Nernst electric light b ut besides the di fficulty of keeping these

lights re a
,

l ly co nstant there is the still more formidable one that

,

the Lo vib o n d glasses do not seem al ways to agree perfect ly in

di fferent sets a l though the greatest care is certainly taken to
,

make them accurate

It is d e sir ab l e t ha
.

t some method sho u ld be found either to

measure direct by the colours of the prismatic spectrum or to ,

refer to those of chemical solutions which could at any time be

accurately reproduced in the laboratory but neither is easy , ,

and it is di fficult to find a mode of st atement which wo ul d be at

the s a me time accurate and definite and convey to t anners any ,
.

clear idea of the act ual colour Fo r the first purpose it is difficult .

23
3 54 P R I N C I P L E S OF L EA TH ER M A N UFA C TUR E -

to find three colour solutions suitable and at the same time ‘

sufficiently pe rmanent and for the second in ad di tion to the

, ,

difficulty of intell igible statement costly and very accurate ,

apparatus wo ul d necessarily be required A special difficulty is

to find a red solution re a
.

ll y permanent to light Coal tar colours

are a
-

l most impossibl e to obtain of the req u isite purity and usu a

.

l ly
fade o r cha an d even cob a
,

l t chloride becomes brown on

‘

n ge , , _

con t inued exposure to light Th e writer has already spent

'

m uch time on research to overcome these di fficulties and with

considerable success a
.

n d hopes to publish detai l s shortly .

It is complicated by the fact that the colours obtaine d (

by s uperposing glasses are complementary to those gi ven by

direct mixture of the light o f correspon d ing colour A b n e y s
-
’

small book on C ol ou r Mea

.

su r emen t or the more r e cent one of 1

,

Lu c kiesh o n the same subj ect may be referred t o for further

2 -

information .

a al
a
1
Ke g n P u Tr e n c h Tr u b n e r Co ( Out p r in t
of )
ad i t a
. .
, ,

2
Lu c kie sh Co l o u r
, n s A pp l ic ti o n s . Co n s t b l e .
3 56 P RI N C I P L ES OF L EA TH ER MA N UFA C T UR E

solution of about 4 lb per 1 00 gallons in which the butts are

. .
,
.

kept in motion are among the safest and most satisfactory Ways
,

of removing surfac e lime and improving the colour b u t even the

-

stronger mineral acids may be used successfully with caution

( see Chapter Dilute solutio n of sulphurous acid made ,

by burning brimstone ( p is also very satisfactory . .

A cids should n e ve r be used of s u ch s t r e n gt h as to materially

swell the butts and the great advantage of the weak acids is
'

that from their l o w ionisation th ey can be used more freely while

stro ng acids must be added in very small a
,

n d repeated doses .

Fo r further partic ul ars see Chap ter X I V .

If hides befor e bringi ng into t h e liquo rs are exposed either to

, ,

t he carbonic acid of the air or that of temporary hard water

a precipitate of lime carbonate is formed in the skin which is '

much more difficult than free lime to remove in a

_

cid deliming
A point of great import a
,

nce is to keep the goods from the time of

unhairing till they go into the liquors under water in which ther e
‘

is always a trace of caustic lime or which at any rat e are free ,

fro m carbonic acid In deliming sole leather with acids it is

-
.

best to give the full dose of acid required at once ; and not gradu e

ally so that it may act most powerful ly on the exterior and

,
“

remove any carbonates p resent b efore it penetrates to and ,

becomes neutralised by the excess of lime In the i nteri or This .

is exactly the reverse of what is advisable with dressing leather ,

where the obj ect of t he tanner is to rem ove lime as uniformly

and completely as possible without excessive acidity o i any part ,
-
.

Of course hides sho ul d not even in the case o i sole leather be ,

-

aa
,

allowed to go into the liquors while any acid swelling of the ' “

surface remains but this will soon dis ppe r if the goods are
,
‘ l

suspended for a ti me in cold water after deliming unless excess

”

of acid has been used ( cp p 2 0 3 et s eq) . . .

Whether acid be us ed or not t he butts are nowusually sus

pended in deep pit s containing o l d a
,

n d nearly exh austed ta ri

liquors These liquors contain a certain amount of lactic and

.

acetic acids derived by fermentation from the sugary matters of

,

the tanni ng materials and also in some cases weak acids origi
na lly present in the mat eri a
, , ,

ls themselves The presence of .

th ese acids is most important to successful tannage and their

'

e ffect is twofold : in t he first p l a

,

c e t h e y n eutralise and remove

~

any lime which still remains in the butts and secondly

'

, ,

they bring the butt into a slightly acid condition which is ,

n ecessary to tannage and in which it remains plump and swollen

,

in the liqu ors while the tannin graduall y penetrates and tans
,

the fibre If as frequently happens especially in modern yards

.
, ,
 VE G E TA B L E TA NN I N G P R OC E S S E S 3 57

where ext racts are very largely used the natural acid of the ,

liquors is not su fficient for this purpose the lime combines with ,

the tanning matters and the butts eit he r b e c o m e di scoloured at,

‘

once o r darken by exposure and oxidation ; when they come to

,

be dried while the pelt remains flat and insufficiently swollen

,
. .

To avoid t his t r o u b l e resort is sometimes had to artificial acidi

fic a A s a gener a
,

t io n of the liquors l rule it may be stated that .

,

it does not answer to mix the stronger mineral acids directly

with the liquors but lactic and acetic acids may be used or even
oxa
a
, ,

l ic acid may be added to the suspenders in such quantities

as to precipitate n d remove the lime which they contain setting ,

free the organic acids with which it had been combined The .

use of oxalic acid should never be pushed further than this as it

a
,

has a most powerful swelling action on the hide and goods ,

which are too much swollen by cids tan dark and brittle The
acidity of such liquors is usu a
.

l l y determined by Procter s lime

’

water test i e the volume of saturated lime water which can be

,
1
. .
-

'

added ( with constant stirring) to 1 0 c c o i the clear filtered “

. .

liquor without producing a permanent cloudiness This test

"

does n o t with any accuracy indicate the swelling power of

the liquo r which depends mainly on its hydrion concentration
,

(p and is much influenced by t he presence of neutral

sa
.

l ts but it does directly give the amount of lime which

,

can be safely carried into the liquor without the risk of pro
du c in g stains Many of the acids p resent in the liquors though
.
,

too weak to cause swelling are still capable of dissolving ,

lime If lime be present beyond this point it does n o t necessarily

.
,

a
produc e immediate stains which are due to the oxidation of the ,

tannin s lts formed by exposure to the air and if this be avoided , ,

the lime may ultimately be got rid of in the more forward liquors
and the hides may remain of good colour a n d this was usu a
,

. l ly .

what was aimed at before acid deliming was introduced The

greatest danger of stains arises when the hides a
-
.

r e allowed to

touch each other in the suspenders In this case whit e patches .

are at firs t formed where the tan liqu ors have not access and -

these may ultimately colour properly when the hides are moved ,

but their edges where there is a lit t le tan and a great excess
,

of lime usually oxi di se and remain as permanently dark map

, ,

like outlines Fo r this reason it is most important that the hides

.

should be freely moved for the first few hours after coming into
the liquors either by hand or by suspending them to a m e c ha
,
ni ,

1
B e fo r e ap p l yi g t h i t
n s e st a aa
t o l iqu o r s c o n t in in g o x l t e s , it is n e c e s s r y a
to re m o ve th e ali a
ox id c c b y t he a
d d it io n o f a
k n o wn v o l u m e o f c l c iu m a
c h l o r i d e s o l u t io n b e fo r e fil t r a
ti on .
3 58 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E
.

call y moved frame If the butts are hung on sticks these may be.
,

all owed to rest on bearers of about 2 inch by 3 inch section at the

sides of the pits with occasion a
- -

l crossbars to keep them parallel

, ,

and are either su sp e n de d b y iron rods from beams above or sup '

port ed on ro ll e r s which should be br a

,

ss or hard wood motion being

, ,

given by an eccentric or crank with about 6 revolutions per minute

and a stroke of 6 inches or 8 inches space for which must be a
,

ll owed ,

in the pits Th e moti on considerably i ncreases the rapidi ty of the

.

tanning and renders possible a better ex hau stion of the liquors

which should usu a
, ,

l ly be run away after use on the green goods

a
.

The pits r e best arranged in a continuous series , t h e t o p o f each

‘

pit being connected by a wooden trunk with the bottom o f the

next weaker a l l the liquors being ru n in at the head end a n d a
.

,
ll ,

the green goods brought in at the other and gradually advanced .

If the goods are brought into susp enders without previous ‘

deliming the first action which takes place is the neutralisation

,

of the lime at the expense of the weak acids of the liquors or if

these are not present in su fficien t quantity a
, ,

t that of the tannin

'

, ,

which forms mostly insoluble compounds with the li me which ,

readily oxidise and produce dark stains if exposed to t he air ;

,

though if protecte d from it they ultimately di ssolve in the more

, , _

acid and stronger liquors If the goods colour quickl y ( with

-
.
'

valonia to a lemon yell ow colour) this may al ways be susp ected

,
-

,
.

A t the same time the plumpness due to the lime disappears

and the goods become soft and spongy a
,

n d if pressed at this , ,

stage do not readily regain their plumpness and p ressure marks

and drawn gra
- -

, ,

i n are apt to remain permanently I f the liquors

'

are o f proper acidity plumpness is gr a du all y r ega

.

in e d by gentle '

acid swelli ng but this should not take place before the surface
,

tanned and no longer susceptible to the effect of acids or the ,

grain will darken and b e liable to crack when dry When hides ,

a
.

are swollen wit h strong acids as is sometimes done in the States

this is a l ways after the surface is f a
, ,

i rly coloured n d even t hen ,

a dark layer is apt to form below the grain where the tannin ,

—
has not had time to penetrate .

If new materials have to be used for making suspender

a
.

liquors the less astringent tans such as g mbier and myro

, ,

balans are most suitabl e and the synthetic tans such as

Ne r a
, , ,

d o l are now much us ed as they are very l ight I n colour

, , ,

and usually rather acid The colour which is given in the .

.

suspenders largely determines that of the finished product .

A fter the hides have remained from ten days to a fortnight in

the suspen ders they are usu a l ly laid in pits called
,
handlers ”
.
,

which are worked in series of Six ei ght or ten pits containing , , ,

3 60 P RI N C I P L E S OF L EA TH ER MA N UFA C T UR E

and the pumping sho ul d never be entrusted as it often is t o an , ,

ignorant and possibly stupid labo u rer

V ery varied materi a
.
, ,

l s are used in the manufacture of sole

leather Oa . k bark is one of the oldest and as regards quality
-

one of the most satisfactory but it is costl y not o nl y on account

a
, ,

of its we kness in tannin but f rom the light weight of leather

which it gives V alonia has been one o f the favourite materials
.
,

gi ving heavy weight and a solid leather in which it deposits a ,

great deal of bloom abut its place has been largely taken by
oakwood chestnut wood mimosa and quebrach o extracts
a
“

, , ,

which save the cost of gri nding and extraction of solid m terials
These extracts are now ve ry largely co nsumed princip a
.

l ly in ,

strengthening the l ayer liquors the great obj ect being not only
l but to save time a
-

to lessen the cost in materi a

'

n d p r o du c e , ,

greater weight and firmness Th e layer liquors in some yards .

-

where extract is used reach strengths of even 1 2 0 to 1 50 B kr ° °

.

( s.
p gr 1
. 1 2 to 1-
while in pure oak bark yards it is di ffic ul t -

to get above 3 0 or 3 5 Bkr and even these figu res are only
° °
.

reach ed by repeatedly strengt hening the same liquor in which ,

large quantities of non tanning substances accumulate The -

opinion of the most intelligent tanners i s however that better ,

-

results are attained by a regul ar change of liquor even if the ,

apparent strength 1 5 less .

When the leather has remained a sufficient time in t h e layers

to have attained all the weight and s o l idity of which i t is capable ,

it is washed up I n a clear and somewhat weaker liquor and is ,

ready to be taken to the shed to be dried and finished This .

simple method has however largely given place to others less

, ,

defensible partl y owing to the fact that sole leather is sold by

,

weight and part ly to the absurd demand of t h e shoe manu

,

facturer for a light colour which he p roceeds t o stain black o r ,

“

to cover up with a fake Th e usual thing now is to suspend

the butts before taking into the shed I n a warm and very strong
liquor of bleaching extract Very heavily b isu l p hit e d This
has the property of dissolving the reds or p hl o b a
.

p he n e s to ,

which the leather owes a good deal o f its solidity as well as its
colour a,
n d r ep l a
c in g the weight with soluble extract leaving ,

the leather bright coloured but more porous and less waterproof
than before Th e synthetic t a n n in s m a
,

.
y be used as bleaching
liquors with good effect A nother mod ern method of weighting
.

is to hang the g enerall y lightly tanned and bright coloured -

butts up till half dry or more and then to drum them with u n ,
“

diluted ex tract ; and this drying and drumming is sometimes

repeated Of course this completes the tannage and makes a
.
 VE G E TA B L E TA N N I N G P R OC E S S E S 3 61

firm and heavy weighing leather but one with an inordinately

-

large percentage of matter which can b e washed out with warm

water The goods a
. r e now taken into the shed to be dried and

fin ish e d
the proportion of free a
.

If cid in the suspender liquors is as it

ought to be it is probably rather advantageous than otherwise
,

for a little lime to remain in the interior of the hide as it keeps ,

the pelt in a plump condition during the first stages of colouring ,

quickens the penetration of the tannin and lessens the tendency ,

to drawn or wrinkled grain which arises when the goods go ,

into the liquors in a flat or fallen condition The ca u ses of .

drawn grain are often a little obscure Of course that case .

needs no elucidation in which the hides are submitted to the

tanning liquor in a creased or wrinkl ed condition which is ,

simply fixed and made permanent This may arise either from .

carele ssness in han dl ing the go ods before t aking into the sus
penders or from t he way in which they are slung to the sticks
,
“

which often draws them into long wrinkles afterwards difficult

to rem ove Drawn grain in genera
,

. l however ari ses from the , ,

grain surface becoming tanned and fixed in area while the sub ,

stance o f the hide is in a more ext ended con di tion than that
which it assumes as tannage proceeds Hides in a flat and u n
s wo l l en st a
.

t e are thinner the fibres are slenderer and looser than

'

when swollen and consequently the hide has a larg er area If

,
.
,

after the grain is t anned the substance of the hide becomes ,

contracted in the liquor either by swelling with acids or by the

,

direct action of the t annin on the interior fibres the grain is ,

cert ain to be shrivelled like the skin of a dried apple A similar

effect produced in a mechanical way may a
.
,

l ways be noted
where a hide h a
, ,

s been coloured han ging grain side out over a

'

pole so that the surface is extended at the bend on which long

, ,

wrinkles are formed as soon as it is straightened .

A hide I n a sh ght l y alkaline con dit ion colours and i s p enetrated

by the tan more quickly than one which is acid though actual ,

tannage does not take place till it becomes faintly acid .

Gambier gives pelt perfectly free from lime a pale bu ff colour ,

but where lime is present t h e colour is always reddi sh and

much darker and this coloration does not di sappear so readily
,

as that with valonia so that if gambier is to be used in the first

,

liquors care should be taken to remove all lime from the surface
,
.

Th e only known tannin which gives no insoluble compound wi th

lime is that of the babool pod ( sometimes c a l led gambia pod
which is frequently used in India as a bate and which would ,

probably prove very useful in colouring liquors ( p .

3 62 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

When s ole leather first goes into liquors it is generally swollen

'

with lime to some extent If the liquors contai n as they usually . .

,

do sufficient free acid ( acetic lactic) in addition to the tannins

these combine with a
, , ,

n d neutralise the lime and the pelt without

.

a
, ,

absolutely becoming flat and thin loses its firmness and becomes , ,
.

soft and spongy This is a favourable condition for the b so rp

.

tion of tannin but care shoul d be taken not to allow the pelt to
,

be squeezed or pressed or water will be squeezed out and the , ,

pelt will not easily resume its plumpness A s the tannage pro .

c e e ds both the tannin and the acid of the liquors penetrate

a
'

deeper into the pelt the former ten di ng to Contract n d the

,

a
latter to swell the fibres Thus a given quantit y of acid will
c use the greater swelling the less tannin is present and there
fore in strong tanning liquors more acid is required The presence
.

.
,

of certain products of b acterial putrefaction has a great but u n

explained effect in preventin g hide from swellin g with acids and
in hot we a ther , much better swelling is obtained by sterilising
a n d deliming the hides with carbolic acid or one of the other
.

coal tar products mentioned on pp 2 7 —2 9 B o ri c acid may

a
-
. .

l so be satisfactorily used for this pu rpose with dressing leathers ,

but shoul d not be allowed to get into sole leather liquors as it

tends to produce a soft and loose tan nage a
,

n d from its inorganic

and indestructible character is a a a

.
,

p t to ccumulate in a yard in
‘

which it is used Th e same reasons render unadvis ble its intro

.

duction into any liquors which are to be returned to t h e leaches

even in the tannage of dressing leather though its presence in ,

the c olouring liquors is otherwis e very useful in less e ning the .

astringency of the tannins m ell o vvin g the liquors and

making a fine grain It s mode of action is by no means clearly
.

explained but is in some way connected with it s t e n de n c y t o

produce conjugated acids pp 3 7 —
.
,

The so called mellown ess of ol d liquors requires a word of

-

comment It is well known to prac tical tanners that old liquors

‘

are much less liable to produce drawn grain and a harsh surface , ,

when used to colour green goods than liquors even equal ly weak , , ,

which have been made from fresh materials This is due to more .

than one cause Most natural tanning materials contain tanning

.

matters of varied degrees of astringency and power of attaching

themselves to the leather fib r e I t is obvious th t if a tanning -
. a
liquor is used the m ost astringent and energetic tannins will be
first removed from it leaving those of a milder character It is
a l so known that the presence of neutral al kaline s a
, .

l ts of weak
acids has considerable influence in producing mellowness the
addition for instance of sodium acetate h a
, s a mark e d e ffect
, .
3 64 P R I N C IPLE S OF L EA TH ER MA N UFA C T UR E

con di tion ; but it absorbs it apparently in larger quantity and at ,

any rate makes a firmer more solid and less flexible leather , , .

It has been mentioned that in the latter stages of the process -

solid tanning materials are generally strewed betw een the butts in
the tanning liquor It may be pointed out that many materials
va
.

r
y in their tanning e ffect accor d ing to whether they are used ,

in solid form or merely in liquors It has been shown by Y oul

and Gri ffith 1 that such materials as va
.

l onia oakwood and chest

'

nut ex t racts and myrobalans which contain both gallot annic

and ell a git a
, ,

a
n n ic acids lo se strength rapi dl y when kept in the
form of liquor and still more rapidl y when heated 2 the ell git a
,

n n ic
“

a
, ,

acid becoming decomposed with separation of insoluble ellagic

'

acid No w it is just this ellagic cid which deposited in or o n

.
,

the leather gives weight solidity and bloom and the investiga
tion points out not only an imp o r t a
, , , ,

n t so u r c e of loss in the tanning

industry but a l so expl ains why valonia which in sole leather

tannage is known to give hard a
, ,

n d heavy leather can be used ,

in large quantities on dressing leathers in Y orkshire with'

,

gambier in the form of liquor giving a so f t and mellow leather

a In this case the va
, ,

l most destitute of bloom l onia is extracted

by boi ling and the liquors kept long on t h e materi a
.

,
l I f weight .

and solidity are required from the use of such materials it is

obvious that t hey must be brought into im m
a
,

ediate contact with

the le ther to be t anned so that as large a part of the bloom ,

as possible is deposited in and not outside the leather With

many other mat eri a
.
,

l s such as hemlock quebracho and mimosa , , , ,

which yield no bloom but diffic u lt l y soluble tannins ( reds or

p hl o b a
,

p h e n es ) the same rule holds since in c ontact with the

‘

hides the sma l l proportion of these materi a

, ,

l s which is soluble
in the liquors is replaced from the mat erials s rapidly as it a
is absorbed by the leather while when liquors or extracts only , ,

are used the great er part of these sol idifying and weight giving
,
-

constituents remain unutilised in the spent t anning materials .

At the same time the long layers afford an opportunity for

the acetic a n d lactic fermentations t o go on which are the
principal source of the natural acidit y of liquors I t must be .

understood that what are called layers in England are n ot to

be identified with the S dtz e but ra t her with the Versen ke of the , ,

German tanner the former being layers given i n much the same
,

manner as was current in England 1 5 0 years ago in which the

]o m m S o c Che m I n d
1
1 428 901 p
a a a a at d f
. . . . .
, , .

2
m
Fo r t h e s e re so n b l o o m y ie l d in g m t e r i l s m u s t b e ex t r c e or

aaly i at al w a a ap ad
-

n s st mp t s o e er ure s o ss ib le, n so m e t ai nn n i al wa
y s s

d t y d a
-

°
es ro t Ce 1 00 .
 VE G E TA B L E TA NN I N G P R OC E SS E S 3 65

leather with thick layers of tanning material between is laid

, ,

in the empty p i t whi ch is afterwards fill ed up with liquor

, ,

of t en of a comparatively weak character In such layers the .

acidification and the s olidification of the lea t her both go on to

a still greater degree ; the acid formed apparently gradually
pe netrating to the heart of the leather fib r e s and producing a -

solidity and cheesy texture which can h ardly be obtained by

layers of the English kind which nevert heless have the advantage ,

in rapidity and cheapness .

In drying sole leather one o f the great obj ects which must be ,

aimed at is to remove the dark coloured liquor with which t h e -

goods are saturated from the surface and to prevent further , ,

portions of it from finding their way there from the interior If

'

a strip of fil t e r paper be allowed to rest with one end in a basin

-

containing a little liquor and be placed in a draught of air the ,

exposed end of the paper will rapi dl y become dark brown or

black the liquor which evaporates there being constant ly r e
,

placed by fresh port ions sucked up by capillary attraction from

the basin A similar action is constantly seen when fil tering
.

liquors through paper if the latter be allowed to proj ect ab o ve

the edge of the funnel Precisely the same e ffect occurs perhaps
a
.
,

incre sed by the oxidation of the tan nins on the edges and ,

other parts of a butt which are most exposed to draughts of air .

The use of oiling the grain is not only to a certain extent to , ,

protect it from oxidation but also to check evaporation and the , ,

a
consequen t accumulation there of the dark coloured solids con -

ta
.

in e d in the liquor A ver y similar r esult is att ined by wetting

the grain side and a
.

l lo wing as much of the evaporation as

,
.

possible to take place fro m the flesh

A s the finishing is almost purely mechanic a
.

l and scarcely ,

comes within the scope of the present volume a very brief ,

sketch must su ffice The mode of finishing which was formerly

. .
,

at least in vogue in Lancashire and Cheshi re may be taken as

,

a type of the best work ( In the present day the various .

methods are so widely known that they have ceased to be local ,

and are varied according to the quality and tannage o f the

goods ) The butts which in earlier times were l argely bark
.
,

tanned are taken wet from the pits and scoured on a rounded
, ,

beam or horse with stone and brush till the bloom is com
p l e t el y removed and are then lightly oiled on the grain half
, ,

dried sammed laid in pile to temper and struck out with ,

t he pin a two handled tool of triangular section The use

'

-
.
,

of this tool has now been largely superseded by Wilson s st riking ’

machine in which knives or sleekers ( or stones and brushes )

, ,
3 66 P R I N C I P L ES OF L EA TH ER MAN UFA C T UR E

held in j ointed arms are made to wo rk on the but t which is

_ , ,

a
extended over a slowly rotating cylinder The obj ect of the .

pinning is not so much to remove bloom or dirt which h s ,

a
been previously e ffected by the scouring as to s m ooth and ,

fl tten the g rain A fter further drying a se cond p mm n g 1 s

.

generally given and the goods are then twi ce rolled first with a
, ,

light weight and somewhat moist grain and then more heavily ,

with the grain nearly dry This was formerly ac complished b y .

-

Fm .
77 .
— ofi a
1 R o ller
'
'
.

a sort of b o x or car heavily loaded with we1 ght s ; supported on a

,

smooth brass roller of about 5 inches diameter and 9 inches long ,

and manipulate d with a long Wooden handle o n a floor of hard

wood or zinc plates One typ e of the m a chin e s whic h have now
.
'

almost entirely replaced this primitive contrivance is sho wn in

fig 7 7 b u t is p ri ncipally used for offal a
.
,
n d c o m m o n classes of
'

goods Fo r better work t ra versing rollers such as Wilson s

.
, ,
’

ingenious double bed roll er shown in fig 7 8 are to be preferred

-
; , .

After rolling the goods are dried pretty rap dl y by t he aid

i
, ,

of moderate heat and afte r polishing with a brush ( hand or

a
, , ,

machine fig are re dy for sale It may be p ointed out that ‘

, . .
,

although the tools are di fferent the process is almost the same
'

as that used for w oke lissé e in France and Belgium and ,

closely resembles that of currying harness leather except that ,

the stuffing with fats and oil is omitted . .

3 68 P R I N C I P L E S OF L E A TH E R M A N U F A C T UR E

to fix the dark coloured liquor and result in better colour t h ey

-

, ,

are then damped back and tempered and heavily rolled under , ,

a rapi dl y moving pendulum roll er which poli shes at t h e same ,

time that it smooths the leather The saving of cost by s o simple -

.

a process is not inconsiderable and somewhat similar methods

a
,

r e gradually being adopted in this country rolling taking the ,

place of striking .

In the West of England much heavy leather has been manu

fa c t u r e d from South A hides t anned with a large pro
portion of valonia a
merican
n d wh ich consequently ,
«

re he vily bloomed

No attempt is made to remove this bloom which would too

aa .

much lessen the weight and firmness but the goods after a light , ,

o iling to preserve the colour are hung up and partially dried , ,

and are then laid in pile to temper The grain side is now wet .

with soap and water with which a little oil is often mixed and
the bloom is struck in with the pin or machine— a
, ,

somewhat .

a
blunt pin being used or a blunt tool in the striking machine
which is held at such an angle as to smooth n d c ompress the
,

grain without taking t o o much hold on it A fter a little further

, .

drying the striking is generall y repeated the goods are washed .

,

over with water and rol led on They are now coloured with
a mixture of pigment c o l o u r ge n e r a
.
, ,

l l y containing a large pro

a
, _

portion of whitening ; or sometimes of French chal k coloured

with ochres chrome yellow and or nge or whatever may suit
,
-

, ,

the tint preferred by the tanner or best imitate t h e colour of a ,

clean scoured tannage and usual ly m 1 x e d with size and oil or

-

, ,

sometimes with oil and tan liquor This mixtur e is well rubbed .

in and smoothed over with a clot h and then polished by brush

, ,
”
ing when the goods are rolled o ff rapi dl y dried and again
, _ , ,

brushed If the work has been well do n e it is not easy to dis

.
,
'

t in guish from clean scouring and is much cheaper ,

.

A method intermediat e between this and the first described ,

and which was formerly much used in London was to proceed ,

“

as above but using more water and hol di ng the pin in the first
,

striking so as to scour out as much bloom as possible and assist ,

ing this by the free use of water and the brush Instead of .

using an opaque pigment colour the goods were generally -

coloured either between striking and the first rolling or between ,

the t wo rollings with a transparent colour such as dissolved

, ,

annatto or a mixture of aniline dyes so as to conceal the traces

, ,

of bloom and to render slight damages to the grain less con

,

s p ic u o u s .

The process of sole leather tanning has been discussed in con

s id e r a b l e detail on account of its simplicity and imp ortance It .
 VE GE TA B L E TA NN I N G P R OC E S S E S 3 69

is now time to point out in what respects the tannage of the

lighter leathers di ffers from it in principle Taking the case of .

ordinary dressing leathers such as kips and shaved hides the first
, ,

point to remember is that these g oods come into the li quors not
merely almost entirely deprived o f lime by bating but in a very
flat a
,

nd fallen condition from the action of the bacterial ferments

of the bate A s a general rule in this country the colouring is
.

done in paddles but where a very smooth grain is required the

,

use of suspenders is to be recommended and in A merica is ,

a
largely adopted Indeed in the States the entire tannage of much
.

of the cheaper le ther is done in suspension and the sides are ,

only removed from the laths to which they have been nailed
when they are required for splitting It is obvious from what .
,

has been said of sole leather that as the hides are brought into
,

liquors in a very fallen and extended condition the grain will be ,

likely to be wrinkled ; and indeed this is sure to be the case

unless by suspension the hide is more or less kept in tension till
, ,

its fibres are fixed by tanni ng The free motion in the paddle .

favours the formation of a pebbled grain since the hide is ,

-
'

bent now this way now that and minute wr inkles and creases are
,

fo r m e d in all directions Fo r many purposes and especially if

.
,

a grain is afterwards to be raised by boarding the curried

leather this graining in the paddl e is not disadvantageous so
,

long as it is not excessive In some other cases it cause s much

.

trouble and labour to the currier before it is removed and if ,

the English t anner and currier are ever to compete with the
A merican in smooth grain finishes it will be necessary for them
a
‘

to obviate this so urce of w sted labour The graining is the less

a
considerable n d the easi er to remove the weaker a
.

,
n d more ,

mellow are the liquors empl oyed in colouring and t he more

gradually their strength is increased .

The production of a soft leather depends on the fibre being

tanned in a fallen and unswell ed cond ition I t is for this reason .
,

a
and to remove the elastin network from the grain layer
'

- -

that bating is in many cases esse nt i l though where somewhat ,

firmer leathers are re quired mere r eduction of the swell ing by

,

removal of the lime is sufficient Fo r the same reason no acid .

swelling is permissible either before tanning or in the liquors and ,

‘

though liquors for soft leathers must be faintly acid they are ,

incapable of removing any large quantity of lime and for the ,

best results the deliming mus t be complete before tanning .

No w that in the light of knowledge very recently acquired we

a
have much clearer ideas than formerly of the exact obj ects of
‘

bating and puering it ought in many c ses to be possible to

,

24
 L EA THER MA N UFA C T UR E
-

37 0 P R I N C I P L ES OF 1

disp en se wit hthese operations altogether in favour of a s oren t ific

system of deliming and reducing the alkaline swelling At a .

certain definite degree of acidity the isoelectric point which , ,

for gelatin is about and for hide is almost iden tical as ,

P orter has r ecently shown ( see footnote p the hide ,

.

fibre is in a neutral conditio n acting neither as an acid nor an

,

al kali and at the same time is in the least swollen condition

,

possible by merely chemical neutralisation It would be im .

possible to maintain this condi tion by the mere addition of any

tolerably strong aci d b u t taking advantage of the properties of
, ,

weak acids and of their neutral salts ( p it can be done .

.
,

and would be very approximately att ained by mixtures of

acet ic acid and sodium ac etate the P of which is little vari ed , H
.

from 4 7 by small additions of acid or alkali but it is very ,

possible that better and cheaper solutions may be devised .

The concen t ration would be regulated and maintained by the

addition of small quantities of acid or of sodium acetate to t h e
neutral point of alizarin red which closely correspo n ds to the
,

a
isoelectric point ( 013 p using the comparator if the liquor
is colo u red Such regulating s lts are usu a l ly c a
. .

. l led
A nother result of puering is the digestion of the elastin of
t he grain and of any remnants of the g lands and hair follicles
which remain and this would be done if nec essary by p a
-

,
n cre o l

or some other tryptic ferment in mixture with ammonium

a
,

chloride and preferably before the neutralis tion as these act

, ,

most favourably in a somewhat more alkaline solution indicated

approximately by the neutr a
.

l point of cresol red The ammonium .

chloride itself acts as a bu ffer .

A s mere bating or puering is mainly designed to reduce swelling

b y t he action of bacterial products ( p
.
and is not a very .

e fficient means of removing lime it is desirable where it is em ,

ployed to supplement it by some more active deliming process

, .

I n the lighter leathers drenching ( p 2 1 4) generally fulfils this .

purpose and many of the more intelligent tanners now give bated
,

hides a bath in boric acid before t anning which not only removes ,

the last traces of lime without acid —swelling but checks the ,

bacterial fermentation and prevents its introduction into the

a
,

liquors In gambier t nnages a decidedly better colour is

.
,

obtained by this trea t m ent ( p .

In most cases the production of bloom is not desired in dressing

leather tannage and is prevented by relying chiefly on liquors
and avoiding the use of bloom giving solid materi a
, ,

l s which include
most pyroga
-

l lol tannins D ressing leather t annages can fr e

. .

quently be advantageously hastened b y drumming which by

'

,
37 2 P R I N C I P L ES OF LEA TH ER LMA N UEA CT UR E

invariabl y prepared for tanning by puering and drenchin g as , ,

colour and softness are the principal characteristics ai med at A .

somewhat interesting style of t annage is occasion all y used for

sheep skins ( roans ) and calf skins in which the skin is sewn into -

a bag flesh side out wit h only a small aperture left for filling l n
, ,

one of the shanks It is then turned grain side out and filled
.

with strong sumach liquor and a little leaf sumach t o prevent

leakage and floated m a tank of warm sumach liquor A fter a
, .

sho r t immersion the skins are piled on a stage so that the ,

liquor l s pressed through them by their weight and when partially

empty they are refill ed a
,

nd t he process repeated Th e tannage

,
.

is complet e in about twenty four hours and the leather is very -

soft .

A lthough the various chemical and physical theories of the

ta n n in g p r o c e ss are discussed at so me leng t h in Chapter XX X II

a
'

.
,

it may not b e out of pl ace here to point out certain chemi c l

facts which are not in dispute and of which the knowledge may ,

help to make clear the reasons governing the me t hods of manu

facture which have j ust b een described In the preparatory “

processes through which the skin has passed whether for sole or
'
.

dressing leather the conditions have b een prevailingly alkaline

, ,

and even if acid deliming is practised the aim is rather to bring ,

-

the s kin to a neutral than an acid condition Fo r the actual .

tannage however it is essential that the reaction should be acid

, , ,

though the actual degree of acidity as measured by the hydrion

concen tration will vary much with the class of leather produced
being somewhat considerable in the case of sole leather a
,

nd but
‘

little on the acid side for the finer and softer leathers Whatever .

the nature of the combination of tannin and pelt it only t akes

place in acid solutions and though it is easy to bring the diffi
reds of qu e b r a
,

c u l t l y soluble tannins such as the c ho int 0

'

, ,

alkaline solution they fail to tan in that condition and recours e

, ,

must be had to such salts as bisulphites which while they have , ,

an acid reaction are so weakly acid that their bases ( soda i n t he

,

case mentioned) can form soluble salts with the weak acids of
the di ffic ul tl y soluble tans A s to the reasons for this pecul iari t y
.

Chap ter X must be consulted but it may be pointed out here

that a l ka
.
,

l ine liquids not o nl y do not tan but actually strip

the tan a
,

l ready deposited and thi s is even true to some extent

of bisulphites Apart from this effect on the t annins the a
,

gids
‘

.
, ,

especially in sole leather tannage have of course a direct effect ,

on the skin itself swelling and separating the fibre bundles of

,

the corium into their constituent fibrils and so presenting a ,

larger surface to the action of the tan, and facilitating its pene
 VE G E TA B L E TA NN I N G P R OC E S S ES 37 3

a
t r t io n the earlier stages of the tanning process the untanned
. In
and freely exposed fibres combine eagerly with the tannin and
while w
,

eak liquors are sufficient to supply this very large ,

volume and rapid change of liquor is required to properly

feed the skin A large proportion of the tot a
.

l tan is absorbed
.

in t he first weeks of the sole l eather tannage and of course ,

in still shorter time by the thinner leathers and this em

p ha
,

sises the importance of rapid and continuous feeding in this

stage There is no reason to doubt that the tannin combines

.

inst antly with the raw gelatinous fibre when it com es in contact
with it but as the tannage progresses and the outside fibres are
,

saturated the liquor can only get at the fibres within by a slow
,

process of di ffusion which is probably rendered still slower by ,

the tanned surface act ing as a more or less semi permeable

“

layer No w di ffusion can only t ake place from a stronger to a

weaker solution and hence the necessit y of continuously in cr e a
.
,

, s

ing the strength of the liquor so that it should always be stronger

than that contained in t he tanne d outer layer a nd this c o ntinues
“

t o b e true throughout the process If the barkometer strength

of a liquor be taken at interva
-
.

l s it wi l l be found to diminish
rapi dl y at first then more slowly a
,

n d finally to remain almost

, ,

constant while the tannage at the same time comes to a stand

,

still On e o f the reasons beside the greater strength of the

.
,

liquors why modern tannages are much shorter than they used
,
.

to be is that more care is taken that the liquors are changed

,

before they have ceased to act and there is no doubt that in the ,

old two years tannage of sole leather much time was wast ed in
-
’

long layers in the latter part of which little or no p rogress was

,

made Most rapid tanning processes depend on t he qu ic ke n in g '

of diffusion by mechanic a
-
.

l means Thus the dru m tannages by .

-

constant fle x u r e of the hide alternately compress one side or ,

the other and thus produce a sort of pumping action which

, ,

forces the liquor through ; in bag tannage and some similar -

processes the liquor is forced through by direct mechanical

pressure while in the Nance High Vacuum process the liquor 1

though only at a temperature o f 7 0 to 80 Fa

,

h r actuall y boils
° °
.
,

in the in t eri or of the hide and so produces rapid interchange , .

In the earlier stages of tanning the liquors penetrate the

1
a t t mp t t
Th e f l iq i t h id b y d i
e t p o orce uor n o e rec r e ssur e or m o d er t e a
a aai d i t h
v cu s t i g f t im b
s one h aa l wa y n e c r e o so n o er, s s r e su l t e d a
in f il u r e
at h p f h id a fill d w it h p a ti a a
, ,

s e o re s o ll y i mp e re e r c c nco r e s s ib l e w t er w h il e
ta a pa t ia lly t a d
,

th f t im b
o se o i i If t h er con n r e r nn e h id e s w e r e d r ie d
im p g a ail y b f d t h
.

b f
e ore t i n l iq ld
re n or uor co u e s e o rce r o u gh t h e m in t his
wa y .
 37 4 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

fibri ls and combine with them ( wheth er chemically or by

adsorption and render them incapable of swelling in water
or of putrescence and actu a l ly converted on the surface into
,

leather 1 but such leather is porous and light weighing and

quite unsuitable for practical use especi a
-

, ,

l ly as sole or belting
“

leather .

A s the tannage progresses the fibres may be assumed to be

'

completely conver ted into leather b ut they are still capable of ,

fixing tannins and especiall y the less soluble tannins and such
, ,

bodies as ellagic acid by adsorption or crystallisation and the

, ,

leather gains in weight and in firmness but t his part of the ,

process must be very limited in dressing leathers The case is .

very parallel to that in the chrome process where after the first , ,
.

stages o nl y the more basic and less soluble salts are fixed A fter
,
.

the completion of the tannage in the yard it is very customary

to va t the leather in the case of sole leather in strong and
warm solutions of highly su lp hit e d extracts but this must rath er
be considered a bleaching t han a t anning operation a
,

s its e ffect

is to remove a par t of the p hl o b a

,

ph e n es and difficu lt l y soluble

’

tannins which have been deposite d and to render the leathe r ,

softer and more porous and permeable to water In dressing . .

leather yards where mixed tannages are used i t is customary '

with a similar obj ect to drum t h e go o ds m a Warm sumach or

'

m yr o b a
la
,

n s l iqu o r but this with the lighter leathers is more

‘

defensible .

Even when the goods are removed to the shed the tannage
can hardl y be sa1 d to be quite complete as no doubt further ,

fixation of the soluble tannins goes on during the drying and

so m
,

e of the non tanning matters such as gallic acid undergo

-

, ,

oxidation and dehydration and exert a tanning e ffect if the ,

fibre is not already fully saturated ( Cp p . .

1
In t his a
g th
st e e m ic r o s c o p e sh o w s n o s ig n s o f am e r e co a
ti g n of t he
fib r e s su c h aK a
s
pp n su p p o se d .
37 6 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

mineral tannage a l so greatly increases the rapidity of the pene

t ra t io n of the ve g e t ab le t a
n s by i so lati ng the fibres and rendering

a
'

, ,

them less gelatinous Once a leather is thor oughly t nned by

vegetable materi a
.

l s it is l ittle affected by subsequent treatment

,

with alumina or even with chrome ; and on the other hand

though chrome and a
, , ,

l umina leathers are still capable of absorbing

considerab le quantities of vegetable t annins they always re t ai n , ,

in a degree the qualities which the mineral tannage has com

m u n ic a
,

t e d to them Th e res ul ting leathers are thus not o nly

. .
‘

mo dified by the different p roportion of vegetable and mineral

tannages which have been gi ven and by the propertie s of the ,

part icular vegetable tannage used but by the order in which

the several treatments have been given and always ret a
,

i n to a , ,

considerable extent the charact eristics o f that which has been

,

first applied We have thus in our hands a power ful means of

.

modifying the character of our leather to suit the special require

ments which it is to ful fil .

So long as tanners were restricted on the one han d to the

a
-

, ,

ordin ry methods of stu ffing tanned leathers with oils and fats
and on the other to the use of egg yolk which h a
,

d long been -

common in alum tannages combination tannage remained of

-

,
-

but secondary importance and it was the application of the

method of fat liquoring by James Kent to his D ongola
-
1

leather which gave them the place they now possess by providing
aCheap substitute for egg yolk and enabling the tanner to obt ain
,

softness and resistance to water without producing the greasy

feel which is common to currie d leathers The process of fat .

liquoring has already been mentioned in connection with chrome

leathers to which it was sub sequ ently applied and we shall
, ,
.

ret u rn to it after having given some further details of the methods

of tannage .

In t he first place we must consider b riefly t he mutual acti o n of

t h e m in e r a
,

l and vegetable tannages on each o t h e n It has been

pointed out by Eitner and also mentioned in connection with ,

the decoloration of extracts ( p that the addition o f z2 p e r

1

cent of a
.

. l u m or aluminium sulphate to tanning liquors l ight e n e d

their colour not only by giving a degree of acidity to the solution
, ,

but by precipitating a portion of the darker and less soluble

constituents and made the solutions y ellower by developing the
colour of the fla
-

vo n e mordant dyestu ffs which are contained in

-

most tanning materials It is therefore desirabl e if these salts

are used to allow the solution to subside or to fil ter o ff the da
.
,

,
rk ,

1
D o n go l a l e a
t h er wa s i n v e n t e d iii t h e t i m e of t h e Eg y p t i a Wa n r,

D o n g o l wa a ay a
.

wh e n s m u c h i n t h e p u b l ic m in d h e n c e ,
it s f nc m -
n e .
 VE GE TA B L E A N D MI N E R A L TAN N A G E 37 7

coloured precipitate Chrome and iron s a l ts no doubt produce

.

a similar effect though from the dark colour of their compounds

,

with tannins the lightenin g of colour do es not take place

Pota ssium dichromate especi a
.

l ly if acidified generall y p r ec ip i
tates oxidises a
, ,

, nd darkens tannins so that it is not practicable in

, ,

combination —tannage ( pp 49 5 50 6) to follow a vegetable by a two

a
.
,

bath chrome tannage though the reverse order m y be pursued , .

Combination tannages such as the Swedish and D anish glove

leathers a
-

l ready referred to are generally first tawed with alum ,

,

and salt with or with out flour and e gg yolk and are then coloured
and more or less tanned with vegetable materi a
-

, ,

ls That em
ployed on the original D anish leather was willow bark ( of S a
.
.

a
l ix
‘

a r en a
ma) In France where this willow is not found the b rk
’

of the commoner S a lix c a a

.
, ,

p r m was substituted and as it is ,

much weaker in tannin additions of oak bark or sumach to supply ,

-

t he deficiency and of madder to give a redder colour were made

, ,

to it Th e dyeing of these leathers is frequently comb ined with

.

the tannage dyewoods or dyewood liquors bei ng mixed with the

,

tanning liquors In the manufacture of glazed French kid indeed

.
, ,

the process is so arranged by brushing on dye liquors mixed with ,

-

tannins as merely to tan the grain surface which is necessary to

enable an a
-

, ,

l u mis e d leather to be glazed b y friction leaving the -

substance of the leather of purely alum tannage .

On the other hand in the green leathers ( so called from

thei r greenish yellow colour a
,

nd largel y made in the West

-

R iding of Y orkshire ) the hides usually rec eive a light gambier

tannage extendi ng over a week or so in weak gambier liquors
,

in handlers and are then cured by han dl ing in hot and strong
solution of salt and a l um in which they are fin a
,

l l y left all night , ,

and then dried rapi dl y without washing out the alu m much of
'

which consequently crystallises on the surface This is slicked .

o ff and the leather damped back and heavily stu ffed with sod
, ,

oil If however the combination tannage is properly carried

.
, ,
-

out , it will stand liberal washing without losing the necessary

alum and of course a tougher and more satisfactory though
, ,

somewhat lighter weighing leather resul ts It is in many cases a

-

,
.

better plan to combine the two tannages in one bath mixing the
alum and s a
,

l t with the gambier and han dl ing or pad dl ing the

goods in the mixture This is the plan usu a
,

l ly adopted for .

D ongola leather in the U nited States Fo r skins which are to

be glazed it is important that t h e su rf a
.

c e sh o uld b e tanned with

the vegetable material and the goods are therefore worked into
gambier liquors to which the salt and a
,

l um are only added after

,

the tannage has made some little progress ; while for dull Dongola ,
37 8 P R I N C I P L ES OF L EA TH ER MA N U FA C T UR E

intended rather to imitate calf kid it is best for the alum and -

, ,

salt tannage to begin first Fo r goat skins for glazed D ongola .

-

kid about 4 lb of b lock gambier lb of alum and 1 lb of salt

'

a
. . .
, ,

re used per dozen and the tannage occupies in all about twenty
,

four hours .

A fter the skins are tanned they are thoroughly washed out
with tepid water to remove loose alum and gambier and are then
re a
,

dy for fat liquoring A s in the case o f chrome leather it is

-
.
,

of great importance that this washing should be done thoroughly

as any rem a i ning al u m wh ich di ffuses into t h e fat liquor will
,

cause it to curdl e A treatment with a weak neutr a

-

. l ising solution ,

say of hyposulphite in the first washing woul d do no harm ; I f

,

the washing is thorough the more neutral the fat liquor the ,
-

better but a more alkaline solution is less liable to curdl e and

the original fat liquor used by Mr Kent wa s the very a
, ,

-
l kaline
liqu or which had been used for washing chamois leather and ,

therefore cont ained a good deal of d egras No w soap and oil

a
.
,

solutions are usually made for the purpose and those described
in the chapter on chrome tann ge a
,

r e quite suitable though fat ,

liquoring is somewhat easier than i n the case of chrome and the ,

better the oil is emulsified the more sa t isfactory is the result , .

A sheet metal cylinder wi th a piston covered with fine wire

-
.
,

gauze does goo d service as an emulsifier and another method is ,

to incorporate the oil thoroughly with a hot pasty solution of

the soap which can be diluted as required If sp eci a
'

,
l soaps are .

made by the cold process (p

“

they can be superfatted in .

making as required Oils containin g a little free oleic acid

a
.

emulsify most easily and sul phonated oils are lso suitable , .

Fo r glazed finishes it is a very common mistake to employ too

— -
1
strong a fat liquor even 2 per cent of soap and 4 per cent of 1
.
-

oil will produce a very noticeable softening effect— but of course

for dull finishes much more m y be us ed Leathers absorb the a .

fat liquor most readily in a sammed con di tion but even if quite
-

wet they soon take up the w hole of the oil and soap leaving only ,

a little turbid liquor i n the drum .

No t only combination — tannages but purely vegetable ones can

be fat and the process is now largely used for coloured
calf and other leathers which r e required to be soft and nourished a
without greasiness Sesame ( Gingelly) oil seems very suitable
'
.

for this purpose East India sheep and goat though they do
.
,

not generally appear greasy are often so heavily oiled with this
'
,

oil ( up to 3 0 p er cent of their weight ) that it is usually desirable

.

rather to diminish than increase it which may be done by wash

ing with soap solutions preferably before a
,

l u m in g Goods may
'

, .
 CHAPTER XX III
G R I N D I NG OF TA N N I N G M A TE R I A L S

B E F OR E the tannin they c ontain can be extracted most materials ,

require to be ground almost the o nl y exceptions to this rul e

being divi divi and a
,
'

l garobilla in whic h the t annin is ver y

"

loosely contained Extracts whether solid or li quid merely

.
, ,

require to be di ssolved in water or liquor m which they are , ,

"

fo r all practical purposes perfectly soluble With the less

so l u b l e e x t r a
.
,
'

c t s i t is generally preferable to dissolve at a tempera

ture of 50 to 60 C with vigorous stirri ng Fo r solid extracts

0 °
. .

some method of mechanical agitation is desirable .

The act ual method of grinding and consequently the machinery ,

employed for the purpose vary not only with the material to be ,

ground but with the method of leaching adopted as it is essential

, ,

that t he mass of ground material should be completely permeated

by the liquor employed in le a ching ; and if it be ground too '

finely or subj ected to too mu ch pressure on account of the height

,

to which it is piled in the leaches it is apt to form a compact

a a
,

and cl y like mass the interior of which rem ins u nextracted

This is speci a a
-

a
, .

l ly important in the press or circul ting systems“

now gener ll y adopted .

In the laboratory where thorough extraction must be com

p l e t e d in a few hours the materi a
,

l can hardl y be too fine

,
but
0n the larger scal e a much coarser product must b e used and ,

leaching requires days or sometimes even weeks and is then

seldom successful in removing a
, ,
"

l l the tannin It is probable

however that in the future these mechanic a
.
_ ,

,
l di fficulties of ex
traction will be overcome and the material will then be as finely
divided and as completely extrac t ed on the large scal e as it is
, ,

in the laboratory at the present time .

On e of the ea rliest methods of grin di ng oak— bark and which ,

a
is still used for sumach ( p consists in crushing it under
.

l rge circular edge stones frequent l y turned by a horse This

-

,
.

process was very sl o w and ineffi cient for barks and both it and ,

horizont al millstones similar to those used for wheat were lon g

ago superseded by iron or st eel mills on t he same principle as the
ordinary coffee mill -
.

These mills consist of a bell O r inner cone covered ,

3 80
 GR I N D I N G OF TA NN I N G MA TE R I A L S 381

with blades or teeth arranged at a slight angle to the vertical

‘

section Of the cone and which are made finer and increased in
,

number towards its lower and wider part This cone rotates
within a
.

n outer hollow con e or casing also provided with blades ,

or teeth which are sloped slightly in the opposite direction to

those of the inner cone so as to meet them at an angle like
, ,

the cutting—blades of a pair of scissors and the angles of the cone

are so chosen that the blades a
,

p
proach each other more closely to
wards their base The outer cone .

is fixed and is provided with a

,

hopper like a co ffee mill while the -

inner cone is so rotated on its axis

that bark placed in the hopper is
screwed down b et wc c n the two and ,

cut finer and finer till it reaches the

lower edge when it drops out Th e
, .

blades or teeth are usuall y Cast in

one piece with the metal cones n d ,
a
sharpened when required by chipping
with cold This operation
shoul d not be conducted in the
mill house o r sm a
-

, l l chippings of Fm 8 —Co e Mil l , 0 . n .

iron may ge t mixed with the bark

and cause stains on the leather This form of mill which is .
,

run in England at ab out thirty revolutions per min ute and ,

nearly three times as fast in A merica works very well with ,

dry material but clogs ba dl y if it be appreciably damp On

,
.

this acc ou nt it is always well to run the mill w ith a fairly slack
belt which will slip before exerting sufficient pressure to break the
machine as in Such operations as gri nding safety clutches are
, ,
-

o i but little use

-

A type of mill var yi ng somewhat from the above consists of

a pair of discs or very obtuse cones the inner one of which runs ,

on a horizontal axis The teeth are generally arranged in con

.

centric rings and interlock with each other so that the opera ,

tion of these mills is a direct sheari ng and not a clipping one .

Th e material to be ground is fed at or near the centre of the fixed

disc and escapes at the edges The construction of this class of
, .

mill will be easily understood from fig 8 1 With damp materials . .

the discs very readily become clogged between the teeth and
sm a
,

l l pieces of iron or steel which get caught between the teeth

will often result in the breaking of the latter and the formation
of iron dust which is a serious obj ection to the employment of
,
3 82 P RI N C I P L E S OF L EA TH ER MA N U FA C T UR E

this type of mill (to which the Schm eija Excelsior the Glae ser
’

”
Favorita and the Devil Disint egrator of the Hardy Patent
,

Pick Co belong ) for grinding barks

Myrobalans a
. .

n d mimosa barks have proved especially trouble ,

some to grind the former from the hardness of the stones of the
fruit and a
,

t en de n c y to clog the mi ll and the latter from their

Disintegr a
patterns r e a
combined hardness and toughness tors of various
made which are capable of grinding both
.

FI G . 81 . Ex c e l s io r Mil l .

these materials satisfactorily and but for their liab ility t o cause
, ,

fire and the larger proportion of fine dust which they make are
, ,

usual ly to be pr eferred to toothed mi lls Fo r these reasons the .

mill house should as far as possible be isolated from ot her parts

-

of the tannery In spite of their di sadvantages however they

.
, ,

have come very largely into use on account of their efficiency

in grinding obstinate materials Disintegrators work on the

a
.

principle of knocking or beating the material to powder by

m eans of very r pidly revolving beaters which in the smaller , ,

machines are driven at 2 500 to 3 0 0 0 rev olutions per minute

, .

The first disintegrator was made by Carr and consisted of ,

two concentric cylinders or baskets of steel bars rot ating in '

opposite directions at a very high speed The material was fed .

between these and was dashed to pieces b y being th rown ag ainst

,

the bars and the outer casing .

3 84 P R I N C I P L E S OF L EA TH ER MA N UFA C T UR E

allowing it to roll on two levelled straight edges n d then filing

“ '

or chipping the beaters on the heavy side until it will remain

-

,
a
in di fferently in any position .

A form of disintegrator has been brought out in A merica by

the V illia
-
.
V
m s P atent Crusher and Pulveriser Company in which
’

FI G . 83 .
— D is in t e gr a
tor o p e n e d , s h o w in g c o n s t r u c t io n .

a series of discs are keyed to the main shaft to the circumference ,

of which a number of sets of hammers are suspended by

means of hinge bolts Each of these steel bars or hammers
-
.
-

, ,

has a free arc movement of and when the machine is in

motion take a position divergent from the centre on account Of
the centrifugal force A fter striking a blow against any mat erial
.

fed on to a plate serving as an anvil the hammers recoil ,

and after passing any material which is not shattered by the

,

blow again resume their normal position leaving t he n ext set

, ,

of hammers to beat against the unground material The hinged .

suspension of the hammers imparts a degree of flexibility to the

mill which is not found in any other machine of this character ,
 GR I N D I N G OF TA NN I N G MA TERI A L S 385

and lessens the risk of serious damage to the machine by t he ,

introduction of pieces of metal along with the bark The makers .

claim that this machine can b e repaired more rapi dl y and with
less expense than any other disintegrator of equal power on the
market Considerable improvements have recently been made
.

in the details of its construction Fig 84 shows a section of this

. .

mill Of course only the end hammers of each set can be seen
.

FI G . 84 —
S e c t i6n of Will ia
ms
’
Cr u sh e r .

in the figure and several impr ovements i n detail have now been
,

made ,

It is necessary that the feeding aperture of disintegrators

.

should be well protected to prevent the escape of fragments .

The writer remembers the case of a girl who lost an eye through
an escaping fragment of glue which was being ground
When myrob a l ans or v a
.

l onia is to be used for leaching it is

genera
,

l ly better to crush it between toothed or fluted rollers

'

rather than t o grind it finely as the cellular structure is just

,

as completely broken up and the flakes formed by crushing al low

,

of much freer percolation than when the material is powdered

by the disintegrator while the consumption of power is also less
,
’
.

The general construction of the machine will be easily understoo d

fro m fig 85 and it is only necessary to point out that the small
.
,

upper roller acts mainly as a feed to the larger crushing rolls .

25
3 86 P R I N C I P L E S OF L EA TH ER M A N U FA C T UR E

In the best mills the rollers r e made up of a series of toot hed

steel discs on a square axis and are on this account e a
a
sil y r e

a
'

placed or sharpened when they h ve become broken or worn .

Several mills have be e n introduced in A merica in which the

bark is sawn or rasped by toothed discs like circular saws but ,

these are onl y capable of dealing with barks of a brittle nature ,

and are imme di ately choked by tough mat erials like the bark of
the mimosa or oak A better form of mill but one which 1 s to
.
, ,

”
some extent subj e ct t o the sam e di sadvantage 1 s the shaving
mill in which blades a
, ,

,
r e fixed like plane i rons upo n a disc -

A .
— My r o b a a
l n s Cr u sh e r .

cones or cylinder and are rotated at a high Sp eed against the

, ,

mat erial which is fed against th em b y toothed rollers at such an

'

angle that the shavings are cut i agonally to the grain These
d
shavi ng mills are largely m use i n A merica for heml ock bark
-
.

with which they are particularly successful The principle of .

the machine is exactly the s ame as that of the machines used in .

cutting oak wo od quebracho and t he di fferent dyewoods On e

-
‘

, ,
.

type of shaving mill is illust rated in fig 8 6 Su ch machines are

“

only suited for cutting rather thick b a

-
. .

rk m long r ind and are ,

quite unsuitable for chopped bark .

It frequently happens that the material is delivered from the

mill in a very unequal sta te of division and it is sometimes
'

necessary to screen it and thus separate the coarser portion either

for use in the leaches or for r e grin din g whil e the fin e r p o rt io n
“ ‘

, _

is more suitable for dusting With disintegrators which .

,

deliver the bark with c onsi derable impetus t he screening can be ,

acc o mplished by placing a screen diagonally below the m ill _ ,

through which the finer parts are proj ected It is however .

, ,

essential that this screen should be quite smooth on its upper

3 88 P R I N C I P L E S OF L EA TH ER MA N U F A C T UR E

described This is frequently done by hand by chopping the

.

bark into pieces about 4 inches long and the operation is kno wn
’

as hatching Machines on the principle of the chaff cutter

.
-

consisting of a fly wheel with curved blades radially attached to

a
-

it r e sometimes used Instead of hatching it the bark is

,
. ,

frequently broken by passing through toothed rollers fitting into

each other and often a t
ta
,

c h ed to the mill the

construction of this machine
will be r ea dil y understood
from fig 8 7 . .

In B elgium and some

'

other bark produci ng dis -

t r ic t s the adhering moss ,

and dead outside bark

are usually removed before
hatching but apparently ,

these impurities are fre

quently r e mixed with the -

bark after the hatching is _

completed A s such barks

often a l s o contain much
FI G 8 7 — B ak B ea
k clay and dirt ; it is g ener
r r er.

ally expedient to p a
. .

ss t he
“

hatch e d bark over a coarse screen before letting it enter the

mill so as to remove the greater part of such rubbish since if
, , ,

left in the bark it produces black and unsatisfactory liquors

, .

In drawing up policies for fire insurance it is usual to charge

a higher rate where disintegrators are used to grind the tanning
material as owing to the amount of dust and the production o f
'

a
«

, ,

sparks by the striking of the steel parts of the machine on ny

chance piece of flint or metal which ma
,

y get in t o it th ere is a ,

greater liability to fire than with toothed mills although with

'
'

proper precautions the risk is really small ( 01 5 p , . .

Al l di sint egrators act like ventilating fans and suck in air

with the materi a
,

l blowing it out again with great force at the

,

periphery This air is heavily laden with dust from the tanning
materi a
.

l which is extremely irritating to the lungs

, Th e diffi -
.

culty is to some extent remedied by an air channel or flue -

( genera l ly cast in the casing of the machine ) connecting the dis

charge with the feed Opening so as to convey the air back to the
disintegrator The air is thus circulated through the a
-

. rrange
ment but some is always drawn in from the external atmosphere
,

and driven out with t he ground material and it is advisable that ,

 GR I ND I N G OF TA N N I N G MA TER I A L S 389

the chamber into which it is discharged shoul d b e provided with

some means of filtering the a i r before it escapes On e convenient .

method is to have a large suspended flannel bag which is blown

out by the air like a b a l loon and out of which the dust can be
shaken when the machinery has stopped A nother e fficient
method is to have one of the wa
.

l ls or the ceiling of the chamber ,

made of canvas or of sacking but in any case the air shoul d be

al l owed an escape where a little dust will not cause annoyance
Cha
a
.

in c on vey or s — While in England the ground material is

-

usually carried from the mill t o the leaches in b rrows or baskets , ,

in A merica t he use of conveyors is practically universal and ,

there is no doubt that they e ffect a great saving of labour at a

comparatively small cost
The most practic a
.

l conveyor for tanning material s consists of

-

a trough through which an en dl ess chain passes carrying scrapers .

Th e chain generally used for this purpose is one consisting of

square links fitting into each other and capable of running over
toothed wheels These chains are made by several firms in
.
_

America and in England by the Ewart Chain Conveyor Co of

, .

D erby wh o supply not only plain links but also t hos e having
‘

proj ections to which buckets scrapers and a variety of attach

a
, ,

ments m y be fixed .

In many cases the trough is V shaped with t h e chain running

'

in the angle in others fla

-

t bottomed as in the illustration or

-

, ,

rectangul ar The scrapers may consist either of metal or of

wood ; and where materi a
.

l s have to be carried up a steep incline ,

buckets instead of scrapers should be employed The arrange .

‘

ment of such a conveyor is illustrated by fig 88

A useful form o f conveyor for dry f m a t e ria
. .

l s consists in a
woven cotton belt running in a smooth trough and with laths
riveted across it at intervals These laths should proj ect slightly
.

beyond the edges of the belt so as to prevent wear Care must .

be taken with belts of this sort that the material does not get
’

between t h e b el t and the pulley .

Chain carriers are often used for conveying the spent tan to
the furnaces from the leaches and occasion a
-

l ly for carrying ski ns

,
.

B eside the malleable cast links which have been spoken of ,

and which are so arranged that they can be unhooked from

each other when the chain is slack various forms of mal leable ,

links are also available

Several other kinds of conveyor are in use in corn mills spir a
.

l -

or worm conveyors which work on the screw principle being

very largely used for carrying corn They are not very suitable .

for tanning materials on account of the coarseness of the latter ,

 MA N U FA C T UR E
-

390 P RI N C I P L E S OF LEA TH ER

by which the friction is greatly increased } they are however , ,

FI G . . a
8 8 — Ch in —
c o n ve y o r .

occasi onally used Those built up of separate blades are special ly

.

to be avoid ed It must b e r e m e m b e r e d that while the smooth

. _
 CHA PTER XX IV
TH E EX TRA C TI ON OP TA NN I N G M A TE R I A L S ,
A ND
M A KI N G
“

TH E OF E X TR A C TS

a a
a
Le chmg —The . material h ving b een reduced to a suitabl e “

state of finenes s is ready for extracti o n Thi s requires con

s id e r a
.

b l e a mount of time as the tannin is contained in c ells of

,

which the walls are o f a woo d like substance ( cellulose and

- - -

ligni ne ) through which the wat er d i ffuses b ut slo wly He nce “

.
, ,

unless the material be very finely ground a long soaking wil l be ,

necessary befor e it becomes spent It should be the aim of .

the tanner to have his barks etc ground so finely that they may

a
_ ,
.
,

be extracted as rapi dl y as possible and yet not be so fine that ,

th ey s ettle t o a compact m ss in the l eaches and so prevent

'

circulation U sing the present methods of extraction on the

.

large scale it is nec essary to have the material only somewhat

coarsely ground or crushed so as to render its percolation prao
t ic a
,

bl e ; but it is quite possible that in the future some bet ter

mechanical means will be found of t reating the dust and
o t h e r fin e l
.
y ground matter so as to bring about a very rapid
extracti o n
Sever a
.

l patents have been taken for continuous extractors

a
,

in which the material is fed in at one e nd of a lo ng rectangul r

tank or trough and g radua lly moved forward to the oth er by
spiral stirrers or some similar device the extracting liquid being
'

continuously run in at t h e end from whi c h the exhausted material

is removed and means being supplied for suitab l e heating It
a
-

.
,

is possible that some such method m y prove practicable for

the treatment of finely groun d material but at present such
machines seem either t o requi re too much water n d make too
weak liquors or not sufficiently to extract the material P ossibly
,
,

a .

they might prove useful I n extract manufacture for a preliminary

or a final treat m ent in conj unction with press leaches A n
.
.

”
apparatus of this sort under the name of A utomat is made
b y Messrs Blair Cam p bell 85 M Le a
.
, ,

n of Glasgow If used for

‘
. .
,

the fresh material in extract manufacture the liquors would “

probably require fil tration

Up to perhaps 1 80 years ago no attemp t wa
.

s made to leach

the tanning material which was simply strewed in layers between

,
 E X TR A C TI ON OE
’

TA NN I N G MA TERI A L S 39 3

the hides and moistened with water Leaching originated in

Englan d and was first applied merely to complete the e xh a
.

us

tion of the material which had been a

,

l ready used for layers but

the use of even weak liquors instead of water in the layers was
found so advantageous that new material was soon applied to ,

make stronger infusions The earliest form of leach was simply .

a pit with a perforated wooden eye or shaft d0wn one corner ,

in which a pump could b e placed to remove the liquor without

b eing choked with solid matter This was considerably improved .

by the addi tion of a perforated false bottom to the pit with

"

which the eye communicated The perforations of the latter .

were found unnecessary and it now serves simply for pumping ,

t hrough or for the manipulation of a plug in a hole communicating

,

FI G . 89 .
— Se c t io n of Le ah Bc ot tom .

with an undergrou nd trunk leading into a pump well Th e -

.

fal se bottom is best made of laths about 1 inch thick and 2 inches
wide cut slanting so as to be wider on the upper than the lower
,

surface which makes the spaces between them l ess liable to

,

choke The laths are nailed on cross battens with copper nails
.
-

which should be long enough to clinch i inch to é inch spaces ,

- -

being all owed between the laths accordi ng to the fineness of the
ground material The lattice bottom sho ul d be in at least two
sections so as to a
.

l low of its easy removal for cleaning and should

, ,

rest on detached blocks which are best nailed to t he underside ,

of the battens A space of 2 inches to 3 inches b el o w t he false

.

bottom wi ll prove sufficient if it is cleared every t im e t he pit is

“

emptied but not otherwise Clearness from obstruction b oth

,
.

below the bottom and between the laths themselves is ver v

important in securing free running in the p ress leach system
about to be described A section of the latticed bottom is shown
.

in fig 89 The laths are easily cut by employing a circular saw

. .

with a tilted table and turning the board at each cut No .

advantage is gained by planing them .

A s a strong liquor cannot be made by the use of a single

leaching pit a series of pits are now a
,
l ways employed and it is ,

the leaching systemati c or otherwise which determines how

,
3 94 P R I N C I P LE S OF L EA TH ER MA N UFA C T UR E

much of the total t an nin will be thrown away and lost in t he

“

spen t tan a
In the c se of properly extracted material s the
spent t a
.

n will no t contain more than 1 per cent of tanning .

matter b ut the degree o f e xtraction which is profitable is de

pendent o n the t anning materi a l employed a
, ,

nd the class O f

W ELL .

E C T I O N A
'

5 B
‘ -

a
.

FI G .
9 0
.
— Pl aad S
n n ec t io n o f B t t er y of Pr es s Le a
ch e s .

leather to be produced Wea k liquors m a y of course be

.

strengthened by evaporation .

The system of leaches now considered to be the best is based

o n the continuous circul ation of t he liquor by gravity f rom the

weakest to the strongest p it In its di fferent forms the p ress

leach is the simplest and in most cases is a
.

,
ll that is requi red .

A plan and vertical section of the lea ches is shown in fig 9 0 . .

A ssuming that the leaches have been working for some time ,

and that the liquor in the strongest leach has been run o ff to the
tan pits or in the case of manufacturing extracts to the de
-

, , ,

colorising tanks or evaporator the l ast vat in the series is now ,

fil led with water o r spent l iqu o r whic h may be heated by steam

‘

,
396 P R I N C I P L ES OF L E A TH ER MA N U FA C T UR E

construction is fitted in the eye of the leach A simpl e square

plunger in a square eye with two hinged flaps is a
.

ll that is
needed and no bottom valve is required as the lift is only a few
inches Such a pump wil l a
, ,

. l so serve many purposes of agitation

and mixing It is hardl y necessary to note that the liquor must
run do wn wa
.

r d through the leaches and up through the vertical

pipes in o rder to prevent mixture of t h e we a ker with the stronger \

.

liquor This will b e rendered the mor e certain if only the tail
leaches are heated as t he wa a
. .

r m weak liquor will always flo t on

,

the top of the cold

Severa
.

l addi t ions and modifications to the system have been

”
made with a view of obviating the so called channel di fficul ty -
.

There has been a fear on the part of s ome tanners that the liqui d
in the leaches may push the material aside and form channels .

through it thus preventing proper extraction of the t anning

,

matter In the Author s opinion thi s evil has been greatly

.
’

exaggerated as unless the liquid b e pumped from the leaches

'

at a very rapid rate while they are in circulation it is not at a

, ,

easy for the formation of such channels to t ke place In any

case it can be entirely avoided by t urning over the material
ll
a ,

in the leaches occasionall y so as to lighten it somewhat and ,

rearrange it a little .

It may also be pointed out that t he p ro v1 s1 0n of a proper

system for pressing or circulating leaches does not prevent their
being pumped o ff as frequently as desired though this is genera l ly
to be a
,

voided since when the leach is emptied of liquor the

,
'

material tends t o s et t l e into a c ompact mass which is not easy , .

to percolate and which is liable t o shrink from the sides of the

,

pit thus causing the very trouble which it is desired to avoid

, .

In this case stirring the material with a po le and running the

leach ba ckwa
,

r ds for a few minutes will somet imes get over t h e

di fficulty by lifting the materi a l There are some advantages

in taking t he first and strongest liquors off t he materi a
.

l in a
separate tank and then finishing the e xh a
,
u s t io n in the press
_
leaches since many materials swell and pack tightly when they
.

, ,

are fir St wetted but on the whole the method hardly pays for
,

its added cost unless it can be done mechanically On the

, .

larger scale the automatic extractor mentioned on p 3 9 2 would

a
.
,
'

seem worth consideration and could b e rranged with a chain ,

-

conveyor to deliver the wet and swollen material to the required

leach .

Th e press leach system as abo ve described is well adapted

for the requirements of f ar mers as its first cost is very small in ,

addition to that of the construction of the leaches themselves it

 E X TRA C TI ON OF TA N N I N G MA TER I A L S 397

extracts the bark well and saves much labour i n pumping and , ,

greatly lessens the tendency of the pumper to miss pits i n t he

series to save time when the master s eye is not on him ’

A not her advantage which is often i m por t ant is that when the
a
.

leaches are full mu ch more th n a single liquor can be run from

,

t h e head leach without pumping on ; and similarly when they

are run down to their lowest level much more than a single ‘

a
,

liquor can be pumped on to the worst le ch before it overflows .

A s the leaches flow slowly in comparison to the rate at which

liquors can be pumped by a go o d steam pump it is very a dv an
ta
,

g e o u s to allo w the pump to discharge into a liquor tank raised -

FI G .
9 1 .
— a
V l v e f o r Liqu o r Tr o u gh s .

to such a height that t he liquor can be run from it into any

leach at a suitable rate for t he circulation and it also enables ,

liquors to be pumped Without waiting till room has been found

for th em in the leaches Si milar tanks are very useful in running
.

liquors for:the yard and esp ecially for t he suspen ders in a sole
,

leather yard enabling circulation to be kept up during the night

a
,

and at other times when the pumps re not runni ng They

may a
.

l so be used as filters for the suspender liquors by fi t ting

.
.

them with false bottoms covered with a layer of nearly spent tan .

The liquors may be distributed to the different pits and leaches

by means of canvas hose pipes or what is often more convenient -

, , ,

by overhead troughs carefully levelled and fitted with discharge

, ,

valves where required Th e latter are conveniently made of

lead in a hemispherical form resting on an in dia
.

r u b b er washer ,
1

supported by a light brass casting or a suitably turned rebate ,

in a block of wood ( Cp p 550 and fig Such valves if good

india
. . .
,

r u b b e r is used wear well and are absolutely tight

In Englan d leaches are usu a
.
, ,

l ly sunk in the ground and are ,

1
a ab
Th e l e d c n
i

e c s b l y ha
at i a it a p d n su s e p r e s se d s t e e l
— b ain s bl ak
c

a a ad wit h t h w i
,

l e d e d t o p r e v e n t it s dh i es o n , n e re l in k su sp en d e d in i t .
398 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

frequently made of brick and cement or of large Y orkshire fla g ,

stones Such leaches are somewhat costly but very durable

.
, .

Square wooden pits pud dl ed outside with clay are also used and
, , ,

last well with cold or even warm liquors but will not stand
'

, , ,

a
direct steaming the wood graduall y bending and allo wing the
,

clay to le k into the liquor causing black stains On the con , .

struction of vats with reinforc ed concrete compare p 5 49 The

a
. .

large rou nd vats of thick pine and often hol di ng 1 0 or 1 2 tons

a
'

, ,

which are gener lly used in the U nited St tes stand boiling much
better and a
,

r e frequent ly Supported above a tramway or con

,

ve yo r into which the spent bark can be dis charged through

,

a manhole in the bottom If this metho d is adopted it must be . _ ,

remembered that bark and indeed most other tanning material s , ,

will not run th rough a hol e like corn but must be cast into it so
that unless the vat is of great depth it is simpler and a
, ,

l most as ,

easy to cast over the top If the manhole is u se d eit h er the

manhole must be a
, .
, .

l most the size of the pit or a central hole must

be made in the false bottom a
,

n d this must be surmount ed by a

copper pipe made in sections of 2 or 3 feet a n d r ea

,

chin g t o the
‘

top of the leach Wh en the pit is to be empt ied the top length
c

.
,

is removed and the tan shovell ed do w ,

n t he hole until the sec ond
len gt h is reached and the process repeated The central pipe
serves a
.
,

l so for the circulation of the liquor when the pits are

boiled and may be used as the ascen di ng pi pe for circulating on
,

the press leach system It is Simply j ointed like a stove p 1 p e .

-
.

I n the U nited States several machines ha ve been introduced

for t he mechanic a l castin g of leaches one of which is shown in ,

fig 9 2 The writer has no experience of their efficiency but

. .
,

their use seems to be practicable and wo ul d obviate one of the ,

most laborious and unpleasant operations of the tannery That .

illustrated is made by the Chas H St ehl in g Co of Milwaukee , . . .

Wis but a very similar mach ine is Cons t ructed by the Carley
.
,

Heater Co Olean N Y and both fir ms sup pl y b rass pitch holes

'

-
. . .
, , ,

and othe r necessary parts The mode of operation will be clear .

from the illustration the rotating shover being lowered into the
leach as the pitching proceeds The same machine can be used for
,

evenly sprea di ng the materia l as the leach is being filled a

.

n d of ,

course can be shifted from one leach to another as r equired The

pitch hole is near the side of the l e a ch a
.

n d Me ss r s St e hl in g inf orm
~
-

me that it is e a
, .

sil y ke p t open by the insertion of a conical plug

'

during the leaching which is Withdrawn for pitching any sligh t

, ,

subsequent choking being easily cleared The leach must of course .

be a round one but may be constructed of timber or reinforced

,

concrete t he latter bein g recommended by Messrs St ehlin g

,
.
40 0 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

be extracted in a sho rt time in a limited number of l eaches , and

where the obtaining of strong liquors is more important than the '

greatest economy of material much more boiling must often be ,

reso rted to and steam c oils are better than open steam In
' '

.
,

A merican tanneries the boiling is frequently done by copper coils

fixed below the fa l se bottoms of the vats but such coils are very
‘

costly a
a
,

nd where weak liquors only are to be heated seem to

, , ,

present no advant ge over a well arranged system of heating by

direct steam in which c a
-

re is taken that dry steam only is used

, . ,

and that all water condens ed in steam pipes and usual ly contain -

ing iron is removed by effective steam tr aps If steam is blow n

,
-
.

into cold liquor through an open pipe a very disagreeable rattling

an d vibration is produced which is not only ann o ying but is very , ,

injurious t o the leaches This evil may be avoided by the use .

of silent boiling j ets on the principle of the steam —j et water

raiser and fol lowing a suggestion o f the writer these je t s m a
\

, y , _

be used at the same time to circulate the water through the

tanning material of the nearly exh usted va t and so wa sh out a
a a
,
’
the l st traces of t n The simplest way to accomplish this is to .

lower t he boiling j et directed upwards and connected with a , ,

movable steam pipe into the eye of the leach ( which is preferably
-

central ) so that the heated Water flows over its top and percolates
'

downwards through the material to b e wa sh e d fi Two forms of

these b oiling and mixing j ets made b y Messrs Ko rt in g are shown

in figs 9 3 and 9 4 and similar j ets are now also made by En glish
.
, ,

engineers .

B atteries of closed copper extractors worked on the press ,

system and similar to tho se used In extracting sugar from

a
,

beetroot h ve frequently been advocated but are very cos t ly

, , ,

and have no other advantage for tanners over open vats than
that the liquor can be forced through the series by pressure
instead of circ ulating by gravity No advantage is gained by .

boiling under pressure since even boiling in open vats has been ,
‘

shown to destroy tannin darken the colour of the liquor and , ,

increase the amount of insolubles and higher temperatures are ,

stil l more inj urious

Closed vats worked at p ressure a
.

re however much used by , ,

extract manufacturers as they certainly enable a higher gravity

extract to be made from the same weight of materi a
,

l principally ,

by bringing certain woody constituents into solution which are

not di ssolved at lower temperatures Such extracts frequently
give the reaction for lignin which is usu a
.

l ly charact eristic of
sulphite cellulose liquors ,
-

Similar obj ections would not apply to working such extractors

 E X TR A C TI ON OF TA NN I N G MA TER I A L S 4 0 1

at so high a vacuum as woul d cause the materials to boil at a

low temperature The boiling would expel liquid from the pores
.
,

F I GS 9 3
. ad 9 4
n —B o il in g ad Mi
n x in g J et s .

which would again be fill ed with fresh liquor on reducing the

vacuum and this would probably lead to very rapid and complete
extraction while all n e c e ss a
,

,
r v moving of liquors would be just

26
40 2 P RI N C I P L E S OF L EA TH ER MA N U FA C T UR E

as well done b y the atmospheric pressure as by steam pressure

'

in excess Where airtight extra

. ctors are available t he method ,

seems well worth try ing .

Figs 9 5 and 9 6 show a battery of extractors such as are used

“

in the manufacture of beetroot sugar To adapt them for use in .

tannin extraction it would probably be desirable to en large the

dischargin g manholes perhaps to the whole diameter of the
,

autoclave “

Heati ng the weak e st leach in the press leach system promotes

the even circulation of t he liquor since the warm weak liquor is ,

FI GS 9 5
. ad 9 6 — B a
n tt . er y o f Su g aE t at
r x r c o rs .

much light e r than the colder and stronger li quors in the forward
leaches and so floats on the top and presses the s tronger liquor
, ,

uniformly downwards It also has the advantage that the

liquors are cooled before they a
.

r e strong enough for the yard ,

While in tanneries where all the leaches are heated expensive

tubular coolers are often employed As the liquor cools much
of the colouring matters a
.
,

n d reds dissolved in the hot liquor

separate and are fil tered out by the tanning material so that

, ,

much brighter and lighter coloured liquors are obtained

Sprin kl er Lea
-
.

ches (
fig 9 7 ) were formerly used in many tanneries
'

and extract facto ri es especially in the United States They were

, .

introduced by A llen and Warren and yi eld a liquor which is at

first very strong but which becomes very r a p idl y we a
,

ker as the
‘

,
40 4 P R I N C I P L E S OF L EA TH ER M A N UFA CT URE

decolorising agent but a paste of blood a l bumen has been placed

on the market which is said to be free from sever a
-

,
l of the dis
advantages attendi ng the use of the crude material .

Th e liquor to be decolorised is run into a mixing vat fitted

with a steam coil capable of raising the temperature of the
liquid to at least 80 C and usu a
'

ll y provided with a simple

°

rotary stirring gear The liquor as run into the mix ing va
.
_ ,

t
must not have a tem
.
, ,

perature of more than 48 C ( I I 8 F ) nor °

.
°
.

a strengt h of more than about 2 o Bkr ( sp gr I OZ O) ° '

The blood or a
. . . .

l bumen dis solved in a little water is added to

the contents of the va t which are t hen well mixed and the
"
'

temperature is raised to over 7 0 C when t he a a

, ,

l bumen co gulates
°
.
,

and carries do wn much of the colouring matter The solution is .

a
run into another tank where the precipitate is allowed to settle
, ,

and the clear liquor is then drawn o ff fo r the evapor t ion The .

muddy portion about 8 inches in depth is p u mp e d t hr o u gh fil t er

presses ( which m a
, ,

y b e cheaply co n structed of wood ) the clear ,

liquors going to the evaporators and t he press cakes being dried ,

-

f o r manure
In addi tion to blood a l bumen severa
.

l other substances such

as lead acetate ( sugar of lead) s a l ts of alumin a a l ka
-

, ,

l ine solutions
, ,

of casein and other albuminou s m att ers and crushed oil seeds ,
-

have been employed in the decoloration of extracts but they are

by no means so e fii c ie n t as a
,

l bumen
De colorising a
.

l ways causes a loss of tanning matter some of

this being carried down with the precipitated c o l o u rin g m a
,
'

t t er ,

and is for this reason to be di spensed with whenever its use is

not really necessary It may oft en be avoided by careful ex
tracti on at moderate temperatures and this is especi a
.

l ly to be
aimed at in the c a
,

se of strong tanning materials which easily

yield battery liquors of much greater strength than 20 B kr a
,

°
nd .
,

which thus if they can be sent direct to the evap orator save
, ,

cost in evaporation which is often an important consideration

, .

A nother method which is frequently used to brighten the

colour of extracts is treatment with sulphurous acid Dilute .

sul phurous acid solution may be used for extracti on but a more ,

common method is to pass sulphur dioxide gas into the l iquor

before concentration Sulphurous acid acts partly as a weak
.

acid in decomposing compounds of t h e tannins and colouring

matters with bases such as lime iron copper but more actively
, , , ,

by reducing oxygen compounds and preventing oxidation .

Bleaching in this way does not actual ly destroy or remove the

colouring matters which are apt to reappear on exposure to the
,

air either in the liquor or perhaps more often in the leather

, ,
 E X TR A C TI ON OF TA NN I N G MA TER I A L S 40 5

t anned with it so that the gain is frequently more apparent

,

than real If present in any considerabl e quantities sulphurous

.
,

acid may also cause inconvenience by its swelling action on

the pelt and a ,
l so by attacking the evaporator b u t is mostly ,

expelled in concentration .

A nother process should perhaps also be mentioned here though ,

not strictly a means of bleaching Several tanning materials .

,

and notably quebracho and hemlock contain large quantities of ,

diffic u lt l y soluble tannins which render the liquors made ,

from their ext racts turbid on cooling These tannins form

soluble compounds with a
.

l kalies and with alkal ine sulphites in ,

the latter case probably setting free the sulphurous acid and -

combining w ith t h e base This has been taken advantage of in .

a patent in which quebracho and other extracts are rendered

1

soluble by heating in closed vessels with bisul phites sulphites

sulphides or even caustic alka
, ,

,
l ies and many soluble quebracho ,

extracts made on this principle are now o n the market In

‘

'
.

this case even where bisulphit es are used the greater part of the
, ,

sul phurous acid after serving its purpose in preventing oxidation

, ,

escapes in course of manufacture and the extracts may remain ,

neutral or alkaline but as they are largely used as bleaching,

extracts the presence of 5 0 2 is mostly desire d There is no

, ,

reason that such extracts sho ul d not prove serviceable in tanning ,

but it has recentl y been shown by Faessler that the alkaline

t annin is not absorbed by neutra l hide —
powder and it therefore ,

may lead not only to discrepancies in analysis but in case of

dru m lt a nn a
, ,

g e where no acid is naturally present to failure

-

, ,

to utilise the whole of the tannin though when added to

_, , ,

ordi nary liquors the acids contained in the lat t er will set free
,

the tannins Dr Le p e t it has shown that qui t e radical changes

. .

are produced in the tannin of quebra cho by autoclave treatment

with bisulphites .

A satisfactory soluble quebracho extract has been made in

Germany by treatm ent with so di um carbonate a n d subsequent ,

slight acidification with a weak acid .

The u se of ferrocyanides has been suggested as a means of

precipitat ing iron and copper present in extracts and it may a l so ,

be p o in t e d o u t that with many red col oured tanning materials

such as hemlock and quebracho the addition of sm a
-

, ,

l l quantities
of a
,

l um to the tanning liquor effects considerable improvement in

colour not onl y by precipitating a part of the diffic ul t l y soluble
,
”
reds but by developing the yellow colour of certain colouring
,

matters ( querceti n myricetin etc ) which may be present Such

, , . .

1
L e p e t it ,
D o ll fu s , ad G a
n usse r , En g P t
. a858
. 2, 1 89 6 .
40 6 PR I N C IPL E S OF LEA TH ER M AN UFA C T UR E

a
an addition d oes no harm i n t he case of so ft leathers but would
pr ob bly be i njuriou s in a sol eleather tannage
Th e liquors whether di rect from the leaches or fr om the
,
.
,

decolorising vats must be c oncentrated by evaporation to syrupy

,

FI G .
98 .

consistency fo r l iqu id extracts or until they will become ne rly

, a
solid on cooling if a solid extract is required A s has already
, .

been stated the action o f heat tends to cause a l oss of tannin

a nd a da
.
,
'

r ke n in g of colour by decomposition and the formation

of insoluble reds To reduce this loss to a minimum the weak

.

liquors are evaporated with as little access of air and at as low

a temperature as possible and these conditions are best obtained
,

by the use of steam heated vacuum evaporators

-

It has been explai n ed in Chapter I X that the boiling tem .

40 8 P R I N C I P L ES OF L EA TH ER MA N UFA C T URE

to s a y and the steam from this again to boil one with still
higher vacuum and lower boiling point the heat of evaporation in ,

the first pan being recovered in the succee di ng one by again c o n

d en sin g the steam to w a ter when as much heat is liberated as ,

was before con sumed Thus in a single effect evaporator I lb

of co a
-
. .

l burnt under the b oiler may evaporate 8 — 5 l b of water .

,

in a doubl e e ffect 1 6 1 b in a triple 2 3 % l b and so on some l oss

-
.
, .
, ,

being incurred by waste of heat at each e ffect till there comes a

point when the s a
,

vm g of fuel will not repay fo r the prime cost

and wear and tear of the apparatus and it is rarely worth while to ,

go beyond three or four effects Each case must be judged on its ‘

meri ts and in some cases a single e ffect is c o mm e r c ia

.

l l y the most
'
‘

economic a
.
,

l .
'

As regards the detail of the pan the oldest fo r m u se d in sugar , ,

concentration was merely a steam jacketed pan with a copper

dome from which the escaping steam was c a
-

a
rried to a condenser
'

and then to an ir p ump ; As the boiling was violent and much

-

spray was produced which carried over sugar it was found _ ,

-

necessary to introduce a spray separator between the pan and

'

the condenser In more modern pans the heati ng is often done

by a steam box inside the p a n with vertic a
.

-
l tubes s o as to expose
a larger surface and cause a quicker circulation ,

To a considerable extent these forms of pan h ve been super

s e d e d by apparatus in whi ch t h e liquid i s sprayed through tubes
a
heated externally by steam the boiling being almost instantaneous , ,

and the liquid b eing evaporat ed and carried through the apparatus
in five or six minutes during which it is never exposed to an ,

ordinary boiling temperature P erhaps the earliest and still

one of the best of these machines is the Ya r a
.
,

1
which i sho wn
'

y n s

in fig 9 8 and its intern a

, ,

l construction in fig 99 In this
machine the tubes are horizont a
. . .
,

a
l In the Kestner 2 Climbing ,

Film evaporator they are vertic a

.

l n d the liquid is carried up ,

in a thin film on the sides of the tubes by the escaping steam

a
,

n d the evaporated liquid is delivered at a considerable height ,

which is sometimes advant ageous ; or the evaporation may be

carried further in a Fa l ling film body These evap orators
“

can of course be combined to mul tiple effects Sever a

.

l of them .

are in successful use in British tanneries where they were in the ,

first instance inst alled to concentrate partially exhausted liquo rs ,

but in some cases are now used for the manufacture of fresh
extract from mimosa bark and other materials Singl e and .

1
Mirrl e e s W a
t so n ay a G l ag w Y r n, s o

a
p a ad E gi i g al ia
.
,

2
K e s t n e r Ev o r t or n n n e er n Co -

Lt d .
, 37 P m r ent St r e e t ,

We st m in ster S W I , . . .
 EXTR A C TI ON 0 F TA NN I N G MA TERI A L S 40 9

triple e ffect climbing film evaporators are shown in figs 1 00 a

-
nd -

1 01
. In some cases the exposure to heat is so short t hat the

I oo — Tr i l e e ff e c t
.
p .

FI G —Sin l e e ffe c t
. 1 01 g .

evaporator is satisfactorily worked at or di nary boilin g te mperature

without vacuum as no perceptible injury is caused to t he l iqu o r
,
'

Somewhat similar appliances the Simplex and Mul ti

,
 P R I N C I P L E S OF L EA TH ER MA N UFA C T UR E
'

41 0

p l ex evap orators a
,
r e made by Messrs Blair Campbell M Le a
,
n
‘

Lt d .
( Govan Glasgow) and the latter is shown in fig 1 0 2
, , . .

FIG . 1 02 .

the evaporation of very viscous liquids as for inst ance

In , , ,

in the manufacture of solid extracts these appl i ances are,

41 2 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E “

materials useless to the tanner for his own extraction and their
carriage even for short distances ma
,

y amount to more than their

total va
a
l ue Even with much richer m aterials extraction
.
_

e ffects a s ving if the carriage is a long one as it rarely pays to

a
,

im port any material containing less than about 2 5 per cent of

tanning matter Even when the strength of t he n tural m
.

aterial
a
.

is considerabl e as in the case of quebracho extr ction may be

profitable if fro m it s hardness or other reasons the material
, ,

is difficul t for the t a

, ,

n n er to han dl e Fo r long voyages andt

especially from the tropi cs solid extracts are m

.
,

ore suitable than ,

a
liquid as the expense of casks is saved and the danger of fer
, ,
‘

mentation is lessened A s it is imp ossible for the t nner to .

j udge by appearance or consistency of the strength or value of

extracts they should always be bought a
,
n d sold on the analysis

o f the particular shipment o r parcel by a competent chemist -

.

Fo r directions for sampling see Chapter XX .

Extracts simply require to be dissolved in a suitable quant ity

of water or w eak liquor a t an appropriate temperat ure to obtain _

a liquor of any required strength Some extracts are completely .

soluble in cold water or liquor but most dissolve better by the ,

aid of heat 40 to 60 C ( 1 00 to 1 40 F ) is generally su fficient

.
° °
.
0 °
.

and probably no advantage can arise from temperatures over 80

( 1 80 B oiling should be avoided as it facilitates the f orma
°
,

”
tion of insoluble reds with consequent loss of tanning matter ,

and darkening of colour The extract should be run into the vat
m a thin st r e a m a
.

n d continuously plunged u p ; where large

'

, _

quantities of extract are to be dissolved a mechanical agitator

is advantageous A silent boiling j et ( p 40 1 ) may be used
fitted into a sm a
. .
,

l l casing immersed in the liquor and open at

both ends and the extract run into the current it produces
,
.

Wh ether in the manufacture of extracts or for direct use in /

the tannery the temperature at Which t anning materials are

,

extracted is of prime importance It is a common mistake to .

assume that the largest amount of tannin is extracted by boiling .

a
Mr A N P almer has pointed out that this is by no means the
. .

case but that each material has n op timu m temp erature of

extraction at which more t nnin is extracted than at any other a
,

though a sm a l l addition a
, ,

l amount can be obtained b yboiling the

extracted residue The method adopted in an a l ysis of extracting
.

as much as possible at low temperatures and only raising to ,

boiling point when half the required volume of liquor has been
obtained is intended to give a maximum extraction of materials
,

for which the op timu m point is not known and is a good principle ,

to follow in practical leaching The question has been carefully .

 E X TR A C TI ON OF TA NN I N G MA TER I A L S 4 1 3

1
investigated by J G P arker and the A uthor with resul ts which
. .
,

are given in the following tables Fo r many purposes the colour

.

ing matter which accompanies the tannin is a serious disadvantage

and it is usu a
,

l ly mostly extracted at the higher t emperatures ,

and on this account it is necessary for the tanner Who will work
his leaches economic a l ly to ascertain at what temperature he
can extract the largest amount of tannin combined with no more
—

colouring matter than he can permit to enter his leather Most

materi a
.

l s are satisfactoril y extracted at 50 to 60 C but as a

° °

gener a
.
,

a
l rule it is best to begin cold or nearly so and only raise
.
,

the temperature s the extraction proceeds The tables show . ,

the percentages of tanning matter and the amount of colour

,
_

as measured by o vib o n d s tintomet er ) obtained by extracting

’

( L
materi a
,

l s in a P rocter s ext ractor p 1 02 p 9 4)

’
. .
,

so long as any colour or tannin coul d be obtained .

]o u m Che m I n d 89 5
1
. .
,
1 , 63 5 .

[ TA BLE S
41 4 P R I N C I P L E S OF L EA TH ER M A N UF A C T UR E

F
u a
m
n
E

o
c
o
n e n w

5
o s
3 8
m o
53
G Q

m
M o
E 5
4
0
o
R
o
G
E o
m H
2 .

w
fi
-
.

P q fl
e
aw z o
.o
z
o
o
H
m
o fi d
m z
z
R
o

z
o
m

w 3
q 8
fl

a 3 3
c 3 & 9
0
5
0
a w
m b b

m
w 0 C

fi 2
o
m

o o o o c
m o u w o
l l l l |
o o o o o
v m o u m
41 6 P R I N C I P L ES OF L EA TH E R MA N U F A C T U R E

N
A

y n 5 b c
e e v o
5
o
“ “ w w o

n
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. .

m E E EE
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fi z E 5
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o o o o o o
v n o u w o
l l l | i r
o o o o o o
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E X TRA C TI ON OF TA N N I N G MA TER I A L S 41 7

m
w m
a
m
A fi A M
y v w V w
e w m H m m
“ o o u u w m

M
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a a
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. .

0 w
3 £ fi E
v
fi
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5 z
0 o
s
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m e o
H m

m a
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e . v y
m v v m
u o m w u

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41 8 P R I N C I P L ES OF L EA TH ER MA N U F A C T U R E

a a
r
s .
m

aa
N
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o
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m
w
m

o o o o o o
w m o u w o
l l l l l t
o o o o o o
m v m o m w
42 0 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

A L fi
v y v
m
.

o v o
n e u c
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m m
w
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A A

y o
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m o e o o
m v n u w

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l
m o o o c o o
H m e m e m w
E X TR A C TI ON OF TA NN I N G MA TER I A L S 42 1

m
r
m
w
a
s
fi

v
u o m m
H H u u

m A I “
w r v v
o u u o
m m m w

A L M A m A N
r N W B F r

8
o
H
o
H
N
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H
H o H
H
H
H

o o o o e o O
m w m c u w o
l l t l l |
m o o o o o o
H m v m o m m
4 22 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

a
0
3
fl
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0
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o

a o
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B v

B
.
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5
0

c
0 Q
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5
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a
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aa
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5 o 9 H
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5 9 S E
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m m
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w 8 0
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m v m o m w o 2
0
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42 4 P R I N C I P L E S OF L EA TH E R [MA N UFA C T UR E

a
s
a am
“
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m
v
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b N
a
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a
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fi ou c
.

B ”
.

z o
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.

sam
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0

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A m
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5
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mm
w o o
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S
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o o o o o o o
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m o o o o o o
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 CHAPTER X XV

FA TS, S OA P S , OI LS ,
A ND WA X E S

FATS and oils constitute a large class of substances of animal or ,

vegetable origin ,which may be solid pasty or more or less viscous

‘
, ,

liquids b ut which in the latter case are co mmonly known as

,

fixed or fatty oils to di stinguish t h e m from the volat ile or

,

essential oils which may be distilled w ithout decomposition

, ,

and which are the source of most of the odours of plants and of
quite different chemic a
,

l constitution Th e term oil is also

applied to various products of minera l o ri gin and especi a
.

ll y to ,
.

those derived from petroleum o n account of t heir si milarity in

app earance and physic a
,

l properties to the fixed oils though

chemic a
, ,

l l y; they form a very distinct class Th e waxes are .

another group somewhat closely all ied to the fats and there are
cert ain fixed oils such as sp erm oil which though very similar
, , ,

in appearance and properties to the fatty oils are chemically ,

members of the group of waxes

A s it is obvious that there is n o chemic a
.

l di stinction between
the fats and fatty oils except that of m elting point i t will be
convenient to treat them together especi a
_ , ,

l ly as what is a solid
‘

fat in o n e climate may be an oil in another Palm and cocoa .

nut oils are cases in point as the first is buttery and t h e second ,

a hard fat in t hi s cou ntry though they are both liquid in tropical ,

climates .

Fo r more detail ed information on the chemistry of fats and

oils the rea der must be referred to the Lea ther I n du s tr i es
La bor atory B oo k sect xviii to chaps x and xi of the Lea ther
Chemists P ocket B oo k or to the larger manu a
.
. . . . .
, ,

l s devoted specially
’

to the subject by Le wko wit s ch Fah ri on and others but a few

genera
, ,

l facts must be recapit ul ated .

The true fat s cont ain carbon hydrogen and oxygen but no , , ,

n itrogen They are all salts of glycerin with organic acids which
.
,
”
are generall y termed fatty acids and which resemble in many ,

of their physical characteri stics the fats themselves 1

Glycerin .

1
Th e n a
m es o f t he n e ut r a
l fa
t s or g l y c e r id e s t e r m in t e in a
t ho s e o f t he f re e aid
c s in ic t hu s t he a
f t o r o il o f o l e ic aid i
c s o l e in It
a a
.

is b e s t t o con fi ne t h e t e r m in t io n in e to t he c o m m erci l p ro du c t s ,
42 6 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E
is a very weak base of the nature o f an alcohol or sugar n d
consequently when a fat is heated with a solution of one of the
, _ ,
a ,

caustic a
,

l kalies the fatty acid combines with the latter and the
glycerin is set free The s a
, ,

l ts thus formed are denominate d .

soaps The reaction with stearin ( gl yce ri n stearate ) the

pri ncip a
.
,

l c o nstituent of hard animal fats is shown in the follow ,

ing equation
S odiu m So dium
Stearin
h ydr a
,

stearate Glycerin
te 1

H
( 1 7 3 5 O O) 3 C3 H 5
C C a
3 N OH 3 C1 7 H 3 5 CO ONa C3 H 5 ( OH ) 3 .

89 0 92

a soap is treated with an acid stronger than its own the

If ,

latter is set free while the new acid combines with the base
.

,
.

The following equation for instance shows the action of hydr o , ,

chloric acid on the stearic soap

Sodium
stearate
Hydro ct
acid
r ic
St e a
ri C a C1 d
'
Sodium
chloride
C1 7 H3 5 CO ON a H Cl C1 7 H3 5 CO OH N Cl a .

306
1
284 8
3 5

any soap be di ssolved in hot w ter and sufficient hydro

If a ,

chloric or sulphuric acid add ed to render the solution acid the ,

latter will turn first milky and (if it be kept warm ) the fatty
acid will fin a l ly rise in a
,

n oily layer to the surface which in ,

many cases will harden as it cools to a solid mass The amount , , .

of fatty acid in a soap may be roughly determined by weighing

2 5 gr m d iss o l vin g in 5 0 c c of boili ng water and addi ng excess
.
, . .
,

of acid allo wi ng the reaction to take place in a graduated

,

cylinder or a flask with a graduated neck in a vessel of boilin g

, ,

water When the fatty acid has risen to the top its volume may
.

be noted and each cubic centimetre may be roughly reckoned

,

as 0 9 grm ( Fo r more exact methods Cp

. sect xvii . . .
,

or chap x ) . .

Soaps are insoluble in strong caustic alkaline solutions and

therefore s ap o n ific a
,

t io n ( as t h e decomposition of fats by alkalies -

a ft
wh ic h re
y o en v er d iff er en t to t h e p ur e f t s a
Th u s t h e d is till e d
la a a
.

l i
o e ne g ly d i r e u se wo o l t e x t il e s
n is m in l y fr e e o l e ic c id t o g e t h e r wi t h
hyd ab aa
ro c l g
r ons n o a
o u s t o m in e r l o il s f o r m e d b y t h e b r e k in g d o w n a of

th a id b y h a
,

e c t e

a a
.

c o m b in e d
1
I t wil l b e n ot ed t h t t he w e igh t of
t h e gl y c e r in n d t he

3 m ols o f st e ai aid i
r c c gr e t e r t h n t h t
s a a a f th o e a a
o r ig in l s t e r in b y 5 4 , t h e

a
.

w e i gh t of 3 mols . o f c o m b in e d w t e r .
42 8 P R I N C I P L E S OF L EA TH ER MA N UFA CT UR E

soap with ca
'

l cium s ul phate is shown in t h e fo ll o win g equation

"

though in practice it is sometimes m o re complex

Stearin Ca l cium So di um Calci um
soap sul phate sul phate stear t e a
2 C1 7 H 3 5 CO . ON a a
C SO4 a
N 2S0 4

This is the reaction which causes the curdl ing of soap by hard
water and is the basis of the soap t est p
True fats cannot be di stilled a
.
,

l one without decomposition .

Wh en di still e d in a current of steam some undecomp osed fat “

passes over but the gr e a t er p a

r t is broken up into free fatty
'

acid and glycerin and hydrocarbons practic a l ly identic a

, .

l with
minera l oils are a l so formed
'

a
.

Fats and oils are insoluble in w ter and in most cases onl y
sparingly soluble in a
,

l cohol but freely soluble in ether petroleu m , ,

spirit benzene and most other hydrocarbons as well as in

, , , .

chloroform carbon tetrachl oride and Carbon di sul phide Petro

leum spi ri t often ca
.
, ,

ll ed benzine is largely used for their extrac

tion and for de gr e a
, ,

sing leather and removing grease from

’

, ,

clothes In the laboratory carbon disul phide or carbon tetra

.
_ ,

chl oride is to be preferred the latter having the advant age of

being non in fla mm a
,

ble Chloroform has lat ely been adopted as

a fat solvent in the an a
-
.

-
lysis of leather by the American Le ather
Chemists A ssociation It extracts rather more th an petroleum
’
.

spirit Castor oil is an exception to the rul e Owing to the

large proportion of oxygen which it cont a
. .

i ns it is r ea di ly soluble
in a
,

l cohol and very sparingl y in petroleum sp irit

, Other oils .
,

when oxidised usually become more soluble in alcohol and less

, ,

so in hydrocarbons .
~

Oils vary much in their tendency to dry or become con ,

verted into solid or sticky resin like substances This tendenc y

is greatest in s ome of the seed oils a
-
.

n d least in olive oil and the

oily part of ani m a l fats ( t all ow oil n e a

,

t s fo o t oil ) Sperm oil a

liquid wax is also very free from this t endency but a
.
, ,

”
,
l l oth e r ,

mar ine oils possess it in a greater or less degree It is not due to

evaporation but to the absorption of oxygen by the u n s a
.

,
tu
rated fatty acids The tendency to oxygen absorption and con .
-

s e qu e n t l y t o dryi ng ( and in the case of leather oils to spueing

’
-

is measured ana
,

lyt ically by the i o dine value the absorption

of iodine ( or bromine ) being proportion a
,

l to that of oxygen ,

while it is much more easily measured .

There are no simple tests by which the purity of oils can be

determined though in a few cases the presence of particular oils
,

can be d etected The colour reactions which used t o be relie d on

.
-
 FA TS , S OA P S ,
OI L S , A ND WA XES
are mostly due not to the oils themselves but to natura l im
, ,

purities which can often be removed by treatment The mixing ]

.

and adul teration of oils is now a science and those who practise ,

it are well acquainted with the customary t ests and take care ,

to adj ust their mix tures so as to meet them Taste and smell .
,

with practice often furnish useful in di cations b ut proper chemical

, ,

examination is the onl y safe guide and since it has become ,

common adulteration has a good deal di minished

Natura
.
,

l oils and fats are invariably mixtures of the glycerides

of several fatty a cids and their qu a l ities depend simply on the
'

character of th ese glycerides and t he proportions in which they '

are mixed The fatty acids form several groups di ffering in

.
,

their degree of 1
or inversely in their power of , ,

taking up oxygen on which their tendency to drying depends ,

.

Th e members of any one of these groups resemble each other

strongly differing princip a ll y in melting points density and
, , ,

o ther physical characteristics It is possible for a glyceride t o

cont a
.

in two or even three difierent fatty acids

Sa tur a ted Fa
.
, , _

tty A cids f— Stearic acid C1 7 H3 5 CO OH and .

, ,

palmitic acid C1 5 H3 1 CO OH are the mos t important . At ordinary

t emperatures they are hard white cryst a
, ,

l line bo di es and melt , , ,

at 69 and 62 C respectively They do not under ordinary

° °
. .
,

circumstances absorb any oxygen or io di ne and are very

little li ble to chemic a a
, ,
.

l change Together with oleic acid they

are the princip a l acids of t a
.

l low and other animal fats while

pa
,

l mitic acid and some lower members of the same group are
more common in vegetable oils Free stearic acid is a n im
'

portant constituent of the di still ed stearines used in curry

ing ; while oleostearine from pressed t ll ow consists mai nl y a
of the neutral fats or glycerides of stearic and palmitic acids .

The glyceri des of saturated acids are hard fats

Liqu id Fa
.

tty A cids N o u dry ing — Oi these oleic acid is much ,

-

.
r -

the most common and important its glyceride olein forming

the liquid part of animal fats and being the principa
, , ,
'

l constituent
of vegetable non drying oils Olive oil consists a
,

l most entirely
of olein with a little p a
-
.

l mitin
,
The form ul a of oleic acid is .

C1 7 H3 3 CO OH thus di ffering from stearic acid in having two atoms

.
,

of hydrogen less The bonds or affinities correspon di ng .

to these two atoms are linked together but can separate and , ,

attach two atoms of io di ne bro mine or chlorine or one of , , ,

1
A s a
t a
t d ur e c o mp o un d is one t he c o n s t it u e n t s o f w h ic h ap re r esen t

1 11 s u ch p r o p o r t io n s t h t ll t h e aa c o m b in in g a
ffi n it ie s of e ah a a
c ti fi re s s ed

b y t he o t hers I o d in e v l u e s e e
. a , p . 1 76 , ad n ]o u r n . Soc . C he m .

I nd .
,
1 9 02, p .
454 .
4 3 0 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

oxygen Th e io dine va
.
1
l ue of pure olein is 8 3 9 ( that is 1 0 0 grm , .

absorb grm iodine ) and that of olive oil about 8 3 An y

oil with a higher iodine va a
. .
,

l ue than olein must cont i n drying

oils though a lower va l ue does not necessarily in di cate their
absence if stearin palmitin or other saturated fats are a
,

,
lso ,

present
Other U n s a tu r ated Li qu id Fa
.

tty A cids — Of these there are

severa l groups differing in their degree of saturation and a
.

, lso ,

probably in their structure Their glycerides together with

olein and sometimes p a a
.
,

, l mitin r e the constituents of the seed ,

oils the drying tendency of which depends on their proportion

,

of unsaturated acids and the particul ar group to which they

bel ong The fish oils cont a
,

i n a peculiar group 0f unsaturated

acids together with olein and usuall y stearin and p a
.

, l mitin , ,

like the other animal fats Linolenic acid C1 7 H29 CO OH one of .

, ,

the acids of linseed oil has six hydrogen atoms less than steari c ,

acid and therefore three double l in kin gs and wil l take up six
atoms of i o di ne It s theoretic a
, ,

l iodine val ue is a 2 7 4 while linseed

oil itself often has an iodin e va
.
,

l ue exceeding 1 80 The io di ne .

value of cod liver oil is sometimes nearly as high B oth oils

therefore cont a
-
.

i n other acids less unsaturated than linolenic .

Fish oils appear often to co ntain also fatty acids with four or
more double l in kin gs and giving o c t o b ro mides on saturation ,

with bromine .

The spueing of leather is often due to the absorption of

oxygen and consequent r e sin ific a t io n of the oils and therefore a ll ,

drying oil s however pure are capable of producing it though

a
, , ,

some are more liable to do so than others (0 p p 4 69 . .

Linolenic acid and probably other llie acids become con

verted by absorption of oxygen into soli d va
, ,

r fiish l ike substances

a
-

which are import ant to the tanner as furnishing the princip l

constituents of j apans for leather in which they are now usu a lly ,

accompanied by cellulose derivatives ( p The unsaturated

acids of fish oils seldom gi ve hard varnishes t ho ugh m en ha
.

d en
'

oil ( p 447 ) is sometimes used as paint oil for outside work

.
-
.

Most fats are liable to become rancid by exposure to the air ,

acquiring a di sagreeable taste and smell and an acid reaction ,

from the liberation of the fatty acids The changes which take .

place are somewhat complex .

R icinoleic acid the fatty acid of C astor oil is of pecul iar con
, ,

s t it u t io n being an oleic acid i n whi ch one of the hydrogen atoms

,
-

is replaced by a hydroxyl or OH group The solubility of .

1
Ox y g e n i s not o ft e n tta
a h c ed in t h i s s im p l e w y b uta , at w
s o —OH

gr o up s or in o t he r more c o mp l e x gr o u p i n gs .
43 2 P R I N C I P L E S OF L EA TH ER M A N UFA C T UR E

taki ng the place of one of the side atoms o f H This makes no

, .

di fference in the ul timate composition of the acid as the sub

stituted H is replac ed by the termin a
,

l H of the side chain and

a
,

hence such acids are iso meri c and usu lly differ but littl e in
—
,

their properties The m ost common and important members

.

of the series are palmitic acid C1 5 H3 1 CO OH and stearic acid

“

, , ,

C1 7 H 3 5 CO n OH but some higher members are fo u n d in the waxes

'

a
, ,

n d butyr ic acid C3 H 7 CO OH is found in small quan tity in

~

butter The genera

, , _

l formula of the s eries is OH

Un s a tur a While in the satura
-
. .

t ed A cids —= ted acids each

.

carbon atom IS uni ted to each of its two neighb ours b y a single
link and its remaining two links are combined with and saturated
,
-

by hydrogen in the unsaturated acids one or more pairs of carbon

,

atoms are united by a double link and are therefore each com
'

b in e d wit h only one atom o f hydrogen T his d 0uble link is

not so s t r o n g a
-

_ .

'

s the single link of the saturated a cids and when ,

treated with chlorine bromine or io di ne or even with hydrogen

itself under the condi tions of the hydr o gen a
, , ,

t io n p r o bes s ( below) ,

one of the linkages is broken and combines with t wo atoms of ,

the new element in the case o f hydrogen being actuall y ,

verted into the corresponding saturated acid Oxyg e n can also . .

combine with the broken hn k and does so in several ways thicken ,

.

ing the oil by producing gummy 0r resinous products in the

dr yi ng oils o r even breaking it e ntirely in presenc e of m ol s
t ure with the for mation of an a
,

,
l dehyde and a new aci d of lowe r
molecular weight This is not without importance in the the o ry.

of oil tannages The number of double linkages vari es in the

“

di fferent series of unsaturated fatty a

-
.

c id s risin g fr m O n e in the
o .

oleic series to three in the linolenic acid of linseed oil which forms
he x a b r o m ides and even to fou r in the acids of some of the
‘

.
,

fish oil s
Hydrogen a
.

ti on — The most important advance in the tech

.

n o l o gy of fats which has been introduce d in recent years is the

method of hydrogenation di scovered by Sabatier Though .

hydrogen will not combine with unsaturated fats or fatty acids

with the same ease as bromine or io di ne it ha s been found that
under considerable pressure ra
,

i sed temperature and in presence of

finely di vided nickel as a cat a
, ,

l yst the combination does take place , ,

ren dering it thu s possible to convert any unsaturated fat into a

-

saturated one or raise it to any degree o f saturation required

'

Thus wh a
, .

l e oil can be converted into a solid fat of the stearin

type and at the same time it is so far freed from fishy taste and
,

smell that it can be used as an edible fat as for instance in the , , ,

manufacture of margarine A minute portion of nickel becomes .

 F A TS , S OA P S ,
OI L S ,
A ND WA X E S
dissolved in the fat but it is so small that it appears to have no
injurious e ffect The importance of the method for soap a
,

. nd

candle manufacture can hardl y be overestimated and for leather

manufacture fats as hard as deer t a
,

l low or A merican oleo

margari ne can be produced from any soft animal or veget a ble
fat , or even from fish oil The process is therefore being very .

largely used
The A cid Va
.

'
l u e is the number of milligrammes of p otassium
hydrate required to neutralise the fr ee fatty acid in a gramme
of the oil or fat It is determined by titrating the oil in the cold
wi th a N 1 0 a
.

l cohol ic solution of potassium hydrate with phenol

phth a l ein as an indicator until a f a
,

i nt pink is produced In ,
.

this way the free acids are neutralised but the fats are not
a
,

s po n ifie d .

The acid value varies with the age and rancidity of the fat ,

and is most important in oils used for lubrication as the free

acids corrode metals It is a
,

l so useful in detecting ad ul teration

'

of tal low with di still ed stearine which consists principally of ‘

free stearic acid The acid value of a genuine tallow ma

,

.
y vary
from 3 5 to 50 but for lubricatio n should not much exc eed the
-

lower va
,

l ue
Sa p on ifica tion Va lu e is the number of milligrammes of p o t a
.

sium hydrate required to combine with the whol e of the fatty

a
acids present in I grm of fat or oil It is dete rmined by boiling. .

the sample with a known excess of lcoholic potassi um hydrate

solution and titrating back the excess It va ries with the .

molecular weight of the acids present and is therefore a very ,

useful characteristic of di fferent oils and its average value is ,

given in a succeeding table ( p 43 6) for the different oils and fats

As petroleum oils have no s a p o n ific a
. .

t io n value and rosin oils

a very low one l o w values frequently indicate adulteration with
,

these substances Their actual quantity is determi ned by com

.

p l e t e l y saponifying the fat and then shaki ng out the soap solution
with petroleum ether which extracts the hydrocarbons ; a
,

nd

evaporating the etherea

,

l solution Waxes and sperm and .

,

bottlenose oils (liqui d waxes ) naturall y contain un

sa a a a
,

p o n ifi b l e l cohols and wool fat and many fish oils especi l ly

that of shark liver contain these in sm a
-

, ,

ll er quantities Fo r
their determin a
-
.
,

tion a similar method is used but ordinary ,

ethyl ether must be substituted for petroleum ether as the ,

alcohols are not very soluble in the latter

Th e s a p o n ific a t io n v a
.

l ue of course include s any acid val ue

present and to determine the ether va
,
l ue
”
or that of the aci ds ,

combined as glycerides the acid value must be deducted ,

.

28
43 4 P RI N C I P L ES OF L EA TH ER MA N UF A C T UR E

The I odi n e V lu e a
is as has been explained a measure of the
, ,

unsaturated double bonds of the fat and is the weight of iodine ,

absorbed by 1 0 0 parts of the fat or oil and is determined by ,

treating a chloroform solution of the substance with a known

excess of the iodising mix t u re a n d titrating back wi t h thiosulphate

in presence of potassium iodi de and starch Severa

,

. l di fferent .

iodising Solutions are in use which give nearly but not quite
identical va l ues that of Ha
, ,

n fis ,
whi ch is a solution of io di ne ,

and bromine in glacial acetic acid being the simplest and

'

, ,

for our purpose the most con venient Though both bromine
.
"

and iodine are absorbed by the oil , the mixture is det er

mined by the an a l ysis in terms of the equivalent quantity of
“

iodine and is so a l ways stated Saturated fats such as pure

stearin or p a l mitin have n o io di ne va l u e b u t in natura l ha
.
, ,

rd

fat s some olein is a l ways p res en t of which t he iodine va

, , ,

l ue ,

is 83 9 This approximat es to the iodine value of pure olive

oil which is mainly olein but cont a i ns some p a l mitin a
a
.

,
nd , ,

probably lso traces of so me less saturated fat In drying oils

such as hn se e d and in fish oils the io di ne va
.
, ,

,
l ue may rise as ,

high as 1 9 0 to 20 0 The higher the iodine value the more

.
,

liable is an oil to spue or produce resinous spots if used for

currying This must be distin guished from the tendency to
.

'

cause a white scum or effl orescence on the leath er whi ch is also ,

”
cal led spueing but is generally due to the presence of hard
,

fats or free fatty acids A s olei n is the onl y unsaturated fat in

a genuine tall ow or anima l fat its qu antity may be c a
.

l c ul ated
from the io di n e value and the higher its proportion the ,
'

softer is the fat .

Physical characteristi cs of fats are sometimes useful in j u dging

of p urity and as they are gener a
, ll y rapi dl y d etermined they ,

must not be overlooked

Sp ecific Gr a
.

vity ( the w eight of a C ll b iC centimetre in grammes )

'

is the most important of these and is easily ob t a i ned roughly ,

by t he use of a suitable hydrometer but much more accurately

by weighing in a gauged bottle or by a Mohr s b a
,

lance As oils ’
.

expand rather rapi dl y by heat the observance of an accurate ,

temperature is important 1 5 C is that usuall y adopted for .

°
.

oils but for hard fats a higher temperature such as the b 0iling
, ,

point of water is more convenien t If a bottl e gauged for

a
.
,

water at 1 5 is used the comp rison will be with water at this

°
,

temperature though strictly an allowance should be made for

the expansion by heat of the bottle itself The va
,

l ue of specific .

gravity as a test for oil s is much di minished by the fact that it

can be adjust e d by mixtures of low gravity mineral oils and
436 P R I N C I PLES OF L EA TH ER MA N UFA C T UR E

AP P R OX I MA TE CONSTA NTS or OILS A ND FA TS

Re fr ac So lidific a
tive I odine tion
Name Of 01 1 °

I ndex , V l uea . Tempera

ture .

B l o wn R a pe 9 67 1 4 81 63
Cast or —1 8
9 65 1 4 80 84
a
R w Lin s eed 1 48 4
-
1 75 1 6 to — 20
Cod liver ( m e d ) "
9 26 46 o
“

-
1 H
_
1 0
-

928 1 4 81 1 65
( brown ) .
-

9 28 1 482 -

Coast Cod ( mixed) 1

9 30 1 4 82

Whale -

9 3 1 1 4 76

Sardine ( Japanese ) 9 25 1 47 9

Se a
- -

l ( pale ) 9 25 1 478
Shark liver ( Sc ym
-

nus ) 9 17 1 478
Mixed Fish 9 29 1 4 80
Cottonseed 9 25 1 475 1 2
A rachis ( earth nut ) - -

9 22 1 474
Maize -

9 22 1 47 7
- -

1 0

Sesame ( Gingeli ) -

921 1 475 5
Olive -

91 6 1 470 2
R ape ( Colza ) 1

91 5 1 47 4
-

98 2
a
Ne t s fo o t -

91 5 1 47 4
-

70 Tender

a
Lard —8 to + 6
1 47 2 79
1

Sheep skin gre se 0 1 1 9 1 7

-
I 468
1
1 97 60 Tender
Egg yolk o il hen
-

91 4
,
-
1 471 1 84—1 9 0 68 + 20
Sp erm and B ottlenose 8 8 0 4 68 2 3—1 3 5 67 —8 1 D ysons ’
-
1 1

spermaceti
Mineral leather oils 1 47 5 1
- — Nil up to 2 0
R osin oils R esin — 8
1 5 0 54 43 4
-

at 60 °
acids
Mutton tallow 95 to 45
"

I 442
'
1 40 44
B eef tallow 1 4 42
1
1 9 6 42 36 38
B one fat 1 45 1 1 91 51 15 1 7

Distilled st e a
-

rm e 1 4 45 Variable 45 53
P araffin wax 1 43 4
-
Nil 4 40 55

NON D R YI NG -
FA TS A ND OILS

a
T llo w ( Fr S u if ; Ger T lg ) is
. the fat of various mamm a .l ia a ,

principal ly of the ox and sheep but occasionally also of th e ,

goat The mixed fat obtained from all part s of the carcass is
known as rendered t a
.

l low while that obtained from the region,

of the kidneys ( suet ) is harder A subs t ance commonly referred

. .
 FA TS ,
SOA P S ,
OI L S , A ND WA XES
to as pressed t a l low or oleo stearine is obtained by press -

ing ordinary tallow in cloths in the hydraulic press The more

l iquid portio n which is expressed is tall ow oil the finer qu a
.
, ,

l ities ,

of which are u sed in making margarine Oleo s t earine must .

-

not be confounded with the distilled stearine obtained from ,

Y orkshire grease by distillation and pressure ( p nor with .

—
candl emakers stearine which is a mixture of free stearic and
’

palmitic acids .

Pure tallow is white and tasteless but much of that sold ,

is yello wish and of a disagreeable slightly rancid flavour

Mutton t a
, .

llow is usually harder and whiter than that of beef .

Goat tallow has a characteristic odour as have the recovered ,

stearines and other waste greases from glue works B uck tallow -
.
,

which is particularly hard has now been largely replaced by ,

oleo stearine
-
.

B eef tallow melts at about 40 C mutton tallow at

°
.
,

In chemical composition tallow consists chiefly of a mixture,

of the tri glycerides of palmitic stearic and oleic acids its hard
-

, , ,

ness diminishing with the increase of the last

Ta
.

llow should when melted b e perfectly clear turbidity

, .
, ,

I ndicating the presence of water or other fore ign matters due ,

either to carelessness in the manufacture or p ossibly adultera , ,

tion Traces of phosphate of lime or fragments of animal tissue

ma
.
, ,

y be present as accidental impurities ; lime on the other ,

ha nd is sometimes added to thicken the tallow and enable it to

,

retain more water starch china cla y whiting heavy spar etc
are also occasionally employed Ta
-

a
, , , , .
,

l low has been not in fre .

quently adulter ted wi th the distilled fatty acids from wool

grease Wh en this is the case crystals of cholesterol ( see
p 1 8 1 ) may be detected by examination of the u n s a p o n ifia
-

.
,

. bl e
matter of the mixture under a microscope Such adulte ration
would also gi ve the tall ow an unusuall y high acid va
.

l ue .

Methods for the proxi mate analysis of tallow are given in the
La bor ato ry B oo k pp 1 8 9 et seq n d in the
,
. ch xi . . .

The fats produced by the boiling of fie shin gs for glue and

'

by the pressing of sheep skins are of the nature of soft t a

,

l lows , .

'

I f the fleshin gs are delimed wi th acid and boil ed fresh the

grease is generally of good colour and with little unpleasant
odour but contains traces of free fatty acids derived from the
,

decomposition of the lime soaps If the fle shin gs have been

a
-
.

dried and the lime carbonated the grease will gener lly be
brown a
,

n d more or less rancid ;

,
but the lime soaps are not -

decomposed unless the scutch or refuse be treated with acid

, ,

when a further yield of g rease is obtained Carbonic acid will .

43 8 P R I N CI P L ES OF L EA TH ER MA N UFA C T UR E

neutra l ise l ime but will not decompose lime soaps The grease
'

from sheep skins is genera

-
.
,

l ly somewhat brown and often smells

-

of t he volatile acids and other constituents of the tan liquors

especi a The se gr e a
-

l ly if larch bark has been used s es are usual ly

'

much improved in appearance and odour if well wa

.

shed by _

boiling or steaming on water or by blowing a mixture o f air

, ,
“

and steam through them or som etimes even by mere heating to ,

a sufficient temperature to evaporate the water and dri ve o ff the

volatil e m tters By a a
l lowing t h e greas e to cool slowly so as
.
,

to favour crystall isation t ill it is of a soupy consistency and ,

“

then pump ing through a filter press with wo ollen cl oths t he ‘

mo re liquid part is separated easily fro m a more solid portion ,

and both may in many cases be used in l eather manufact ure

the tall ow for currying a nd the oil in place of n e a
,

t sfo o t o il
Ha rse f a t and e speci a
.
,

ll y that from the fatty portions of the

neck ( Ger Ka mmfett) as well as var ious other anim a
-

l greases
a
.
, ,

r e used in the manufacture of leather They di ffer from tall ow

chiefly in that they have a lower melting point and con ta
,

in ,

more olein in proportion to the stearin and p almitin than true

tallo w and are consequently somewhat softer ; Tho ugh often
‘

almost white these greases are somet imes darkened in colour

”

by the products of putrefyin g anima

,

l mat ter b ut this d o es not , ,

as a rule interfere with the oil being used for leather dressing
They are usu a
, .

l ly so cheap that they are but little adulterated

means of determining their purity are however given in , ,

p 1 91
N ca
. .

tsf oot oil is a y ellowish nearly o dourless oil of bland

“ '

taste which is l argely employed in the dressing of c a

,

,
.

,
l f kid It -
.

has a similar composition to tallow oil and t he other oils Obtained

by subj ecting the soft animal fats to great pressure at a low
temperature It is often adulterated with bone oil lard oil and
.
'

, ,

cottonseed oil , and occasionally with mineral oil and recovered

wool gre a se
As n e a
.

t s fo o t oil is so mewhat costly curriers may wit h

advantage often us e ordinary anim a
,

l greases (horse fat etc )

after they have had the harder t a
-
.
,

l low extracted by cooling and

pressure the product thus obtained being chemicall y the same
as n e a
, , ,

t s fo o t oil and in every respe ct as suitabl e while it is

a
, ,

much less liable to dulteration

The t r ue n e a
.

t s fo o t oil is prepared by boiling the feet of cattle ,

and sometimes of sheep and hor ses with water and skimming , ,

o ff and clarifying the oil which is thus Obtained For use i n .

fat liquors it shoul d be

-
racked or filtered at freezing “

point .
4 40 P RI N C I P L ES OF L EA TH ER MA N UFA C T UR E

hydrocarbons strongly rese m b hn g mineral oils Th e distillate is .

separated by cooling and pr essure into a liquid oleine and a

solid stearine Th e latter forms a very valuable s t u ffi n g
a
a
.
_

grease which in Engl and largely t kes t h e place of t he oleo

,

ste rine used in the United States with which ho wever it , , ,

m ust not be confounded

D is till ed Ste a r in e prepared a s above describ ed is a p a
.

, l e yellow ,

or brown fat which varies in h ardness and in its melting point

,

accordin g to the con di tions of its preparation It has a charac .

t e ris t ic odour which is very persistent and it consists largely of ,

free stearic and palmitic acids most of the liquid hydro carbons , .

”
formed b y distillation being removed with the oleine
Olive Oil ( Fr H u ile d olive ; Ger Oli ven oel B a
.

u mo e l) finds
’

extensive use in leather dressing and especially in the m a n u fa

. .
,

c ,

ture of fat liquors ( p p 37 8

-
It is extracted from the
.
,
”

fruit of the olive tree by pressure and of late years from the , ,

residues by extraction with volatile fat solvents Although

it ch emically resembles f a
-

ll o w and lard oils very strongl y its ,

adulter ation with these substances m ay usually be detected _ ,

at any rate roughly by the taste and odour of the Oil It is

“

princip ally characterised from a chemic a

.
,

l point of view by
containing the glyceride of palmitic but not t h a
, ,

t o f stearic acid ,

and by having a much larger proportion of olein to solid glyceri des

than most of the non drying animal oils A t low temperatures-

olive oil solidifies to a product which can be separated by pressure

into a solid tal lo wlike fat and a fluid oil consisting essentially
-

of tri olein-
.

Olive oil is the type of a non drying vegetable oil b u t though

it does not thicken m a t e r ia
-

ll y o n exposure it becomes rancid p , __

somewhat rapidly and is thus rendered unsuitabl e for lubrica

,

t ion t h e free acids attacking brass and copper

, _ Unl ess t he .

acidity is excessive it does not appear to injure the oil for leather
manufacture and for some purp o ses is actual ly an dvantage
,

as aiding emulsification Free acids in oils may be removed .

a
by shaking with sodium carbonate solution
Ohve oil a
.

l ways contains some free acid which is of impor

tance in the preparation of fa t liquors as it facilitates the pro -

duction of an emulsio n This quality may be increased by the .

addition when necessary of a little oleic acid or of sulphated oil s

, , .

Olive oil is frequently adulterated with other vegetable oils

Probably the most useful criterion is the iodine va
.

l ue which is ,

rais ed by the addition of any seed oil except cast or The

refractometer a
_ .

a
l so a ffords useful indications Cottonseed sesame .
, ,

and arachis ( earth nu t ) oils are the most frequent adulter nts of
-
 FA TS ,
S OA P S ,
OI L S ,
A ND WA X E S 44 1

the better qualities and in m any cases may be recognised by ,

special tests
Ca
.

s to r Oil
( F r H u il e de r ic in Ger R i cin u so el
.
) is the oil .

expressed from the seeds of R icin u s commu n is and is a trans ,

parent colourless o r pale yel lowish liquid having a faint odour

, ,

and a di sagreeable taste A t a low temperature it thickens and .

deposits slightly and at 1 8 C it solidifies to a pale yellow mass °

Castor oil is distinguished from a

.
, .

ll other natural fixed oil s

by its high density ( 0 9 60 to 0 9 64) and viscosity and by its
solubility in a
,

l cohol and its insolubility in petroleum ether .

Genuine castor oil is completely soluble in an equal volume of

absolute alcohol or in four times its volume of rectified spirit
at the ordinary temperature It is practic a
,

l ly insoluble in petro .

leum ether but can dissolve an equal measure of that liquid

,
.

Fo r the purpose of the leather manufacturer the ordinary ,

hot pressed oil such as is used for lubricating machinery is quite

-

, ,

as good as the more costly cold pressed oil which is used for
'

medicinal purposes It is generally importe d in tins hOl din g .

about 40 lb of oil Castor oil and castor oil soap made as

. .
,
-

described on p 42 7 are very good for fat liquors seeming to inter

.
,
-

fere with dyeing and glazing less than most other oils B oots .

oiled with castor oil may be blacked at once and will take a ,

good polish .

The only oils which are usually mixed with castor oil are
blown or oxidised seed oils or resin oil A n y other oils would ,
.

so seriously lower the specific gravity as to render their use im ~

practicable Fo r the detection a nd estimation of these the

La bo r a
.

‘
‘

tory Boo k should be cons ul ted or if fuller details are

required t he reader is referred to Lewko wit s ch s Oil s Fa ts a
,
’

nd

Wa x e s or to A llen s C ommer ci a l Org an ic A n a

, ,

ly s is vol 1 1
’

.
, , .

Sulphonated ( perhaps mo re properly sulphated castor

oil o r Turkey red oil is now largely used for f a
'
-
t liquoring -

fo r which it was probably first employed by the author about

1 89 0 . This materi a l — which must be careful ly distinguished
from the ol ive oil preparation which is also used for dyeing cotton
aTurkey red colour— is made by treating castor oil with one
-

quarter of its weight of strong sulphuric acid ( specific gravity

adding the latter in very small quantities at a time and
'

1 ,

taking care that the temperature of the mixture at no time

’

exceeds 3 5 C Th e mixture is then allowed to stand for twenty

°

four hours with occasional stirring and is w

.

,
ashed with its own ,

volume of wat er allowed to stand until the water has all sepa ,

rated and the oil is then syphoned o ff If desired the oil may
, .
,

b e further washed once or twi ce with a solution of strong brine ,

442 P RI N C I P L ES OF L EA TH ER MA N UFA CTUR E

but this is of doubtful advantage and shoul d in n o case be

excessive The washed oil is finall y neutra
,

. l ised by the cauti ous

addition of about one hundredth of it s volume of strong ammonia -

solution (sp gr 0 . .

If properly prepared Turkey red oil ( sul phonated castor

oil ) will when l a
-

rgely diluted with water bear the addition of

ammonia to a l ka
, ,

hn e reaction without showing any turbi di ty

'

even on stan di ng severa l hours If a t urbi di ty is produced it .

,

in di cates that the castor Oil used was impure and contained some

a
oil rich in stearin
The l cohol test described on p 441 may a
.

l so be applied as
the oily layer will be entirely soluble if castor oil a
.
,

l one was used

in t h e prepar tion of t h e red oil a .

Turkey red oil usual ly contains about 50 per cent of fatty

-
.

acids (A llen) .

Linseed Oil ( Fr Huil e de lin ; Ger Lein oel) is used by leather

a
. .

manufacturers i n the prepar tion of the j apan for making paten t “

leather ( p and to some extent a l so in currying for oiling

'

.
,

off levants and moroccos though for these purposes it has been ,

largely super seded by mineral oils It is obtained from the

seeds of the flax plant Lin um u sita
a
.

tiss imu m chiefly grown in

The R ussian seed is usu a
, ,

R ussi and I ndi a l ly mixed with that

from hemp which a
.

l so yiel ds a dryi ng o il to the extent of about

, ,

2 0 per cent While that from India being grown as a mixed

.
, ,

crop with mustard and rape is never perfectl y pure The B altic , .

oil is considered best fo r j apans , and is improved by storing for

a considerable time in tanks in a warm place .

When obtained by cold pressu re of the seeds previously ground

and damped linseed oil is of a bright yellow colour if a
,

highe r
'

temperature be used in the extraction the o il is more or less

brown and t astes much more acrid On exposure to air lins ee d
,
.

a
oil turns easily rancid absorbs oxygen and if spread out in a
'

, ,

su fficiently thin fil m it dries to a neutral subst nce (linoxyn )

which is insoluble in ether but pretty soluble in a
,

l cohol This
property is the one o n which the chie f va
.
.
,

l u e of linseed and other

'

dryi ng oils depends .

Linseed oil is chiefly ad ulterated wi t h other seed oils cotton ,

seed being the most often used for this purpose though men
'

haden and vari ous other fish oils are occasion a

,

l ly employed
A s the density of r a
.

whn se e d o il varies between 0 9 3 2 and 0 9 3 6

at 1 5 C the addi tion of other seed oils or of minera
1

l oil would
°
.
,

cause an appreciable lowering o f this figure whilst rosin or rosin

'

oil woul d raise it A j udicious admixture of both minera

,

. l and
rosin oils wo ul d give a prod uct of normal density but would ,
4 44 PR I N C IPLE S OF L EA TH ER MA N U FA C T UR E

a
and polymeris tion perhaps accompanied by the formation of
anhydrides of t he fa
,
'

t t y acids and a portion of the drier remains ,

dissolved in the boiled oil These driers may be detected by

a
.

boiling an ounce o r so Of t h e oil with dilute hydrochloric acid

, ,

l lowing the mixture to separate into two layers and then s yphon
i n g off the lower into another vessel and testing for met a l s ( lead , ,

manganese zinc ) or acids ( boric oxali c etc )

, , ,
.

Black j apan for patent leathers is made by boiling linseed

oil without blowi ng air through it for at least seve n or eight
, ,

hours with Prussian blue o f with oxides of iron The j apan is .

brownish rather than blue in colour and it is probable that the ,

Pru s sian blue serves merely as a source o f iron oxide which acts _ ,

both as a colouring matter and a drier Other driers such as .

,

litharge are sometimes added and for coloured enamels other “

, ,

pigments are substituted for the P russian blue Most j apans .

now contain nitro cellu lose dissolved in suitable solvents -

( see p
C otton seed Oil ( Fr H u il e de co l on ; Ger Co tion oel or B a
.

um

woll en s a
. .

men oel) is now expressed in enormous quantities in the

’

United States on the continent of Europe and in Great B ritain

, , .

Th e crude oil contains a very character istic colouring matt er

which though natural ly ruby red is sometimes so intense as to
,
-

make the oil appear to be nearly black This colouring matter .

causes the oil to produce stains and i s therefore rem oved by a ,

process of refining , and a product of a straw or golden yellow -

colour is thus obtained The refining is usually effected by

a
.

shaki n g the crude oil with a cold 5 per cent solution of c ustic .

soda using about ten times as mu ch oil as soda solution

, .

Cottonseed oil is on account of its price seldom or never

adulterated but is itself frequently employed as an a dul t er a
, ,

nt of

olive and n e a
,

t s fo o t oils It is a semi drying oil and unsuitable "

for most purpose s in leather manufac ture Fo r a

-

.
,

description of
it s characteristic properties both chemical and physic a
.
_

l the
r eader is referred to Le wko wit sch s Oil s F a ts a
n d Wa
, ,

xes or ’

to Allen s Comm erica l Orga n i c An a

, , ,

ly s is vol ii
’

S es am e Oil ( Fr Ha il e de s es ame ; Ger S es a

. .
,

mo el ; Teel oil
’

.
.
,

Gingeli oil ) is another seed oil usually o f paler colour than cotton ,

seed oil but resembling it in having scarcely any odour and

, ,

possessing a bland and agreeable though not very characteristic , ,

taste It is often used as an adul terant of olive oil

. .

Sesame oil is a no n drying oil which does not easily turn -

rancid When present in other oils it may be detected by

.
,

agitating I O c c of the sample with 5 c c of concentrated hydro

. . . .,

chloric acid in which O I grm of white sugar has previously '

.
 F A TS ,
S OA P S ,
OI L S ,
A ND WA X ES 44 5

been dissolved A fter shaking together for at least ten minutes

the oil and acid are a
.

l lowed to separate when if sesame oil be , ,

present the acid layer will have a marked rose colour the in
, ,

tensity of which increases with the amount of sesame oil in the

samp le ( B audouin s test ) ’
.

Sesame oil is largely used in India for oiling tanned sheep

and g oat skins -
P ersians and has the characteristic property
of being assimilable in large quantities by leather without the
latter appearing oily East India tanned skins often contain 2 5 .

and even 3 0 per cent The oil is applied to them in the wet .

con di tion before they are dried It is easily detected in the oils .

extracted from these s kins by B audouin s test The oil seems ’

.

well adapted for many purposes in leather manufacture

Co d Oil ( Fr H u il e de mor a Leber thr a
.

e ; Ger
. n ) is by far the .

most important oil used by leather manufacturers and is obtained

from the liver of the common cod fish ( Ga dn s M orrhn a
,

) and
severa l other members of the genus Ga
-

dn s Th e chief seats of .

the cod fishery are the coasts and banks of Newfoun dl and Nova ,

Sco t ia the Gul f of St Lawrence the coasts of Norway Denmark

a
and Germ ny the Dogger B ank in the North Se aand the
, , , ,

, ,

shores of Al aska in the P acific Ocean .

The oil was formerly obtained b y keeping the livers o f the

fish in large wooden vats stirring constantly until so much

a
,

decomposition had taken place that the cells containing the oil -

burst , and the oil thus released rose to the surface and w s
skimmed o ff with wooden ladl es Th e crude oil was a l lo w ed to .

deposit any suspended matters by sedimentation in a tank and ,

was then poured into casks ready for sale The brown oil .

so often used by tanners was obtained by boiling the solid matter

left after extracting the oil as above in iron tanks until a
.

l l the
water had evaporated the oil thus liberated was then strained
o ff clarified and put into barrels

Th e purer qu a
, , .

l ities of co d liver oil are now obtained by boiling -

the livers with water and skimming o ff the oil which rises to the
surface Three grades are on the market at the present time
me di cin a
.

l or ordinary bright
, an inferior light brown
”
and dark brown or
-
tanners oil I t is probable that
,
’
.

these steam extracted oils are much more liable to spue

-

than those extracted by the old method at a higher temperature ,

since Eitner has shown that seal oils extracted at a low tem
1

p er a
t u r e spue badly but lose the tendency if heated for some
,

time to 2 50 to 3 0 0 C ° °
.

Genuine cod oil as suitable for use in leather manufacture is

, ,

1
G er be r , 1 8 80 , p . 2 44 .
 44 6 P R I N C I P L ES OF L EA TH E R MA N UFA C T UR E

always m ore or less bro wn in colour of specific gravity about ,

o 9 28 and refractive index 1 4 82 A t present prices it can

“

~
, .

onl y be adulterated with other fish oils rosin or m ineral oil or , , ,

with water gelatine or mucilage Of these rosin oil and petro

, ,
.
, ,

leum are the most frequently employed in sophistication .

An inferior variety of oil k no wn as coast cod made from

the l ive rs o f various fish such as ling haddock and b a ke is a
, ,

l so
’

, , , ,

sold b u t , as it is frequently mixed with oils from other fish refuse

a
-

, ,
_

it has a very poor rep ut tion .

Cod oil together with fn o s t of the other oils obtained from

'

fish livers has the property of producing an intense reddish violet

,
-

colour when a drop of strong sulphu ri c acid is dropped upon

t en or fifteen drops of the oil contained in a white porcelain
tray or saucer The re a c t l o n succeeds still better if instead of
.
'

the oil itself its solution in chloroform carbon di sulphide or

, ,
.

tetrachloride is employed This test although very useful for

the detect ion of liver oils when they a
.
,

re present in o ils of a
totall y different c haracter such as rape or olive oils does no t in
any wa
, ,

y indicate whether a sample of fish oil is pur e or othe rwise

A v ery simil a
.

'

r reaction is given by choles t erol which is present

in wool fat
S ha ( Fr H n il e de r ega ifis chthr a
-

Ger Ha
.

r k l i ver Oi l n ) is

a
in ;
'
-
. .

”
obt in ed from the liver of the basking shark or ice shark .
,
-

chiefly Caught o ff the coast of Norway but the livers of the dog
fish which is a miniature shark a l allied fish a
n d s e v e ra l s o are
'

, ,

sometimes substituted
a
.

Shark oil h s been employed in tanneries as a substitute for

“

cod l iver oil but accordi ng to Le wko wit sch and to All en it is
-

, , ,

a
no longer emplo yed in England From its pale colour it is .

probably principally used to improve the appe rance of darker

oils A ccordi ng to Eitner it s use causes leather to sp ue
'
1

a
/
.
,

b dl y if not previously heated .

Shark oil is characterised b y the very notable proportion of

u n Sap o n ifia
_

b l e matter which it contains which is of the same

a
,

character as that o f sperm oil and not easily removed from its
soap solution by petroleum ether n d where shark o r simil a
,

r ,

oils are suspected ethyl et her should be used for extraction It

,
.

gives a strong violet blue colo ration with concentrated sul phuric -

acid the reaction b eing even more marked than with cod liver
,
~
-

oil itself and of a bluer violet

Wha l e Oil ( Fr H u il e de ba l eine ; Ger Wa llfischtkr a
.
,

n ) is ex

tracted from the blubber of various species of wh a

. .

l e and often ,

contains traces of spermaceti the substance which characterises ,

1
Ger be r , 1 8 86 , p . 2 66 .
44 8 P R I N C I P L E S OF L EA TH ER MA N U FA C T UR E

It s iodine V alue is also high It is not a good leather oil being .

-

very liable to spu e .

Many other varieties of oil extracted from the bodies and not
)

from the livers only of fishes are classed as fish Oil s Menhaden
, .

oil is the principal of these but Japanese oil sardine and he rring , ,

oils and those obtained from the refuse of other fish are scarcely
,

less important though as they are derived from such di fferent

,

sources it is not possible to quote any definite characteristics by

which they may be ide n t ifie d whe n mixed with more valuable '

oils They are usually very liable to spue

Fish Ta l l o w which according to Eitner is a good a
. .

, ,
n d cheap ,
‘

substitute for d egras is the solid grease o btained from di fferent

,

kinds of fish oil by subj ecting them to a low temperature and

separating the matt er which is thus precipitated or ( as in China
a
,

n d Japan ) the solid fat which is extracted at the same time as

the oil from the body of the fish Formerly fish tall ow was only .

obtained from and with Japanese train oil but it is now obtained
from whale blubber This l a
,

tter yields a very pure form of the

.

tallo w which does not nee d any rectification but the Japanese
,

variety which is obtained from fish of the herring family con

tains a sort of fish glue which greatly deteriorates the qu a
.

, ,

the product .

mat ter may be remove d; and the refined produc t has none o f the
,

By careful purific tion however this glutinous

li ty of
a , ,

leather staining properties so characteristic of the crude t a

-

-
ll ow .

Th e refined tallow is sold in square flat cakes melts at 42 C

°
.
, ,

and is not quite so sti ff as ox tallow

D égr a
.

s and 5 od Oil are pro ducts of chamois leather dressing

p
( 45 9 )
. which are used in curry i ng Skins are treated with .

marine animal oils and submitted to oxidation and the surplus ,

and partially altered oil is recovered In the French metho d

'

whale and seal oils as well as liver oils are used and the oxidat ion
is slow and gradual and the residu a
,

l 01 1 being liquid is recovered

, , ,

by pressure and constitutes moell on of which t he first pressing

, ,

(p re m i er e t orse) is the best This is never sold for currying

in its original purity but mixed with further qu a
.

ntities of fish
,

oils tallows and sometimes wool fat it constitut es the ordinary

, ,
-

d egras of commerce The additions though they lower the.

,

value are not to b e considered as simple adulterations since

,
'

the moell o n alone would be less suitable for the purpose A fter .

removal o f as much oil as is possible by dipping in hot water

and pressing a further quantity is recovered by washing with
solutions of potash or soda from which it is separated by addi
tion of acid and constitutes alower quality of d egras The
,

.
,
.

mo ell o n is of such value as a currying material that factories are

 FA TS . S OA P S ,
OI L S ,
A ND WA X ES 44 9

ri min which c ha m o rs rn g 1 s carried on solely for its production ,

the skins being oiled and oxidised repeate dl y till reduced to

rags It is also manufactured by direct oxidation of marine oils
. .

In the Engli sh method of chamoising liver oils are almost

exclusively used and the oxidation is much more rapid and
intense the skins being packed in boxes or piled and a
,

,
l lowed
to heat The pro duct obtained in this way is much more viscous
.
,

and can only be recovered by scouring with alkalies ; and the

product recovered with acid constitutes sod oil In many
, ,
.

En glish factories a modified method is now adopted and a ,

product recovered by pressure which scarcely di ffers from moell on .

A n important peculiarity of d egras and sod oil is its ready

emulsification with water which from its mode of preparation it ,

always naturall y contains and which should be present in a ,

good degras to the extent o f not less than 20 per cent Su ch a

mixture containing water is a sort of natura
.

,
l fat liquor and is ,
-

absorbed much more perfectly by the skins than an oil alone .

So d oils however are frequently evaporated or deprived of ’

, , ,

water by heating above 1 00 C with the obj ect not onl y of e ffect °

a
.
,

ing a fancied improvement but of getting rid more completely of ,

the sul phuric acid which the water is p t to contain This makes .

them more homogeneous and consequentl y much darker in

colour I t is not easy to neutra
,

l ise the acid in an aqueous sod

oil by dire ct addition of alk a
.

li ; possibly ammonia is best adapted

for the purpo se or a suggesti on I think due to Eitner may be
, , ,

adopted of incorporating a small quantity of a suitable soap

, .

In any case very co mplete mixture is r e qu ir e d

,
I f the sulphuric i
.

acid used in recovery has been insu fficient for complete neutrali
sation of t h e l kal i the sod oil will natur a all y contain soaps and
sometimes also free a l ka Free acid and free alka
’

, ,

li l i are both
‘

inj urious to leather the former i f anything the more so darkening , ,

the colour and even rendering the leather tender Wh en d egras

,
'
.

is used in mixture with other fats care should b e taken not to ,

-

raise the temperatur e of the mixture so high as to drive off the

water to which a good dea
, l of its special efficacy is due .

The chemical changes which take place during the chamo1 s

ing process are as yet incompletely understood A large pro “

portion of the g lycerin is dehydrated during the heating

“

fo rming acrolein ( acrylic a

,

l dehyde ) to the action of which it is

very possible t h a t t h e actu a
,
'

l conversion o f the s kin into leather

1
is due while the fatty acids also un dergo oxidation D egras
“

.
,

1
Th is is n eg a
ti ved b y t h e d is c o v e r y of Mr J T
'

Wo o d a
t h t go o d c h a
m i o s

ab d b y a aid a a
. .

in g c n e on e t he fr e e f tty l c s on e, b u t t h e r e si d u e is not

s a
t i fa
st y d eg a(
c or r s se e p .
 P RI N C I P L ES OF L EA TH E R MA N UFA C T URE
“

4 50

therefore a l ways contains considerable quantities o i oxi di sed .

fatty acids which are sometimes a ssociated with ni t rogenous

,

products from the skins and which are soluble in alcohol but , ,

insoluble in petroleum ether To these products Simand gave

the name of D egra Fr dégr a
.

s bil dn er ( d egras former g en e

) and -

,
.

it has been considered a measure of the quality of the degras

but it s exact va
,

a
l ue and functio n is rather doubtful A ccordi ng .

to Sim nd a genuine d egras shoul d contain not less than 1 5 to

,

2 0 per cent of the d egras former as estimated by his method

a
-
.
,

calculated on the dry oil n d a smaller percen t age is also pres ent ,

in the original fish oils ( Fo r method o f estimation see

"

p . It is now known to be simply an oxi di sed oil product ,

and only accidentally contains nitrogen

'

A s the process of d egras manufacture is o b vio u sl y mainly one _

of oxidation many attempts have been made to produce it by

,
-

di rect oxidation of fish oils without the agency of skins both ,

by bl owing air through the oil and by addition of oxidising ,

agents such as nitric acid Eitner states that such oxidised oils
a
.
.

are more liable to spue than the original oils as they alre dy
'

con t ain large quantities of resinised products but this is certainly

not true of a l l artifici a l d egras some of which answers its pur
pose perfectly as a
,

currying material though it is very probably ,

j ustified in other cases Of course the meth ods of successful .

manufacturers are kept as profoun d secrets .

D egras and sod 0 1 1 W hen deprived of water are dark and

a
_ , ,

viscous oils of high specifi c gravi t y ( 0 9 4 5 to

,
n d there

fore heavier than the oils which have been employed in their
manufacture
WA X E S as has already been stated di ffer in their chemic a
.

l
character from true fats in that their fa a
, ,

tty c ids which are

'

, ,

mostly of high molecular weight are combined not with glycerine

but with a l cohols a
, ,
'

l so o f high mol ecular weight and of wax like

,
-

consistency Most waxes are solid b odies of high melting point

.
,

but some oils especially sp erm and bottlenose oils are chemically
, ,

liquid waxes ; wo ol fat Contains a considerable proportion of -

waxes and many marine oils such , for instance as shark liver
contain waxes in sm a
-

, ,

oil ( p . l ler quantity in mixture with

true fatty oils
Sp er m Oil ( Fr H a il e de c acha Ger Sp erma ceti o el Wa lr a
.

l ot . t o el) .
,

is obtained from the sperm whale an inhabitant of the A ntarctic

( Ger D o eglingtkr a
,

seas A rctic sperm

. n ) is a very similar oil .

obtained from the Bottlenose whale These oils are very fluid .
,

do not dry and are excellent lubricating oils for light machinery
and a
, _ ,

l so good lamp oils They contain little if any glyce rides .

,
4 52 P R I N C I P L E S OF L EA TH ER MA N UFA C T UR E

that it is acomplicated mixture of severa

-

l of the higher alcohols

and acids
ja a a
.

p W is not a true wax, but a fat consisting mainly of

n x

the glycerides of palmitic acid and completely a p ifiabl It , s on e .

is a pale yel low hard waxy substance obtained from the berries
of a sumach ( Rhu s su cceda n ea
, ,

A t ordinary temperatures ,

its specific gravity is exactly that of water and it melts at 5 6 C ,

°
.

A n y admixture With other fats would lower the melting point ,

a
but j apan wax is oft e n adul terated with 1 5 to 3 0 per cent of
water I t is chiefly va a
.

. l u ble to leather dressers as substitute .

for b ees wax on acco unt of its lower price

’
-
.

V OLA TILE on ESSE NTI A L 0 1 1 5

These oils are distinguished from those describ ed in the

previous section in that they are capable of dist ill a t 1 o n Without
undergoing a ny serious amount o i deco mposition
'

and are ,
‘

chemically of quite di fferent constitution They occur to some .

considerable extent in Nat ure but those of most importance to ,

the leather trade are produced by the decomposition of more

complicated materials They a ll have characteristic odours
‘

a
.
,

n d often considerable antiseptic power

B ir ch Oil is by f a
.

r the most important of th 1 s class of oils so

“

far as the leather dresser is concerned since it is the substance “

which give s to R ussi a

,

n leather its characteristic odour .

The oil is obtained by destructive distillation from the white

outer bark of t he birch B eta la a lbaand the process by which , ,

the peasants conduct this is one of the rudest that can be imagined “

A cauldron is fill ed with dry birch bark closed and heated over -

, ,

a fire Th e vapours which are evolved are carried by means of

.
,

a pipe t o another vessel which is buried in the groun d and are

, ,

there condensed The dark brown liquid ( birch tar) is allowed

.
-

to cool and the tar which rises to the surface skimm ed o ff The
,
.

tar is sometimes distilled and an oil is thus obtained which does

not give the true birch oil scent very strongly though occasion a
,

-
l ly ,

sold as a refined oil The true odorous substance is evidently

.

of very high boiling point and remains mainly in the tar

The birch tar is a
.
,

l m o st entirely u sed for givi ng leathers a

Russian odour for although it smells somewhat strongly of
,

tarry products the oils causing this smell are far more vol atil e
, ,

than the birch scent itself and therefore di sappear on storing

the leather a short time Ta
,

r obtained from various species .

of pine is sometimes substituted for birch tar but it may rea di ly ,

be distinguished from the latter by the odour and the di fference

 FA TS , S OA P S , OI L S ,
A ND WA X ES 4 53

in the specific gravity Birch tar has a specific gravity of 0 9 2 5 .

to 0 9 45 whilst fir tar has one of 1 0 2 t o 1 0 5 thus the former

,
- -

floats on water while the latter sinks if it b e entirely free from

a
.
,
~

enclosed air Fir tar too gi ves up a yellow colouring matter

.
, ,

to water shaken up with it while birch t r leaves the water ,

colourless B irch tar has a di stinctly acid reaction and must

.
,

not be kept in iron vessels ( see p

Th e leaves and t wigs of A merican black birch ( B eta la l en ta
.

) when
distilled with water o f steam yield an oil which is practically
identical with that of Ga u l ther i ap rocn mben s ( Wintergreen ) and ,

consists almost ent irely of methyl salicylate 1

It is clari fied and .
,

to some extent d ecolo ri sed by fil tration through woollen blankets ,

and redistillation A ton of brushwood is said to yield about .

four pounds of oil This oil has quite a different odour to that .

of the real R ussian oil and cannot be used in the scenting of

leather Sa nda
,

R ussia l wood oil wi t h a little black birch or

W intergreen oil is sometimes employed for scenting sm a
.

ll fancy
articles and bears considerable resemblance to the true R ussia
,

leather odour Black birch aniseed sassafras and vario u s other

essenti a
.
, , ,

l oils are occasionally used in small quantities as pre

se rvat ives and to cover di sagreeable odour in blood seasonings
a
-

, ,

cements and other products used in t he le ther trad e The

,
'

methods employed for their detection and estimation do not ,

however c o m e wit hin the scope of a work such as the present

' i

one Most essenti a

,

. l oils have considerab le power as antiseptics ,

and in preventing mildew and the attacks of insects .

MI NE RAL OILS A ND WA X ES
class of bodies is totall y di fferent in chemic a
This l c o n s t it u
tion from the true oils and waxes containing neither glycerides
fatty acids nor a
, ,

l cohols but consisting of carbon and hydrogen

, ,

only approximately in the proportion of one atom of the former

,

to two of the latter They occur in underground lakes from

which they are obt a
.
,

i ned by springs or borings o r in shales from ,

which they are separated by distillation It is commonly sup .

posed that the y have been formed at some remote peri od of ,

the earth s his t o r y by the decomposition of animal and vegetable

’ ’

matters at a high temperature and under great pressure ( op 2

.

p .

1
Me t h yl a I t h aap l aat d
s a
l i yl a
c t i e s now a
m d e sy n t h e t ic l l y s e s n o o ur,

m wh a t f m t ha a a
.

so t d iff
e t f th t l p d t
e ren ro o e n ur ro uc

p i g a t h i a a
.

Oil f m w ll
2
s ro lly ll d p t l
e m ils or s r n s re ec n c c e e ro e u o s,

th f m
o se hal ropaaffi il b t h mi a
s ll y t h ie d fi it r n o s, u , c e c ,
er e s no e n e

d ist in c t io n .
4 54 P R IN C I P L E S O F L EA TH ER MA N U FA C T UR E

The m ineral oils and waxes are largely capable of being dis
tilled without decomposition but if heated to high temperatures ,

are rea di ly cracked or broken up into simpler and generally

more volatile compoun ds — afact which is employed in the pro
.

duction of gas and the utilisation of some of the heavier products

,

for motor spirit .

They di ffer greatly in their gra vity and boiling point but ,

not much in their ultimate composition co n sisting largely of ,

saturated or nearly saturated hydrocarbons p and henc e .

are little liable to oxidati on , and acted on by few chemical r e

agents From their constitution they are of course u n s a
,

p o n ifi
able a
.

n d in this way can be separated from fats and oils with

“

which they have been mixed ( Fo r particul ars of the method . .

see p 1 7 8 and . ch xi ) A ttempts have been

,
. .

made by oxidation to give them an acid character and fit them for

soap making and by means of emulsifying agents considerabl e
-

quantities can be incorporated in soaps

Th e heavi er miner a
.

l oils are a good deal used in mixture with

‘

other oils and fats for stu ffing leathers those of a speci fic gravity ,

of 0 8 80 to 0 9 00 being usual ly most suitable They are quite .

incapable of spueing and are useful in lessening that tenden cy

,
.

in other oils with which t hey are mixed They have not however , .
,

the same affinity for the leather fibre as some of th e true oils and
are to a certain slight extent volatil e and should genera
,

l ly be
used in mixture rather than a
,

l one .

Most mineral oils when held so that a strong light ( daylight

_ ,

01 electric light rich in ultra violet rays ) falls upon t hem show -

a green or Violet fluorescence or bloom This is very persis .

tent even when the oil is mixed with a large volume of other
,

oils and is often relied upon as a means of detecting them when

,

used as adulterants The test is however not infallible sin c e

.
, , ,

the effect is due to impurities which may be removed by puri

fic a t io n ; or masked by the addition of such subst a nces as nitro
benzene or nitronaphthalene and it also occurs in the hydrocarbon ,

products produced in the distillation by steam of animal oils ,

and is occasionally seen to some extent even in oils which have

not undergone di stillation
Va s e l in e an d Va
.

selin e Oil are the most viscous and d ensest

‘

of the petroleum oil products They di ffer from the solid

pa ra ffin s in chemic a
.

l constitution though their ultimate composi ,

tion is almost the same and some of them are ring compounds
a ra
-

( cyclo p
-
ffin s) T hey are often
. useful constituents of stu ffing
greases
Pa ra fiin Wa
.

x c o nsists of a mixture of hydrocarbons similar

 4 56 P RI N C I P L E S OF L EA TH ER MA N UFA C T UR E

a
fi bl e ,
but often contain small amounts of soap forming material -

( rosin acids )
'
.

The d e t e c t io n and estimation o f 1 0 5 m oils is often a matter

of considerable di fficulty but further particulars on this point Will
,
'

b e found in p 1 80 From their cheapness they are

. .

considerably employed as adulterants of other oils and their ‘

high gravity makes them convenient for adj usting the gravity of
mineral oils when used for th is purpose as the l tter are usually , a
lighter than the fatty oils As currying oils they are not par
t ic ul a
. .

h
a
rl
y suitable thoug often
,
employed in stu ffi ng pick er bands
and other he vily greased leathers They have co nsiderable
antiseptic powers a
.

n d for this reason are useful in leath er greases

, ,

preventing heating and checking mildews

R osin itself is occ a
.

sionally used as an addition to stu ffing

greases and 1 8 said to increase the waterproofness of the leath e r
, ,

and to give it a dri er feel In mixture with about half its weight
.

'

of paraffin wax , and with a little grease if necessary to soften the

_

mixture it is often use d in w aterproofing mixtures which can

, ,

be made to melt at 50 to 60 C Leather will bear immersion

° °
.

in t h e melted mixture without scalding if thoroughly d ried in a

hot stove at a temperature of not less than 50 C before dipping °
. .

A n y great increase of the proportio n of paraffin wax causes the

rosi n to separate R osin consists mainly of free acids which
easily combine with a l ka
.

l ies and alkaline carbonates in boiling

a
.

It is hence largely used in the manu facture of soaps on ccount

o f its cheapness and to render them more s oluble in water The
rosin acids are not so strong as many o f the fatty acids a
.
_

n d rosin

a
,

soaps are therefore somewh t strongly alk alin e R osin soap .

,

precipitated among the ground paper pulp in the rag engine

by addition of alum or sul phate of alumina is l a
,

rgely used as a ,

sizing for co m mon papers .

 C HA PTER XXV I
OI L TA N N A GE S , A ND TH E U S E OF OI L S A N D F A TS
IN C UR R Y I N G

TH E conversion o f skin into leather by the agency of oils and

fats is probably one of the most primitive methods and is used ,

in di fferent ways suited to the skins and fats which are available
by savage races in a l l quarters of the globe In its simplest form
it consists merely in oiling or greasing the wet skin a
.

n d kneading ,

and stretching it as it slowly loses moisture and absorbs the fat .

U nder these con di tions the fibres become coated with a greasy
layer which prevents their adherence after they are once separated
,

by the mechanical treatment A t the same time some chemical .

change takes place in the fibre itself which has a part in its ,

conversion into leather varying in importance according to

the method and fat employed and of which the chemistry will ,
'

be best di scussed after some slight sketch has been given of the
methods themselves .

Th e finest furs are still dressed by ful ling or trea di ng with

oxidisable oils but the most complete sort o f oil leath er is that
,
-

produced by chamoising or oil dressing a process applied to -

the or di nary chamois or wash leathers ( now made from the -

fle sh split or lining of the sheep skin ) and t o the manufacture

- -

of bu ff leather for military purposes The proc ess varies .

somewhat accor ding to the character of the leather but the ,

manufacture of the common wash leather may be taken as a -

type Fo r this purpose the sheep splits are fre ed from the loose -

a
.

and fatty middle layer ( p 62 ) by frizing with a sharp knife

.
.

on beam similar to that used for fleshin g ( fig 3 4 p but .

,
.

much more steeply inclined The process is rather o n e of scraping

.

than cutting and was originally adopted to remove the grain from
,

the deer skins which were largely used for glove—leathers since
-

oil dressing does not easily penetrate a skin with the grain surface
-

intact The fleshes are usually delimed by drenching but

.
,

removal of fat is unimportant A fter being well drained they.

are stocked for some time with sawdust till they become
partiall y dry and porous the common faller stocks shown in
fig 2 6 p 1 64 being gener a
,

.
,
. l ly employed
,
During the stoc king .

45 7
4 5 8 P R I N C I P L E S OF L EA TH ER MA N UFA C T URE
care m u s t b e taken that the goods are not overheated by the
r
‘

friction produced When the skins have become opaque from

.

the inclusion of air between the fibres they are according to the
.
,

Continental method sha ken out and oiled on the table and , ,

after folding into bundles are put back in the sto cks
'

In
En gl a
.

n d t h e oil is usually added in small quantities , during

‘ '

the stocking and becomes rapi dl y and evenly distributed by

the motion of the skins In England cod oil is almost ex .

c l u sive l y employed bu t on the Continent a considerable pro

“

portion of seal and whale oils is used A s the goods are apt to .

heat not only from friction but from the oxidation o f the oils “

empl oyed they are removed from the stocks at interva

, ,

l s and
allowed to cool usu a
,

lly hung on hooks exposed to the air In

France this exposure to the a
, .

i r is much more considerable than

in England the skins being hung for eight or twelve hours after
,

each stocking The drying rooms are kept moderately warm

.
,

and a good deal of oxidation of the oil takes place in them ,

which material ly affects the character of the product and esp e ci

a
,

l ly o i the residual oil or d egras which is afterwards squeezed ,

out of the skins and used for currying (p Great care is .

required to prevent any parts of the ski ns becoming dry before

they are compl etely saturated by the oil which would cause ,

hard and transparent patches which the o il will n o t afterwards

'
‘

penetrate A fter each expo sure to t he air the skins are oiled on
.

the table and ret urned to the stocks Th e stocking has to be .

continued for many hours even for wash leather ; and as it ,

-

proceeds the Skins lose the smell of limed skin , and acquire a
peculiar mustard like odour from the volatile products of
-

oxidation of the oils When the skins are completely saturat ed

.

they are accordi ng to the English method packed in boxes and

a
, ,

l lowed to heat spontaneously by oxidation of the oils during ,

whi ch great care is required especially at the outset that the t em “

p e ra
, ,

t u r e does not ri se so high as to destroy the ski ns To prevent

“

this they are removed at intervals from the boxes and spread on
the floor to cool and then r e packed and this treatment is con -

t inu e d until th e oxidation is complete and the skins cease to

heat During the heating l arg e quantities of volatile and very
pungent products are given o ff and especi a
.

l ly acrolein ( acrylic ,

aldehyde from the dehydration of the glycerin ) which is e x c es

, ,

sivel y irritating to t h e eyes The German method is not unlike .

the English but in France the packing in boxes is omitted and

, ,

the oxidation is completed in warm stoves in which the goods

a
,

are hung on hooks The heating in this case is much more .

moderate and the oil less thickened result Which is partly ,

460 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

German cabinetmaker named Kl emm by whom the secret was ,

sold to Prell er who manufactured it in Southwark under the

,

name of Crown leather Klemm used flour o x brains .

,
-

butter milk and soft fat which was made int o a paste with
, , ,

water and spread on t he limed drenched and par tiall y dried

, , ,
.

skins which were rolled into bun dl es and drummed in slightly

, ,

warme d drums for some hours taken out again dried slightly , ,

and coated with the mixture and again drummed Fo r thick , .

hides the process was repeated a third time drumming in each

operation for about eight hours The leather Wa
,

s us ed for laces

picker bands light belts and other purp oses where gr e a

.
,

,
t t o u gh
, j
~

ness and flexibility were required It was found by further

.
.

experience ( if indeed it was not known to Klemm himself) that the

only really essenti a l ingre di ents of the mixture were the soft
fat s and flour and even the latt er could for some sorts of leather , ,

be di spensed with It was further ascertained that only the gluten

.

or albuminous part of the flour was absorb ed by the leather the ,

starch serving mainly to facili tate the emulsification of the fats .

Th e pr oportions used in t he paste are about se v en parts of flour ,

seven parts of soft fat such as horse grease two parts of tallow , ,

four parts of water and a little salt or ni tre to act as an anti

septic Other greases su ch a s mixtures of t a
,

l low and oil can '

.
, ,

be substituted for the horse grease and pipe —clay o r ochre may
'

to some extent take the place of the flour while soap may a
,

a
l so ,

be dded and fish oils are occasionally used The similarity of

the mixtures used to the tawing paste in c a
.
.
,

l f and glove kid -

dressin g (p p 2 47 2 52 ) is obvious and Klemm had an earlier

\
.
, ,

process in which the operation j ust described was pre ceded by a

slight al um tannage a n d which was al most identical in its detail
,

with the methods now in use for the production of s o cal led raw -

hide On the other hand it is nearly allied to the production of

.
,

R iems or raw hide straps in Sou t h A frica for which a long

,
-

th ong rs cut spirally from a hide and wound into a sort of skein ,

which is suspended from a crossbar with a heavy weight at its

lower end and oiled and twisted with frequent ch a
,
n ges o f posi ,
.

tion until the water is dried out and the thong is saturated with
,

fat forming a very tou gh and durable leather A similar material

can be made by full ing or otherwise working grease into ar a
.
,

w
'

hide prepared for tanning Eitner examin ed samples of Crown

leather chemic a
.

l ly by removing the gluten of the flour with

an alk a
,

l ine sol ution and found that an i m perfectly chamoise d '

leather remained which when restu ffed with fat was much less
, , ,

full and carried a much smaller quantity of grease than before

,
.

V arious theories have been proposed to explain the reaction

 OI L S A N D FA TS IN C URR YI N G

which takes place 1 n the production of oil leathers Fahrion

ha
-

s shown that chamoising can be done with vegetable dryi ng

oils such as linseed and the white Japanese leather used for
,

brace tabs is produced with rape oil Knapp supposed that it

a
.

was merely case i n which the small est fibrils of the hide were
coat ed with the products of the oxidation of oils and so prevented ,

from adhering together and protected from the action o f water

,

by the sort of waterproof coating which was formed This . .

explanation is scarcely feasible in the face of the fact that chamois

leather can be treated even with hot dilute solutions of the caustic
a l kal ies without destruction while cotton fibres waterproofed ,

by treatment with drying oils have their coating entirely removed

by treatment with alkalies Lie t z m a n n supposed that the whole
.

of the gelatinous fibres were removed in the li ming and subsequent

treatment , and that the finished leather consisted only of the
skeleton of yellow or elastic fibre which exists in the skin and
which is remarkable for its resistance to heat acids and a
,

l kalies , ,
.

U nfortunately for the theory t h e proportion of these fibres in ,

the entire skin is a very small one and they exist mainly if not , ,

entirely in the grain which is removed by splitting their

, , ,

occurrence at all in the fle sh split being doubtful We know -

.

that aldehydes are capable of converting gelat inous substances

into a materi a l very sim ilar in its power of resisting hot water
and a l ka
l ine solutions to the fibre of chamois leather but the vi ew ,

that acrylic ald ehyde which is derived from the glycerin in the
,

heating of the skins is the active agent is no longer tenable since

, ,

J T Wood has shown th at excellent chamois leather can b e pro

‘

. .

d u c e d b y the use of the free fatty acids of fish oils from which the
glycerin ha The a
-

s been entirely removed l dehyde theory is not .

entirely di sproved by this since aldehydes are produced ( see

'

pp 43 2 449 ) from the splitting of oxi di sable oils at the double

linkage and in a
.
,

,
l l cases where perfect chamoising is produced
intense oxidation takes place but it must be admitted that it ,

seems less probable than formerly and we have still to look for a ,

complete explanation There is no doubt that the coating of the

.

fibres with oil products does take place and it is possible that ,

they enter into some sort of combination with the hide substance -

which is no longer soluble in alkalies Such a coating is probably .

a powerful factor in the leathering of Crown leather and other

similar products which are not washed out with a l kaline solutions
Kn a
.

'

p p p ro ve d by treating raw pelt which had been dehyd rated

'

with alcohol with a very dilute alcoholic solution of stearic acid

,

that a thin coating of stearic acid on the fibres wo uld confer

great softness and considerable resistance to water Even where .
462 P R I N C I P L E S OF L EA TH ER MA N U FA C TUR E

r1 c or other fatty acid is purposely added to a

no s t e a l cohol u sed
for dehydrating pelt traces are present from the decomposition
,

FI G . 1 03 .
— S c o u r in l
g ag
r e a
Se l —s kin s b y H ad
n .

FIG . Io 4 .
—Sc o u r in g Ma
c h in e

of the natural fat of the skin and there is little doubt that this
is the cause why such a
,

l cohol leathers are much m ore di fficult

to wet back again to the state of pelt than wo u ld a p r i or i be
'

expected and why hide powder dehydrated in this way is u n

,
-
 6
4 4 P RI N C I P L E S OF L EA THER MA N UFA C T URE

but is present s o metimes ev en in a higher degree in tanned or

tawed leathers in which the fibres are already so far isol a
, ,

,
ted
as to make the access of the fat easy Even the possibilit y .

of oil tannage is not excluded where the fibre is not already com
-

I o 6 — Sh
. aiv ng a
M c h in e .

FI G . 1 0 7 .
—B a
nd -
kn if e Sp lit t in g Ma
c hin e .

saturated with o th er tanning agents or where these gents

p l e t el y
from their nature have not so firm a hold on the fibre as to be
,
,
“
a ,

incapabl e of being displaced by the action of oil products It is -

therefore obviou s that we may apply some of the ideas which we

have formed with regard to oil —tannages to the action of fats
.

a
upon tanned l eather In the first place it must be remembered
that gelatinous matters r e as a rule insoluble in fats and vice
,
 OI L S A N D FA TS IN C UR R Y I N G 4 65

ve rs athat
,
fats are incapable of penetrating dry and solid gela
timous fibres If the skin becomes dry in the chamoising process
that part rem a
.

ins raw I t may therefore be concluded that fats

.

and oils have little power in themselves of isolating t he fibrils ,

and that this must be accomplished by other agencies since if

they a
,

re still adhe r ing together the fat s cannot penetrate them .

Hence the necessity of moisture which keeps the fibres soft and ,

di visible and wit h raw hide t he importance of powerful

‘

mechanical treatment which will work t he minute glob ules of ,

fat between the fibrils In the case of tanned leathers the last .

condi tion is less important since the fibres are already isolated ,

by the tannage and capill arity assists t he penetration Even in

,
.

this case the distribution of the fat is much assisted if it is already

in a s tate of fine divi sion ( emul sification) and if the surface ,

tension ( p 88) between it and water is low as is the case with

‘
.
-

d egras and other partially oxidised oils On this rather than

on any speci a
.

l chemical affinity probably depends the importance

of the d egras former and o t he r p r o du c t s of o x idation which
‘

a
-

r e pr esent in d egras and the di fference in penetrating power

,

of di fferent oils So long as oil remains in an un divided con

.

dition so long can it be squeezed out and the leather will feel ,

and appear greasy ; while when it is thoroughly emulsified

and a dh erent to the fibre it can no longer be expell ed by m ec ha
,

ni

ca
,

l means No doubt the di fferent power of different tannages

to carry grease without appearing greasy is a
.

l so related to
the degree of isolation of t h e fi bril s and their surface tension
with regard to fats We may j udge that the more rea di ly an oil
.

can be emul sified the more freely and completely it is likely to

,

fix itself on the leather fibre Fo r this reason and for their .

,

power of emulsifying other oils the sulphonated fish o il s n o w so ,

'

largely used on sole leather would probably be useful constituents

of stuffing greases .

It is a practically invariabl e r ule that the leather fibre must

be wet when it is stu ffed Th e surface tension ( see p 8 8)
“

between the water a nd t he fa

. .

t s is less than that of eithe r with

'

regard to air ( p 9 0 ) and therefore as the water dries out of the

small interstices of the leather the fat follows it in and gradu a
.
,

l ly
a
, ,

takes its place Gener l ly speaking the amount of water should

.
,

be such that some exudes in minute drops when the leather is

pinched that is that not only the minutest spaces between the
, ,

fibrils are fil led but to a considerable extent even the larger ones
,

between the fibre bun dl es

han d s ta
.

In ffing the leather is now coated on the flesh side

or occasion a
-

l ly on both sides with dubbing which is a pasty , ,

30 .
4 66 P RI N C I P L E S OF L EA TH ER M A N UFA C TUR E

mixture of fats usually mainly composed of cod oil and tall ow ,

Which is applied rather thickly With a br ush and smoothed down

with the fleshy part of the forearm Wh en such constituents .

are melted together the harder fats dissolve in the oils and
a s the mixture cools much of the hard fats again cryst a
,

llises out .

To make a good dubbing the cooling fa t s must be stirred con

t in u o u sl y till cool as otherwise the mixture separates into little
,

globular masses of crystals with liq uid 0 1 1 between them instead

of forming a uniform body of s a
,

l ve like consistency Th e pro

portions of the hard a
-
. .

n d soft constituents of the dubbing sho u ld

a
be adj usted to the seas on and to the temperature at Which the “

drying of t h e stu ffed leather is to tak e p lace so th t on the one “

, ,

hand the dubbing will not melt and run o ff and on the other
, , , ,

that it sho ul d n ot solidify more than is necessary as only the ,

liquid solution which remains entangled among the crystals can

be absorbed by the leather Th e solid crystall ine fats remain
on the surface and a
.

r e scraped o ff by the sleeker in finishing as

table grease which is gen erally r e melted and used over again
-
'

a
.
,

I t does not answer in hand s t u ffin g to carry this r e use t o o far

- -

as the t able grease contains only the harder p rts of the fat
-

with a continually increasing proportion of stearic acid so that if .

,

a dubbing be made continuously of table—grease and oil in the

.
,

end little but the latter will be absorbed by the leather while ,

wh ere fresh tallow is used a portion of its softer constituents

rem a
,

ins dissolved in the oil The principal function of the .

harder fats is the mechanical o ne of retaining the oil on the

'

surface of the leather ; and to a certain extent they may

"

be replaced by other solids such as steatite French ,

or perhaps other pulpy materials Th e use of a .

.

portion of soft fat such as bone—fat or the better sorts of, ,

glue grease is quite practicable especially if mixed with t h e

-

a
, ,

harder table grease -

The drying of hand —stu ffed le ther sho uld b e slow to allow ,

time for the absorption of the grease ; and t he temperature

shoul d be so regulated as to keep the dubbing in a soft but not
liquid condition In winter if t h e temperature of the outer air
.
,

b e raised su fficiently for this the drying will b e t o o keen ( Cp , _

.

p. and t he water will be dried out before the grease is

properly absorbed It is therefore best in cold weather to
.
, ,

maintain the ventilation mainly by circul ating the air in t he

roo m with little admission from the ou tside and in extreme
cases even artifici a
, ,

l damping of the air may be advantageous .

Sometimes the tendency to mildew during slow and warm

drying is very troublesome This may be prevented by the .
4 68 P RI N C I P L ES OF L EA TH ER MA N UFA C T UR E

set out with the sleeker on the table while yet warm and d ried
'

under much the same conditions as have been describ ed with

regard to hand stu ffed goods .

In drum stu ffing t h e hardness of the grease is limited by its

melting point which must not be So high as to damage the
,

leath er bu t it may be as soft as is desired A s the grease 1 s forced

,
.

by mechanical means into the interior of the leather there is no

danger of its running o ff but the drying must ta ke place at such
a
“

a temperature as to keep it at l east in a p rtially soft conditi on

a
,

s the dr u mmi ng o nl y fo rces it into the coarser spaces of the

leather and does not c o mp l e t e it s distribution o n the fibre By
'

.
, o

the use of exceedingly hard greases such as stearine ( p 440 )

a
.
,

n d oleo stearine ( p 4 sometimes with addition s of paraffin

a
-
.

wax it is p ossible to introduce I mmense quantities of grease n d

, ,

e t to obtain a leather which wi l l board up to a good colour I

y n .

A merica it is not unusual to reckon 1 00 or even 1 1 5 lb of greases .

to 1 0 0 lb of leather weighed dr y after scouring or estimated

from its wet weight a
.
,

n d the wh ole of this 1 s abs o rbed scarcely

, ,

anything co ming o ff in settin g The leather as it comes from

“
.

the drum 1 s dark brown but when bent sharpl y l n boarding ,

to form the grain after cooling and drying t h e very hard and
, ,

c rystalline fats crumble into wh ite powder and the leather ,

takes a light and pretty colour Such leather would of course .

darken at once if it were held to the fire but would again brighten ,

So me portion of
”
o n cooling and br e aking up with the board “
.
. .

liquid fats such as d egras or fish oil should be contained in

, ,

the stu ffing grease as the solid fats alone wil l not penetrate to
,

the heart of the fibres but will leave the leather dry and ,

harsh .

By drum — s t u ffin g it is possible t o incorpo rate solid matter

“

with the leather and barytes ( ground heavy spar or barium ‘

-

a
,

sulphate) was formerl y much used for this purpose but has now
'

been abandoned as too easily detected Organic fillers such s .

,

flour c ase1 n r o srn or rosin soaps might probably be used in some

,
'

, ,

cases with advantage and most colloidal precipitates would be

'

'

absorbed Glue is often used as a s ti ffener in rolling splits for

.
'

insoles Glucose is still used as an adulterant of leather but is

.
,

not introduced in the drum but by painting the goods with ,

a
syrup before stuffing It not only adds weight and gives the .
_ ,

leather a lighter colour than n equivalent quantity of grease ,

but at the same time lessens its toughness and absorbs moisture ,

and ought to be prohibited in England as it already is in Germany

On the detec t ion of adul teration of lea
.
,

ther see p 21 2 . .

D rum st u ffin g is in this country mainly appl ied to shoe leathers

-

,
 OI L S A N D F A TS I N C URR YI N G 469
‘

b ut in A meri ca with the hot air drum is coming i nto increasing

,
-

use for h arness and even belti ng,

"

A method of stu ffing is used in Germany for heavy belting

and the like which a p p ea rs a
.

t first glance to contradi ct the _

axiom that leather must be stu ffed wet It is calle d Ein br en n en

,
.

( to burn in and consists in first drying at a high temperature

( 50
°
C ) to ensure the abs e nce of a l l moisture and then either
pouring hot melted t a
.
,

l low over the leather on a table and holding

it over ab r a z ie r to all ow the grease to sink in
‘

or dipping it
completely in a b a th of m elted t a
,

l l o w f The exception is only

_

ap parent because though the leather is at t his stage completely

saturated with t a
, ,

a
l low it is only after wetting and drumming
,

th t it attains the flexibility due to true stu ffing Similar methods

are applicable to a
.

l u m e d leathers and even to chrome leather

and so c a
,

-
l led waterp roof or anhydro us leather is made by
immersing thoroughly dried l eather in a bath of 2 parts of rosin
and 1 of paraffin or some similar mixture If the leather is not
,
.

first th o roughly dried it is scal ded and destroyed b ythe hot grease
-

, .

The most troublesome defect to which stu ffed leathers are

liable is known as spueing and is of two kinds of which the , ,

first and less serious (perhaps more p roperly distinguish ed as

striking out consists of a white e fflo r e s c en c e rather like
incipient mo ul d which is easily wiped o ff but generall y reappears
, , .

This is due to the crystallisation of the harder fats and especial l y ,

of the free f atty acids on the surface of t he leather and is almost

, ,

sure to occur in greater or less degree when the hard fats such as
tall ow or stearine are combined with a non drying oil such as
n ea
-

t s fo o t ; o r wh e n soft fats are present in the leather I t is

'

sometimes combined with actual mildew fro mwhich it is rather

.

difficult to distinguish even under the microscope and may be

caused by fungoid plants which not onl y mechanic a
, ,

l ly expel
“

the fats by their growth but probably promote their rancidity ,

and the separation of the crystalline fatty acids It is at most .

only a defect of appearance and does not in any way inj ure the
leather : I t wa s constantly present in calf kid from the n e a
,

t s fo o t -

oil used in finishing and was in this case rather liked by the
,

buyers who for some reason regarded it as a proof of quality

, .

A very similar app earance may be c aused by the use of s olutions

of barium chloride a l um or other mineral salts for weightin g
, ,

or other purposes but is persistent when the leather is held to

the fire while the cryst a
,
l lised fatty acids melt and disappear .

The fatty acids are at once removed by a drop of b enzene or

petroleum spirit but unaffected by water while with water
, ,

soluble salts the reverse occurs .

 P R I N C I P L ES OF L EA TH ER MA N U F A C T UR E

Th e second form of spueing is of a much more troubl esome

character and makes its first appe arance as min u te spots or
,
.

pimples of resinous matter raised above the surface of the “

leather which if removed genera

,
l ly reappear and which may ,

become so bad as to form a sticky resinous coating over the

whole surface The exuded matter consists of the oxidised
.

products of oxidisable oils but the cause of its appearance is not

a
.
,

l ways easy to explain The currier generally attributes it to

'

adul terated oils and 1 t m ust be admitted that some oils almost
,

invariably produce it but it appears occasionall y when o nl y the

,

purest and absolutely genuine cod oil has be en used It can _ .

onl y be produced from drying or semi drying oils which include -

all the ordinary fish oils and most of the vegetable seed oils but
can never arise from t a
,

ll ow or stearine from mineral oils o r ,

-

vaseline or from genuine non drying oils such as tallow neat s

foot sperm o r minera
-

, , ,

,
l oils nor probably from rosin oil : It is
, , , ,
.

favoured by causes which promote the oxidation of oils such as ,

moist heat with li mited access of air and by the presence of

oxygen carri ers such as iron s a l ts in blacks and possibly a
,

,
l so by-

the presence of free acids A large amount of free fatty acid in .

the oils themselves is suspicious not only because the free acids ,

oxi di se more freely than the neutral fats but because their ,

presence is an evidence of t he tendency to rancidity and change

in the oil It is also said to be caused by p revious mildewing of
the leath er and cert a
.

inly often occurs where the grain has been

rendered porous by bacteri a
,

l action in the soaks limes or bates , , ,

probably from the greater quantity of oil absorbed by these parts

Wh ile it is easy to say which oils m a
.

y p o ssib l y spue there is

'

no known chemical test which will foretell whether a given

1
sample is likely to do so under ordinary conditions Eitner
states that se a
.

l oil extracted at a low tem perat ure is very liable

to spue but that when heated for a considerable time to a tem
p er a
,

t u re of 2 5 0 to 2 9 0 C it darkens in colour and loses the

a
° °
.

tendency This is probably true of m ny other marine oils

.
,

and may be one cause of the frequent trouble with modern oils ,

many of which especially the lighter coloured kinds are extracted

, ,

by steam at a temperature below boiling point It is very .

probable that one e ffect o i heating to a considerable temperature

-

is to dehydrate and separate albu minous or gelatinous matters .

which are present in the fresh oils and which probably increase ,

their tendency to decomposition Many of these substances .

separate as foots from oils during long storing and such old ,

oils are said to be less liable to spue than those of recen t manu
1 8 80 , p
G e rb e r , 1 . 243 .
47 2 P RI N C I P L ES OF L EA TH ER MA N UFA C T UR E

ment for the leather If a

a
means of emulsifying olive lard or
.
.

, ,

tallow oil ( with the addition of a little palm oil ) with lbuminous
matter as perfectly as in the egg could be discovered the problem ,

of an egg yolk substitute would in all probability be solved

Milk and cream are a
.

l so natural fat liquors -

.

Emu ls ion s are suspensions of one liquid 1 n another in which ,

bein g freely suspended the globules always take a spherical

,

form . If oil be shaken up with water a system of this sort is

formed but quickly separates the oil floating to the surface
, , ,

but under suitable conditions such mixt ures may remain per
m anent This is promoted by smallness of the globules By
sufficiently vigorous me chanic a
. .

l mixing tolerably permanent

emulsions may be formed of oil and water alone and the globules
of butter in milk can be so broken up by the centrifuga
,

a
l emul sifier
th t cream will n o longer rise on standing Mere shaking is .

not the most efficient way o f producing emulsions in the centri

fugal emul sifier the m ixture is forced out through a narrow slit .

between the edge s of two di scs so that the oil i ssues as thin .

sheets which break up into minute globu les and o n the small
, , ,
’

scale a very e ffective appliance consists of a cylindri cal vessel

,

with a piston covered with fine gauze or perforated metal ,

through which the oil is force d in thin streams preferably not of ,

,

circular form which also b reak up into globules ( see p

,
.

While it is possible to emulsify oil and water simply the pro

cess is much facilitated b y t he a
,

ddit io n of some third substance

'

which lowers the interfacial ten sion between t he two liquids or

-

coats the globul es wh en formed so as to prevent their subsequent

coalescence and usually both e ffects are combined S oaps of
,
.

various sorts are among the most usual and effective additions ,

and probably act i n both ways lowering t h e tension between ,

a
the liquids and coating t h e globules when forme d These soaps
,
.

are not alw ys added directly All commercial animal and .

vegetable oils contain at least traces of free fatty acids which

are s a p o n ifie d by the addition not only of caustic a l ka
,

l ies b u t
‘

even of a mm o n ia or a l kaline carbonates and where the oils are ,

a
'

almost neutral emulsification is greatly assisted by the ad di tion

cid With m in er a
,

t o them of a little commercial oleic l o il s

which are u n s a p o n ifia b l e alkalies a
.
,

l one have little saponifying

e ffect and t he a
,

ddition of soaps in some form is necessary

A lmost any soap will assist s a p o n ific a
.
,

t io n and ordinary ,

domestic soaps are often used but fo r so m e purposes are u n

desirably alk line B y the cold s a a p o n ific a
,
_

. t io n process described
on p 42 7 perfectly neutral or even superfatted soaps are easily
made from any s a p o n ifia
.

bl e oil and if su fficient excess of oil ,

 OI L S A N D FA TS I N C URR YI N G

be used the soap dissolves at once to a fat liquor Fo r many -

;

purp oses of leather manufacture castor oil has been found par
t ic u l a rl y suitable The quantity of soap used should not be
‘

too large ; 2 to 4 p e r cent is gene ra

.

ll y su fficient and larger

quantities are less effecti v e R a
.
,

in or steam water should be us ed .

,

as the p resence of the lime and magnesia salts of hard waters

ca uses precipitation of insoluble soaps which do not assist ,

emulsification and may make the leather sticky or produce other

, ,

ill effects .

Sulphat ed oils ( p 4 41 ) have come larg ely into use for pro
.

du cin g e mulsion s Th e earliest of these to be used was the

'

.
_

Turkey red oil of the textile trades which is sulphated castor

and after neutr a l isation gener a
-

, ,

l l y with ammonia is miscible

with water in a
, ,

ll proportions U sed alone it produces nice soft .

,

leathers though Eitner states t hat they are apt to harden and
becom e tender with time but genera
,

l ly it I s used to emulsify
,

other oils .

Ot her sulphated oi l s however are now more largely used , , ,

and especially sulphated fish oils have become an important

article of commerce These as they are put on the market
'

.
, ,

are usuall y inte nded for direct application to leather and ,

especially to assist in retaining the colour of sole leather during

drying and they frequently contai n a large proportion of mineral
,
.

oil Fo r use in fat l iquors however it would be better to em

.
-

, ,

ploy the sul phat ed oil alone and mix the mineral or organic ,

oils as desired On the analysis of s ul phated oil s much has

been written lately and r ecent volumes of the A merica
.
.

Lea ther Chemis ts Jou r n a

,

l and of that of the must be

L
’

a
con sulted .

In fat liquoring chrome leathers so p is an import ant con

-

s t it u e n t ,not merely as promoting emulsification but in fixing ,

the basic tannin g chrome salt by forming with it an insoluble

soap The same thing m a
,

.
y take p lace with alumina and other
mineral tannages It is very important that before goods are “

fat liquored a
.

l l the soluble salts should be removed by washi ng ,

or rendered insoluble by so called neutralisation as otherwi se -

they will bleed into the fat liquor and precipitate the s oap in it -

as an insoluble sticky substance which will adhere to the surface ,

of the leather and render subsequent dyeing and glazing impossibl e .

Em ul sion may be brought about by other means than those

j ust described Viscous substance s such as dextri ne gums
.
, ,

and proteids such as albumen render emulsion easier, either by

lowering the surface tension or by coating the globules or by
rendering them less mobile and so l ess in clined to coalesce a
,

nd , ,
47 4 P RI N C I P L ES OF L EA TH ER MA N UFA C T UR E

fine powders such as starch may also coat the gl obul es

‘

. Th e
starch of the flour used in tawing pastes and in the manufacture
of Crown leather are useful in this way though they are not
,

directly absorbed by the leather and some mineral powders have

,

the same effect but could not be used in fat liquors

,
-
.
47 6 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E
blind to co nceal the secret A pparently the first j apanned leather.

was put on the market in 1 82 2 Whil e enamelled was not made

till 1 83 7 The n ext patent was in 1 854 for details of m a n u fa
,

. c

ture when the varnish ordinari ly used was stated to consist of

,

oil amber Prussian blue litharge white lead ochre, whiting

asphalt and sometimes copal and the use of in dia
, , , , , ,

, r u bb e r is ,

claimed .

A n y or dinary tannage of dressing leather can be j apanned

but as little fat of a
,

n y s o r t can be used in currying the tannag e

k
,
“

should be soft and mellow for shoe leathers and on the other
hand for the thicker leathers used for h a
, ,
'

, rn e ss t h e
grain must
be firm and not inclined to pipe A n essential point is that .

the leath er must not contain grease or fatty oil which causes ,

the j apan to throw o ff or ru n unevenly or dulls its lustre , ,

a
and even traces of grease or oil brought in contact with the
'

finished j apan m ke it soft and sticky Th e wri ter has known .

a case where contact with dyed and finished East In di a sheep

skins used as lining ruined a parcel of dress shoe uppers though
- -

they showed no sign of greasiness but were proved by analysi s ,

to contain 2 0 per cent of sesame oil The beam work shoul d

therefore be planned to remove a s much natur a
. .

l gr ease as possible ,

but it has now become alm ost universal to degrease leather

with solvents which is intended for j ap anning Fo r sh o e leath ers

a
.

it is most i mportant t hat the leather sh oul d not st retch as ,

a
otherwise the j apan cr cks and gapes in lastin g and therefore ,

prob bly the bati ng or puering should be very moderate if indeed ,

simple deliming is no t sufficient since the more the elastin is

'

removed the greater the tendency the leather has to stretch .

The same points must be considered in chrome l eather intended

for j apanning and especi a l ly that of the absence of stretch
'

Ca
.
,

rry ing — This is much like that of other leathers and of

’

course dependent on the nature of the goods b u t here again all ,

op erations must be directed to remove stretch The leather must .

be made as level in substance as possible and for j apan must be ,

shaved ve r y s m o o t h but for enamel this is less important as the

'

, ,

goods are flu ffe d or whitened b efore coating and generally lightl y ,

buffed on the grain The goods are set out thoro ughly on a clean
.

table lightly oiled on grain with linseed oil and either dried out
or printed when dry enough A will ow g rain is that usu a
, ,

l ly
'

given .

Dubbing containing any animal fat must be carefully avoided ,

but cod oil may be sparingly used and on the Continen t and in
A merica dégra Fa
,

s is generall y empl oyed t liquoring seems a .

-

likely way of getting softness with a minimum of suitable oil ,

 ]A P A NN ED A N D EN A M ELL E D LEA TH ER S 47 7

but experiment is desirable as to the oils which may be safely

a
employed and their quantity .

When dry goods f o r en melling are either flu ffe d or whitened

, ,

and if too hard they may be softened by sleeking on the flesh

and lightly gra i ned with cork board on the flesh side -
.

In the United States many large hides are finished in dull

coloured enamels for upholstery A very thin buffing is taken

a
.

o ff the grain with the b and knife which is often fini shed bright -

a
and smoot h in colours for h t sweats and the like The u p -
.

ho l st e ry leathers r e probabl y printed before enamelling and the

grain is r a
,

ised afterwards by boardi ng

a a
.

— In the o rdinary English process the goods are

j p n n i n g .

now nailed down on large boards perhaps 6 feet by 8 feet which , ,

fit int o the stoves like drawers and which are covered first With ,

thick felt and then with brown paper B efore nailing on any holes .
,

in the hides which the j apan might pass through are patched with
brown p a p er a n d glue I t is said that a coating of fullers earth
’
.

is sometimes gi ven at this stage to remove t he last traces of

'

grease but the writer has never actually seen it done and it is
, ,

probably quite unnecessary wi th benzine degreasing Some .

times the leather is darkened by the application of a blac k or dark

blue dye before j apan ni ng
There is no secret about the actu a
.

l application of the j apan ,

which is ( or used to be ) done b y labourers hired by the master

j apanner The skins first receive a coat of a thick j apan l a
‘

i d on
wi th a finely toothed sleeker ( r a cl e tt e r a
.
,

ili ke) and d ri ed in the

stove and this process is so m e t im es re p e a
, ,

,
t e d till the coating is
sufficiently thick when it is smoothed down with a pumice stone
,
.

This used to be done by hand with a s t one shaped somewhat like

a
a horn but in Germany a rotating stone carri ed on a double
'

, ,

j ointed r m driven by belts and moved over the leather by hand

is usu a
,
'

l ly employed while the leather is supp orted on a stone

,

slab .

The English drying Stoves are mostl y unventilated and heated ,

by a close gri diron of steam pipes on the floor to a temperature -

which may be as high as 7 1 C ( 1 60 F German stoves do not

° °

much e x c e e d 6o C ( 1 40 E ) but a portion of the drying is a

.

l ways
'
° °

done in the sun A mericans are said for speci a

.
,

. l purposes to go
as high as 9 3 C ( 20 0 in which case the leather is previously
° °

prepared with a solution of a

.

l um and borax 2 oz of each to the ,

.

gall on D rying is there also completed in the sun

In the German and A merican methods the skins are usu a
. .

ll y
stretched on frames often fitted with screws or toggle j oints
,
-

at the corners to ad mit of their expansion after the skins are

47 8 P R I N C I P L E S OF L EA TH ER M A N UFA C T UR E

stretched instead o f on boards The skins are put o n the frames

da mp a
.
,

a
n d often r e ceive their first coat in this stage so t h at t h e
'

damp and the thick natur e of t he j ap n may preven t its pene

t ra
,

t io n while in others the skins receive a coating of size somewhat

,

similar to that used on waxed calf In Germany the first coats

a a
.

r e often applied with a sort of s patul on a stone slab b ut later ,

coats are thinned with turpentine and applied with a broad

a
"

brush ( n en e de m ora e) In France t he preliminary coatings are

.

applied on frames b u t the finishing is on boards and the goods

'

, , ,

are expose d to the sun aft e r the coatings are so far dried in the
stove a s not to retain the dust No exact statement can be made
.

of t he number of coatings applied as the practice di ffers in ,

di fferent works and with different classes of goods

P r ep a ra ti on Of j a a — The foundation of a a a
.

'

p n s l l j p n s is l inseed

oil and with this and Prussian blue alon e it is p o ssible to make a
,

good j apan .

The purity of the oil is of the first importance and it 1 5 con

ceded that B a a
,

l tic and B el gi n seed is the most suitable most ,

oth ers being more o r less mixed with other see ds grown at the
same time R ussi an linseed is generally mi xed with a certain
proportion of hemp but it is doubtful ho w far this is dis a d va
.

ta g e o us as hemp oil itself makes a very fine lacquer a

,

,
nd is much ,

used fo r t his purpose in R ussia The o il is best bought in large

'

.
'

quantities from a reliable presser and stored in large tanks in a

warm place ; s o that clear n d well s ettled oil is always available a -

for boili ng It deposits at first a good deal of foots but if

.
,

left in the tanks these graduall y disappear or subside to a very

small bul k so that even after years the deposit is very sm a
,
ll .

Th e foots probably consist principally of water and a little

mucilaginous matter emulsified with the oil
Ch e m ic a
.

ll y l in s ee d oil consists for the most part of t he gly

,

a
,

c e r id es of one or two highly unsatu rated fatty acids of which

linoleic and linolenic are the princip a
,

l These have the s me .

number of carbon atoms as stearic acid but the former has two ,

double links or pairs of unsaturated bonds and the latter three

pairs ( see p They are thus capable of absorbing much
oxygen and a
.

,
l so of polymerisation or the linking together of ,

two or more molecules int o more complex ones thus giving rise ,

to resinous products o f which the constitution is not well under

stood but which become more soluble in a
,
l cohol and finall y ,

even in water as the oxidation proceeds This change and not .

,

evaporation is what constitutes the drying of oils B y the

,
.

limited action of oxygen or more slowly of air drying oils are , ,

converted into a sort of j elly which is much used in the manu ,

-
4 80 P RI N C I P L E S OF L EA TH E R MA N U F A C T UR E

and collate the various information at our disposal and try from
it to evolve a clear and connected scheme H ennig 1 gives .

considerable detail of which the following is an abstract He , .

advises very clear and ol d oil and purifies (he states from “

pa
, ,

l mitic acid ) by exposing to t h e sun in shallow trays on a 1 0

per cent solution of ferrous s ul phate The clear o il is then
“

. .

heated to 50 to 60 C and mixed with 2 5 to 3 0 grm o f red

"
° °
.
, .

fuming nitric acid in l arge pots hol di ng 3 0 litres and provided _ ,

with a seri es of holes e n e above another for racking in which it

is stirred for fo ur days and a
,

l lowe d to settle and t h e clear layer "

gradually drawn off and fil tered in a warm place through a paper

previousl y saturated with oil This purified oil which a
,

l ready .
,

dries pretty quickly is placed in a boiler of about doubl e the ,

capacity of the oil used to allow for frothing heated for an ho u r , ,

up to about 1 50 C and 2 % per cent of l itharge added wel l

° 2
. .
_
, ,

stirred in and the boiling is continued Towards the end of the

, .

operation much pungent and combustible vapour 1 s g1 ve n o ff

'

which must be c a
,
'

rried to a chimney The oil is now allowed to .

cool and settle for two or three days in upright casks with taps
4 to 5 cm from the bottom Th e lowest possible temperature
promotes the settling of the p a
. .

l mitate of lead
a
.

The cl rified oil is now returned to the boiler and a saturated

'

solution of potassium permanganate is added at the rate of 2

“

grm of the salt per litre o f 0 1 1 well stirred till the mixture turns
brown and heated to 1 30 till a
.
,

l l the water is driven o ff when

°

7 to 1 0 per cent of Prirssia

, ,

n bl u e in the finest powder . sifted ,

through silk is dusted in through a sieve to prevent caking

,

and thoroughly mixed and the temperature is raised with con ,

t in u o u s stirring till brown vapours are given o ff the operation ,

lasting two to four hours Wh en the sample draws in threads

between the fingers on cooling a
.

nd make s a dark brown laye r ,

without greasy edges on writing paper the boiling is nearly ,

done but may safely b e continued a l ittle longer Fo r very

,
.

fine varnishes 3 per cent of finely powdered gambo ge may be .

added and the boiling continued two hours l onger at 1 50

,
°

The lacquer is now allowed to cool slowly and t o settle for a ,

week or two in a warm place It is deep brown by transmitted .

light but deep black by reflected and is a thick syrupy liquid ,

"

1
a
Che m ike r Z b t 87 8 p i t d i e i tu n
g ou 1 re r n e n D e r Ger ber 1 87 8 p 53
ad i t h L a M a f at
.
, , , ,
_
,

n th
n e 89 p 63
e er nu c u r er , 1 2, 1

q a f l it h a ail y l ag
. .
,

2
Th t it y e g u d m n o r e u se se e s u n n e c e ss r r e, n ot more
t ha 5 p n t b i g mp l y d i
er di a
cen y e n e o e n or n r o il b o il in g N o d e t il s a of

ahigh t m p a
-

ad
7

t im a g i
. .

e wh t h
re ve n , o r t e er er e er u re is u se d tow r s t he en d o f
th p a
e o ti er on .
 ]A P A N N ED A ND E N A M EL L ED L EA TH ER S 4 8 1

at ordinary temperature but thin enough to flow from the brush ,

when warmed 1
.

I n the writer s o wn experience the oil underwent no previous

’

preparation but long settl ing and he has no reason to think that ,

litharge was used but a small quantity of ros e spirit was ,

added in the boiling which was believed to brighten the j apan

'

, .

R ose Spi ri t is one of the dyers mordants and is probably a

’

mixture of tin chlorides and nitrates Fo r the first grounding

’

.
~

j apan a common Prussian bl u e of a paler colour and con

ta ining a large proportion of precipitated a
,

l umina was used but , ,

for the later coats o nly pure Prussian blue of the best quality
The a
.

l umina no doubt served the purpose of a thickener or

fil ler and the writer s experiments with finely g round kaolin
’

were quite promising The final finishing varnish is the same as .

the j apan but with the addition of copal varnish which is usually
, ,

that sol d by the varn ish maker Vill on 2 recommends the follow .

ing — 1 per cent of finely powdered potassium bichromate is

added to the oil at 1 00 C retaining that temper a ture for h a
.

lf
0
.
,

an hour and then raising to

,
adding 1 0 per c ent of Prussian .

blue and boiling as described and finally adding 3 0 per cent of

, , .

a Copal varnish made by heating 1 00 parts of boiled oil I o o

parts of gum cop a
, ,

l 1 00 parts of shellac 3 00 parts of s p rr l t , ,

of turpentine and 2 5 parts of ceresine or mineral wax in an

autoclave to 3 50 for half an hour Cop a
, ,

l can only be dis

°

solved by heating in this way Cop a

.

l varnishes are now largely .

superseded for j apanned leather by solutions of nitrocellul ose ,

which are much more elastic .

D avis 3 gives considerable detail of A merican processes of

_

japanning which appears to be gathered from a good source

,
.

Th e following is a summary referring mai nl y to the large split ,

hides used for upholstery which have been already spoken of ,

.

Th e hides are stretched wet on frames dried by heat with fan ,

ventilation taken o ff the frames and softened by a pin block

, ,
-

machine in which a head something like that of a sole cutting

, ,
-

press but studded with short rounded pins comes down on a

, ,

block with corresponding larger holes or grooves and finally ,

by boarding on a table An y holes are then patched with paper .

and glue to prevent j apan running through and the hides again , ,

1
Th ead d it i f p m ag aa t t m ly
on id i b t f
o i h a er n n e no er e ox se s , u u rn s es

ta a f ma ga aid f l l y id i d b y
'

i m t d i Li l i
‘

cer n o un o n n e se r er n o en c c u ox se

ma g aa t yi l d t t a y t ai a t f t h ga
.

per n n h yd id
e Th e bj s mb g e r rox s e r c c . e o ec o e o e

is n o t o b v io u s , b u t it s u seis m e n t io n e d b y o t h e r w r it e r s
a aa a ai
.

2
V il l o n Tr i te a ’

pr t i qu e d e l F b r i c t i o n de s C u i r s P r s, 1 8 89
Da Il[ a f a fL a P h il a
d l p h ia 8 9 7
.
, ,

3
v is , The / t nu c ure o th e er, e ,
1 .
482 P RI N C I P L E S OF LEA TH E R MA N UF AC T UR E

stretched on frames now receive a heavy coat of daub or

first j apan made as follows : — R a
,

w linseed oil is boiled in an

open p a
,

n over fire
1
for about twenty four hours extending -

over two days and being stirred continuousl y during boiling ,

with a perforated i ron paddl e During the first twelve hours .

it is graduall y raised to a temperature of about 3 0 0 C and is °

.
,

then allowed to fall to 20 0 before leaving for the night On the °

second day it is a
.

gain raised to 3 0 0 to 3 2 0 and cooked to a ° °

j elly and again cooled to 2 00 and the fire completely ex t in

,
°
,

gu ish ed and even the bricks cooled with water and petroleum
naphtha u p to about one third of the volume of the oil 1 5 a
, ,

dded and -

well stirred in and this is repeated till about 1 % times the volume
,

of the oil has been added much of the naphtha being evaporated
Th e workmen c a
,

by the heat of the j apan ?

l l this sweet
meats and it does not form daub till lb p e r g a
-

,
ll o n of good .

lampblack free fr Om grease has been added and well mixed The .

daub is applied with a steel slicker about 1; inch thick and 1 0 5

1
I

inches long well worked in and the excess slicked o ff It is then

, , .

thoro ughly dried in air or sunshine and a second coat is given “

, ,

which is dried in the stove at 45 to 50 C Fo r enamels two coats ° °

of daub suffice b u t for smooth j apans a

.

t hir d is generally given

, _, .

Enamels now receive a slicker coat boiled to about the thick

ness of treacle a
-

nd put on with a s m al ler and thinner slicker and

, ,

after drying about twelve hours in the stove are pumiced and ,

receive a coat of enamel varnish which is made of linseed oil

and about 2 to 6 oz per ga
,

ll on of Chinese blue and is boiled .

,

about eight hou rs and thinned with naphtha t o the same con
'

( The wr it er h a
, .

sistence as the slicker coat s not been able to -

.

ascertain definitely t he composition of Chinese blue but it is ,

pretty certainly some form of Prussian blue ) The goods are again .

1
a
St e m b o il in g is not pr at i a
c bl c e, fr o m t h e ver y h igh t e m p e r t u r e s a
r e qu ir e d a a
E l e c t r ic l h e t in g wo u l d b e p o ss ib l e
aa a a a
.
.

p p r e n t l y w s t e f u l p r o c e ss is p r o b b l y b s e d e x p e r ie n c e
2
Th is
“

on

a a a ad p l y m i d
.

P e t r o l e u m n p h t h is n o t go o d s o l v e n t f o r t h e o x id ise d n o e r se

ja
p a ad if m i d a
t a am li a
-

o il f th
s o e n, t mp a
l w n t th
xe o er e er u re n e u s on r er

t haa t l ti w ld lt t h gh a t a h ig h t m p a ou t th tw r e su ou

a
n ru e so u on e er ure e o

l iq id a m t a a
,

u s lly l bl
re Th t
u u l m dy w ld b t m i
so u e l e n ur re e ou e o x c o o er ,

ad a ga i h a t i aa l ae t ill k p l a b t w it h la
.

n t
n e l ti n t n u oc t il v so u on oo ce, u s o vo
’
e

al iq id ap t l m — a
u p ht ha
s t hi w e ld p
ro e u d a y h igh p
n s ou ro uce ve r r e ss u r e

P ba b ly a p a ti a l m a w d il t t h j a p awit h a
.

ro m ld b fi t t
o re r c c e ns ou e rs o u e e n

mm
co l t on h at p ti
so v e n ad t h t a dd t h
su c a
p ht ha s ur en n e, n en o e n

a b d i wh i h d i l b t h t h
.

C mmo l ont so v e n s re t ito t tes b c sso v e o e con s uen s o e

m i d ad if a
xe dd d i nffi i t q a t it y g e a lly l a d t
n th i m t a
su l
c en u n en er e o e r u u

am d a q a f a l h l w ill b i g a
,

so ul ti Thon t t it y
us o er b t th e u n o co o r n ou e

f wa ad t h
.

co mm l ti o n so u t on o er n e er .
 8
4 4 P RI N C I P L ES OF L EA TH ER M A N UFA C T UR E

and for c ell ul oid varnishes usually acetone and amyl acetate with
some camphor but du ri ng the war a va r ie t
y o f other solvents
'

were used for dopes for aeroplane wings and among others ,

trichloroethylene epichlorohydrin chloroform ; and other organic

, ,

chlorine compounds but these though quite effective have been

, , ,

largely abandoned as their fumes were found very poisonous to

,
-

the work people If used at all very effective ventilation is

-

, ,

necessary which should be downward and away from the opera

,

t iv es as the vap ours are very heavy

, A solution once made .

can frequently be diluted without injury wi th other solvents ,

such as alcohol benz01 or petroleum spirit Celluloid is soluble

'

.
, ,

in acetone alone but forms a viscid j elly rath er than a true solu
'

tion and the addi tion of amyl acetate is necessary to produce a

,

bri ght and coherent coating .

F o r Some sorts of leather where a very thin coating is desirable

“

, ,

it is probable that celluloid so l ii t io n alone with a small proportion ,

of nitrate d or even of ordinary castor oil and either mixed with

, , ,

or applied above pigment —colours might be useful In the ,

.

U nited States pigment finishe s for li ght leathers have come largely
into vogue for covering grain and dyeing defects and these seem ,

someti m es applied with a celluloid me di um and by spraying ,

though in other cases water solutions are used in a manner very

similar to the sole leather finishes described on p 3 68 The . .
‘

Ne w Explosives Co Lt d at Stowmarket supply cell ul oid . .

solutions suitable for such purposes and could no doubt give ,

much useful advice as to their use They also I believe supply

a small sprayer suitable for experiment a
.
, ,

l p urposes U pholstery .

leathers sprayed with a cellul oid varnish would be to a great

extent waterproofed so that they could be used for automobiles
,

and the like .

A s regards drying by ultraviolet rays t he usual method seems ,

to be to carry the skins in frames suspended fro m a slow moving

«

Chain or some similar d e vrce past a battery of mercury lamps ,

.

These lamps must be blown in quartz as glass is much less per

meable to the ultraviolet rays The arc is struck by a
,

l low .

ing the mercury to flow from one bul b to another A good

pattern is made by the Thermal Syndicat e Lt d Wa
.

l lsend o n é .
,
-

Tyne Some care is necessary in their use as the li ght is very

.
,

injurious to the eyes which should be protected by dark red glass

in loo king at the lamps and the rays a
,

l so produce unpleasant
,

sunburns especially on parts of the skin not usual ly exposed

,
.

It will be remembered that the light is often used by surg eons in

extirpating malignant skin diseases
Ultraviolet rays have a powerful ionising action on the a
.

ir
 ]A P A N N E D A ND E NA M ELLED L EA TH ER S 48 5

through which they pass leading to the production of some ,

oxidising substance generall y supposed to be ozone which has

an inj urious action on the leather and s e ve r a
l pa
,

t e n t s have been
'

taken fo r its removal especially one by D oerr and R einhart of ,

Worms which cover the use of ammonia gas 1 in the drying

chamber A very competent manufacturer h a
,

.
s expressed the
opinion to the writer that the i n j uri ous vapours were no t those ,

of ozone but of oxides of nitrogen and that with sufficient ,

.
,

ventilation the d i fficulty was not a serious one A s the e ffect

, .

is produced by ra di ation and not by temperature there seems ,

no reason why the ventilation shoul d not be as free as that of ‘

o p en air drying though experiments are desirable as to whether

-

it might not be supplemented and quickened by heat app lied

in other ways .

The present mode of dryi ng in hot unventilated stoves seems

repugnant to common sense since we have known the great part ,

which oxidation take s in the process and the dryi ng wo ul d prob ,

ably be more rapid and c Om p l e t e with better ventilation even

“ ‘

if the temperature w
,

ere somewhat lower D rying in tunnels

in a current of hot a
.

ir the frames being carried on trucks wo uld , ,

seem wo rth trying where goods of uniform sort and size Were
manufactured ( op p Th e process does not seem to be . .

wholly one of oxidation for gl ass lights and other cooler points ,

in the stoves b ecome coated i n course of time with dark brown

sticky matter -

A s r egards laboratory experiment much may be done Small .

j apan boiling experi men t s may be made as described on p 47 9

and experi ment a
-

.
,

l sampl e s of j apan either on leather or on g lass ,

plates may be dr ied in an or di nary water oven regulated b y a

,
-

thermostat to the proper temperature and though the same finish ,

and smoothness may not be got as obtained in the works it is at ,

least p ossible to see whether the j apan dries with a smooth bright
surface su fficiently hard; and yet not brittle I t would be
, .

interesting to try comparative experiments in boiling in closed

flasks to o b serve the effect of oxidation and perhaps drying under ,
.

the same conditions might throw light on the question of ventila

tion Di fferent driers and mixtures should be tested It is
. .

probable that precipitated hydric ferric oxide in fine powder

,

might be substituted for the expensive Prussian blue and ferric ‘

1
Th e f o ll o w in g p t e n t s m y b e a a r e f er r e d to
a 9 9 37 8
U S P t 1 0

j gh a E g P a
. . .
,

un t 97 n s, n 1 0 1 1 9 1 2 1 9 1 2, 69 4
J gh a F P a
. . . .
,

un t 443 4 6 n s, r 0 1 9 13 Col l , 1 9 1 3, 337

adt
. . . . .
,

D o err R e in h r , D R P. . . 26 7 5 24 Co ll . .
,
1 9 1 4, 4 1 .
486 PR I N C IPLE S OF L EA TH ER MA N UFA C T UR E
‘

resinate and borate also suggest themselves Th e use of very

’

finely levigated ultramarine especially in the bottom coats to

correct the brown black of the j apan seems a
,

l so wo rth t rial as
it is comparatively cheap and wo ul d probabl y be un a
-

, ,

,
l tered by
the boiling When j apanning was first introduced Prussian
blue wa
.

s probably the cheapest blue known and the idea was to

,

correct t he brown of j apans made with lampblack .

Cell ulose acetate has been recently much used for dopes
a n d v arnishes as well as for non in fla
, mm a
-

b l e films n d is prob ,
a
ably applicable in j apanni ng .
 4 88 P R I N C I P L ES OF LE A TH E R . MA N UF A CT UR E
of water and alcohol and the maj ority of them combine with the ,

fibre of the leather wi thout the use of any mordant so that in ,

most cases it is o nl y necessary to apply a solution of t he dye

direct to the leather though their suitability for the purpose ,
.

varies considerably A few which are onl y solubl e in oils or .

hydrocarbons are not suitable for leather dyeing though they ,

may sometimes be utilised in conj unction wi t h fats i n currying

or j apanning ; and there are also certain c olours which are not
applied to the fibre ready formed but are developed on it by ,

subsequent chemical treatment and which have only been ,

applied to a limited extent to leather .

A number of the coal tar dyes which are produ ced in the
crystalline form have a tot a
-

l ly di fferent colour when solid to

,

that of their solutions and to the colour they produce when

dyed A well known instance of this is magenta or fuchsine
.
-

which forms glist ening green crystals while in solution it is a ,

brilliant red dye The colours of t h e crystals are usually com “

p l e m en t a
.

r y to those of the solution thus several blues have the

appearance of metallic copp er and violets such as methyl violet
are greenish yellow genera
a
, , ,

l ly with a pronounced metallic lustre

-

,
.

This peculiarity is the cau se of the defect in dyeing known s

bronzing in which the dye when applied in too concentrated
, ,

a form takes a surface shimmer of its complementary col our

a
, ,

nd is utilised in
, bronzed leathers by applying the dye in a

a
concentrated and often al coholic solution
Th e coal t a
.
, ,

r colours re mostly either

-
acid or basic .

Th e former are t he salts of organic colour acids with inorganic

bases (generally sodium ) and are usu a
-

l ly readily sol uble in

“

water but frequently do not fix themselves on the fi bre till

,

the colour acid is set free by the addition of some stronger acid
-
“

to the bath and m many cases the free colour—acid 1 8 of different

,

colour to its salts The basic colours are salts of colour bases
.
-

( organic bases of the nature of very complicated ammonia deriva

t ives ) with acids (mostly hydrochloric sulphuric or acetic ) Most , , .

of these in commercial use are soluble in water though a few ,

require the addition of alcohol The colour bases themselves are

usually insoluble in water and therefore precipitated by a a
-
-
.

l k l ies , ,

and in som e cases they are also colourless The basic dyes have .

generally greater intensity of colour than the acid dyes but larg e ,

classes of them are very fugitive when exposed to light and in ,

strong solution many others are very liable to bronze a defect ,

which is generally less marked with the acid colours 1 A cid and .

1
It h ab s e en sh o w n a
b y _L m b t h t m a ay b ai n s c colo urs am re u ch f at
s er

t o l igh t on a
l e t her t h a
n on t e x t il e s .
 D YE S A ND D Y EI N G 4 89

basic dyes cann ot be employed in mixture in the same dye bath -

-

as they usually precipitate each other .

“

A s it is not obvious at first sight whether a given dye is acid

or basic a reagent to disting uish them is useful Fo r this purpose
,
.

a solution of I part of tannic acid and I part of so di um acetate

in I O parts ( by weight ) of water is co nveniently employed which ,

gives coloured precipitates with basic dyes but is not a ffected ,

by acid ones The fact that basic dyes are precipitated by

.

tannins influences their use in leather dyeing not o nly as regards ,

their fixation on the leather fib r e by the tannin which it contains -

but as the cause of their precipitation in the dye bath if great -

care is not taken to avoid the presence of tannins in a soluble

form either by very thorough washing or by fixation of the
tannin by metallic s a
, ,

l ts such as tartar emetic ,

p The .

use of the sodium acetate is t o combine with the mineral acid

of the colour salt which if left free wo ul d p revent complete
-

precipitation by substituting acetic acid which is much weaker

, , ,

especially in presence of excess of sodium acetate ( op p . .

In using the terms

-
acid and basic with regard to dyes ,

it is not to be understood that the dyestu ffs as employed are

acid or a l kaline in the sense that vinegar is acid and soda basic
but merely that the actu a
,

l colour constituent of the salt is in -

the one case of an acid nature and set free b y stronger acids ,
-

,
~
and in the other case is basic and liberate d ( and often p r e cip i
ta
, _

t e d ) by stronger alkalies .

There are several general theories with regard to the fixation

1

of colours in dyeing organic fibres a n d it is probable that no ,

one of them affords a complete explanation in all cases On e .

holds that the action of dyeing is mechanical rather than chemic al ,

the colour adhering to the fibre by surface attraction another -

that an actual chemical compound is formed between the dye

‘

and the dyed material or one of its constituents a n d a third ,

the solid sol ution theory o f Witt is in a sense intermediate '

, ,

holding that the colouring matter is actually dissolved in the

dyed fibre Th e idea of a solid solution strange at first o ffers “

little difficul ty on consideration The colouring metall ic s a

.
, ,

l ts .

in tinted glasses exist obviously in solution in the melted glass

-

and can hardl y be said to change their condition in this respect

when the glass b ecomes solid Gelatine in dia r u b b e r and perhaps

a
.
, ,

ll other colloid bodies absorb water or other liquids without

‘

1
Co m p a t h i f d y i g wit h t h wit h gad t t a i g m
re eo r e s o e n o se re r o nn n en

t io n e d in Ch a
pt X X X II Th
er i m h i mm b tw th tw er e s uc n co on e e en e o

ad Z ah aiah a h w t h a t ma y d y t ff h a a tai g
.

p r o c e ss e s , n c r s s s l o n n es u s ve so nn n

p r o p e r t ie s .
 L EA THE R M A N UFA C T URE
“

49 0 P R I N C I P L ES OF .

losing their solid form and these liqui ds may fairly be said to ,

be dissolved in the solid Al l animal and vegetable fibres are '

.

in this respect like gelatine and during the process of dyeing ,

are swollen with water It is quite easy t o dye a mass of gelatine .

throughout with most water solubl e dyestu ffs (Compare on -

.

these points what is said in Chapters IX and X on the physical . .

chemistry of hide fib r e ) The distinctions between solution and

at t ra
-

molec ul ar su r fa
.

cea c t io n o n the one hand and certain forms of ,

chemical combination on the other are not wide ones and prob
ably a
, ,

ll three theories are true in di fferent cases and shade o ff ,

into each other by imperceptible gradations Th e subj ect .

o f leather dyeing is in fact a very complicated o n e since we are

, , ,

not dealing with a fibre of uniform composition but with one ,

which has had its structure ( both chemical and physical ) altered
by the processes to which it has been subj ected during its
c onversion into l eather .

A lthough strictly speaking the constitution of the gelatin o us

, ,

fibre of the skin is unknown we are quite justified in stating 1

.

that like the amino acids which are i mportant proximate pro
,
-

ducts of its decomposition it contains both acid and basic groups , ,

and is therefore capable of attracting both bases and acids It .

is well known for instance that neutral hide fib r e is capable of

withdrawing sulphuric acid from a decinorma
-

, ,

l solution w ith
s uch vig o u r that the residual liquid is n eutral to litmus paper

and it will a l so absorb caustic a

.
_

l kalies with perhaps equal avidity 2

.

It is thus readily dyed b y colouring matter of either basic or

acid character and in many cases will even dissociate their s a
,
l ts ,

dyeing the characteristic colour of t he free dyestu ff b ut possibly ,

at the same time fixing the liberated base or acid with which
t h e c o l o u r in g matter has been combined Many tanning pro
cesses con sist in a somewhat an a
_ .

l ogous fixation of weak ba ses

and acids and it is therefore to be anticipated that they will
,

profoun dly modify the colour fix in g properties of the original

a
-

fibre as indeed proves to be the case Exactly wh t the result

,
.

of a particul ar tanning process in this respect will be is less easy

to foresee .

In the ordinary vegetable tanning process the tannins which ,

are of acid nature are freely fixed by the fi bre It is therefore

, .
, ,

not s urprisin g th at vegetable tanned leather most readily fixes

the basic colours especi a
-

l ly as these form insoluble compounds

,

with the tannic acids so that it is quite probable that the dyeing
,

is mainly e ffected by the formation of tannin colour lakes on the - -

fibre rather than by actual fixation of the colour base in com

,
-

1
Pro c t er, j o u rn . S oc Chem b
. . ut ,
1 9 00,
p . 23 .
2
Cp . a
Ch p t e r X .
49 2 P RI N C I P L ES OF L EA TH ER -

MA N UFA C T UR E

dark colour by action of the tannin On subsequent treatment .

with a soluti o n of potassi um ferrocyanide a deep blue is formed

'

( Prussian blue ) I f copper acetate or ammoniac a l solution o f

copper sulphate be substituted for the iron s a
.

l t a deep red
brown ferfo c ya n ide is produced Y ellows are sometimes dyed .

by first treating tanned leathers with lead acetate which is ,

fixed b y the tannin and then with potassium bichromate by , ,

which yellow lead chromate is produced A more important use

of lead is in the so call ed lead bleach which is re a
.

-
l ly a white -

pigment dyeing with lead sulphate The tann ed l eather after

washing is first treated with a solution of lead acetate ( usu a
-
.
,

,
lly
brown sugar of lead of about 4 gr m per litre ) and sub s e .
,

quently with a di lute sulphuric acid o f about 3 0 grm of c on

c en t r a
.

t e d acid per litre and then t horoughly wash ed to free ,

it from acid The proc ess is often used as a preparation for

dyeing p a
.

l e shad es as many of the aniline dyes are easil y fixed

,

on the bleached leather but is subj ect to the di sadvant ge ,

“

a
attendant on all pigments containing lead of becoming rapi dl y
da r kened by traces of s ul phur or sul phuretted hydrogen such as

are constantly cont a ined in lighting ga

,

s or arise from the putre

faction of organic matters The use o f acid is a

,

l so liable to
'

a
_ . _,

cause early decay of the leather if not thoroughly removed .

1

A large proportion of the co l tar colours contain amino -

groups ( NH2 groups) which when treated on the fibre with ,

ni trous acid ( or an aci di fied solution of sodium nitrite) become ,

di azotised ( converte d into N N groups with elimination

“

of OH2) On further treating the dia

. z ol c o mp o un d with solutions

of amines or phenols combin ation takes place and new azo , ,

colours are formed in or on the fibre often remarkably fast to ,

washing or rubbing Since these qualities are less important .

in leather than in t e xtiles and the process is moreover som ewhat ,

delicate and the nitrous acid is apt t o affect the leather inj uriously
these processes have been little used in leather dyeing and a
, ,

re ,

only mentioned here for the sake of completeness

;

The use of the natural polygenetic colours in dyeing leather

of vegetable tannage which was Once univers a l is gradually

a
, ,

di sappearing except for the production of b lacks

,
Leather .

cannot be very satisf ctorily mordanted for these colouring

matters but they have some nat u ra l attraction for the leather
it s elf a n d are generally dyed first
, _
and their colours afterwards ,

developed by metallic mordants such as iron chrome tin salts

a
, , ,

n d alum which act not only on the absorbed dyestu ff but

, ,

ai m a
1
B lt ar u s s c nn o t be u s e f u l l y s u b s t it u t e d fo r t ho s e of l e d, a at h s ey

ha att a
ve no ti f r c on or t he t a nned fib r e .
 D YE S A ND D Y EI N G 49 3

frequently on the t a n n 1 n and colouring matters derived from the

tanning materi a ls Fo r black dyeing t he use of coal tar colours

either a
-
.
,

l one o r to deepen the colours produced by i ron is ,

gradually exten di ng Fo r sui table colours see Ap p C A s

co a
-

. . .

l tar blacks are mostly dark violets rath er than dead blacks
-

their colour may be deepened by the admixture of suitable

'

yellows or browns and this is frequently done by the colour ,

manufacturer A part from the coal tar colours black dyeing

.
-

,
“

is generally produced by the action of iron (and chrome) either ,

on the tannin of the leather itself or on logwood A s the leather

is frequently gre a sy a
.

'

n d the satisfactory formation of a tannin

,

o r logwood lake can o nl y take place in presence of a base to

-

absorb the liberated acid of the iron salt the skins are either
brushed with or plunged in a logwood infusion rendered a l ka
,

, l ine ,

with soda or ammonia or the tanned leather receives a pre ,

liminary treatment with weak soda or ammonia solution A s .

such solutions act powerfully on tanned leathers rendering them ,

harsh and tender great care must b e taken to avoid excess The ‘

effect of this a
, .

l kaline treatment is not only to assist the wetting

”

of the greasy surface , but to prevent too deep penetration of the

dye by causing rapid precipitation of the colour lake In recent
,
-

times however leathers are so metimes demanded in which the

, ,

colour goes right through and in this case it might be well to ,

reverse t he treatment beginning with a weak solution of a ferrous ,

salt perhaps with addition of sodi um acetate or potassium

tartrate and finishing with a l ka
,

,
l ine logwood as without alkali ,

the full colour is not developed The use of iron sal ts is not very .
‘

satisfactory in regard to the perm anence of the leather ; and

in this respect it is of great importance that they should not be
used in excess and that any strong acids they cont a
,
i n should be
saturated with permanent bases and if possible washed out , .

Leather surfaces blacked with iron almost invariably ultimately

lose their colour becoming brown if tannins and red if logwood
,

has been employed and at the same time the leather surface
‘

usually becomes brittle or friable This is to a large extent .

due to the e ffect of iron oxides as oxygen carriers Exposed .

to light they become reduced to the ferrous state oxidisi ng t h e

organic m a
.
,

t t ers w it h which they are combined and in the dark ,

they r e oxi di se and the process is repeated It is therefore of

-

, .

the first importance that excess of the organic colouring matter

should be provided and that the quantity of the iron shoul d ,

be as small as possible and in stable combination These points

are greatly neglected in practice especi a
.
,

l ly where blacking is ,

done by the application of iron salts without logwood when the ,

 P R I N C I P L E S OF L EA TH ER MA N UFA C T UR E
“

49 4

evils mentioned are in t e n sifie d b y the actual removal of part of -

the tannin of the leath er and perhaps by the combination of ,

ferric oxide with the skin fib r e itself forming a bri ttle iron
leather Treatment with a
-

l kaline sumach gambier or logwood

.

solutions both before and after the application of the iron would
lessen the evil Iron logwood blacks a
, ,

r e much less permanent

a
-
.

and fade more r pi dl y under the influence of light and air than
iron t annin blacks The use of iron blacks on curried leathers
-
.

seems considerably t o increase the tendency to spueing a

Copper s a
,
-

defect due to oxidation b f the oils ( see p l ts .

mordant logwood a very dark blue which is m uch more stable “

a
,

than t he iron compound and henc e are of ten used advantageously

in mixture with iron s a
,

l ts In practice iron blacks r e generall y .

,

oiled in finishing and this renders them more permanent both by , ,

protecting the lake from air and by forming iron soaps which
a r e stable Th e use of actu a l soaps in blacking and finishing
.

is not unknown and probably deserves more attention H ard ,

.

soaps of soda and stearic ac id form an exc ellent finish where a

1
‘

mo derate glaze is required the soap j elly being applied with a ,

brush very thinly allowed to dry thoroughly and polished with a

flannel or brush or glassed Ma ny a
, ,

c id colours are soluble in ,

.
_ _

such soap j ellies which may thus be employed for staining ,

.

Similar but harder finishes and capable of b eing glazed to a

“

high polish are made b y dissolving shellac with dilute borax

,

or ammonia solutions 2
B oth of these finishes are useful in .

lessening the tendency of iron blacks to smut or rub off a failing ,

which is due to the precipit ation of Io o se iron lakes on t he surface

instead of in combination wi th the fibre and is particularly ,

obviou s where inks o r one solution blacks are employed or _

-

where the mordant and the colouring matter solutions are

all owed to mix on t he surface of the leather Such inks are
generally made with a ferrous s a
.

l t and logwood or tannin together ,

with some aniline black and the c olour lake should only b e form ed ,
-
.

on oxidation Chrome is not much employed in blacks with .

1
On e of c at i us c so d ai n I O to 1 5 of a
w t e r b o il e d w it h 8 ai aid
o f st e r c c

a ad wa ta
,

t il l cl e r, co ol ed d il u t e d w it h 4 0 0 t o 8 0 0
to 25
°
C n t w it h
er , t co n s n

a a bta S m wh a
.

s t ir r in g , t il l wh it e je ll y o f s u 1 t b l e c o n s is t e n c e is o -
i dne t o e

a a aa a a wa fa tty a
.

s im il r b u t h r d e r p r e p r t io n s m y b e m d e w it h id
’
x e s, or c s

tha t a Sa ifi d J ap awa w ba
, ,

s t il l h igh ier p n s e r c on e n x ou ld p b ly p
ro d ro uce

ag d g l a
.

oo z e

a a a a a a a
.
2
Fi p t
ve f h l l d i g tr d w m w it
s o h w t ds 3 f m m e i c es e r 1 00 er n o on

f t
or f b a If t h l t i i
or 1 o d aa
or a i g f gl a
x zi g e so u on s u se s se so n n or n

t h w ay m a pa a t ad i g h d b y ha
.
.
, ,

e tt
x w hi h t er ld b mi ki gc se r es o n s n n s ou e xe s n

b f e o re u se A a a i h at .
g l ti s h ld b vd ad t h w a rn s ,
s ro n e r so u on s ou e use n e x

s kim m e d o ff .
49 6 PR I N C I P L ES OF L EA TH ER MA N UFA C T UR E
place of a norm l a a
l umina salt a basic salt is employed such as , ,

may be obtained by partial neutralisation of the sulphuric acid

with soda satisfactory tannage may be accomplished without
,

salt a basic compound is absorbed and the leather is much less

, ,

a ffected by washing In the analogous case of chrome tannage

.

this basic compound may be still further deprived of its residual

acid by washing t he tanned ski n with a l kaline solutions leaving ,

a leather which is extremely resistant even to hot water and

a somewhat similar resul t _may be ob tained with alumina though
with more difficulty as apparently a very sm a l l excess of a l ka
,

li

a
,

destroys the qualities of the leather ( 015 p .

_
.

The results on dyeing are almost wh t might have been fore

seen Wh ile ordinary a l u m e d leather absorbs both acid and
basic dyes rea di ly the basic chrome leather has practic a
.

,
l ly lost
it s affini t y for the latter . Both chrome and alumina leathers
'
‘

readily ab sorb vegetable tannins thus supporting the view that ,

the acid fi xin g groups of the gelatin molecul e are still u h

a
-

sat urated ( tannins are cap ble of tanning pel t swollen with
‘

sulphuric acid and apparently of expelling the acid) In the

,
.

case of chrome leather the effect o f r e tanning with tannins is -

greatly to lessen its stretch and if carri ed too far to destroy its , ,

toughnes s but it at once b ecomes capable of fixing basic dye

stu ffs This property is frequently made use of in dyeing but a
,

.
,

a
the e ffect on the leather must not be di sregarded where softness
and stretch are important as in t he c se of glove leathers ,
-

P olygenetic dyes are of course fixed on alum or chrome leathers

, ,

by the alumina or chrome mordant though apparently the bases ,

are not present in the most favourable con di tion for fixing colours
Thus logwood extracted without a
.

l kali dyes vegetable tanned

leather yellow a
-

l u m e d leather violet blue and chrome leather

,
-

blackish vi olet and some of the alizarine group dye very well
-

on chrome as its resistance to hot water allows much higher

'

temperatures to be used than with most other leathers The .

tannin contained in dyewoods has the e ffect of l essening the

stretch of chrome leathers but at t he same time g1 ve s them a ,

full er feel .

Something should perhaps be said on the dyeing of oil and

a l dehyde leathers but the subj ect has as yet been scar cely
‘

treated scientific a
,

l ly and our practical knowledge of the subj ect

,

is insu fficient to j ustify theorising ( see however p

Wash leather which has been bleached with perm a
.
, ,

-
nganate
( p 4 59 ) can be dyed pretty readily with mos t dyes and if brown
shades are required it is not necessary to remo ve t he ma
.
,

n ganic
oxide formed .
 D YES A ND D Y EI N G 49 7

D efects
in the colour of the finished leather are due to a
variety of causes b u t many are produ ced by want of cl e a
, n li

ness and system during the dyeing itself The greatest care is .

needed in this respect and in brush dyeing a di fferent brush ,

-

should be used for each di fferent colour as it is impossible to ,

remove thoroughly all traces of dye by the ordinary methods of

cleansing .

I rreg ular and surface dyeing Sometimes occurs o wing to too

rapid fixation of the colours while in other cases the affinity of
the dye is too small to a
,

l low of reasonable e xhaustion of the

bath A ddition of salts of weak acids such as potassium
.
,

hydrogen tartrate ( tartar ) or of those like sodium sulphate , ,

which form hydric salts lessen rapi di ty of dyeing with acid

colours while acids generall y increase it and it is a
,

,
l so often ,

increased by addition of common salt which lessens the solu

Weak acids such as formic or acid s a
,

b il it y of the dye . l ts , , ,

such as so di um bisulphate are generally to b e preferred to ,

sulphuric acid as an ad di tion to t h e dye bath and if the latter is

1
‘

used great care is desirable in its complete removal There is

, .

no doubt that the rapid decay of leather bookbindings and

upholstery is largely due to the careless use of sulphuric acid in
cleari ng and dyeing the l eather 2 and even if it is fully
removed it has saturated all bases such as lime which are
, ,

natural ly present in leathers in combination with weak acids

a
,

nd which would otherwise act as som e protection from the

s ul phuric acid evolved in burning coal gas A bath contain ing .

the salt of some strong base with a weak acid such as sodium
acetate or potassium tartrate used after dyeing would lessen , ,

both these dangers .

”
Bronzing the di chroic e ffect produced by light reflected
,

from the surface of many colouring matters complementary to ,

that transmitted by them and reflected by the surface of the

dyed material is not peculiar to basic colours but is generally
, ,

more m arked in them than in acid ones B asic c o l o u r s / fr o m their .

great affinity for tannins and consequent rapid dyeing are apt , ,

to dye irregularly and without su fficiently penetrating the leather

, ,

and if the soluble tannin is not whol ly washed out of the skin s
previously to dyeing it bleeds in the dye bath and precipitates
,
-

insoluble tannin lakes which waste colour and adhere to the ,

1
Se e R e p o r t of Co m m it t e e of So c ie t y of A rt s on B o o k b in d in g Le a
t h ers
1 901
aid at i aid h ap a
.

2
Fo r m o st c co lo urs ce c c s ro ve d t o o w e k t o b r in g o ut

t h e ir f u l l c o l o u r in g , but f mi a
or id i q it c c s u e s a
t i fat s c o ry If s u l p h u r ic

aid i aw al t t ha
.

c s u se d, e ig h t e
q u t f t h dy
o o e e s t u ff is su f fi c ie n t
49 8 P R I N C I P L ES OF LEA TH ER
"

MA N UF A C T URE

surface o f the leather Th e inconvenience of basic colours due .

to their too rapid fixation may sometimes be lessened by slight

acidification of the dye bath with a weak acid such as acetic or -

_
,

lactic The acid may be still further weakened if desired by

.
“

the addition of its neutral ( so di um ) salt The precipitation of .

tannin lakes in the bath may be prevented by previous fixation

of the tannin with tartar emetic with titaniu m potassium ,
'

oxalate or lactat e, or some other suitable metallic salt ( see p

Th e fa
.

3
din g of the colours of dyed goods b y exposure to light
'

,
.

is a defect which has been much more investigated i n the textile

industries than in leather manufacture though in the l atter case , ,

and especially w ith regard to bookbi n ding and furniture leathers ,

it is of even greate r importance It is probable that no colours .

are actually una ffected by strong sunlight but in many cases the ,

action is so slight that it may practically be disregarded some

of the co al tar colours a nd especi a
,

-
l ly some of the alizarines being , ,

practically permanent while others and particularly the aniline

a
, ,

colours belonging to the triphenylmethane group such as ,

magenta are so fugitive s to be practically bleached by a week

’

of strong sunl ight Chrysoi d ine and the eosins a re a

,

l so very '
-

bad in this respect The fastness of colours to light is a good .

_
,

deal influenced by the material on w hich they are dyed and but ,

little has been published of the results of direct experiments

on leathers but Mr M C Lamb has carried out a research of
,
. .

this nature 1 and t he subj ect is now receiving a good deal of

,

attention in other quarters Experiments are easily made by .

exposing samples to sunlight under glass or in a south window

"

a part of the leather being covered with wood or thick brown

paper for comparison The results are often compl icated by
the tendency o f all leathers t a
.

n n e d wit h tannins of the catechol

group , and especially with turwar ( ca ss ia

) bark ( p m l mo s a .

and quebracho to darken and re dden in sunshine or even by

, ,

exposure to diffused light Pure sumach tannages are nearly .

free from this defect and are also much less easily destroyed by ,

the action of gas fumes ( sulphuric acid) and the other injurious
influences to which books and furniture are often subj ected ?

Want of fastness to friction or rubbing is a defect genera l ly

mo re important in textiles than in leather where it is usually
'

prevented by glazings or other finishes applied to the surface ,

but in some cases , and especially in black leather it is apt t o b e

“

annoying I f suitable colours are used t he defect is generally

.
,

—
1
Se e ]o u r rz S o c Che m b ut 1 9 02,
p p 5 6 1 58
1

Le a
. . . . .
,

2
Cp . R ep o rt of So c ie t y o f A rt s Co m m it t e e o n B o o kb in din g t h ers ,

1 901 .
5 00 R I N C I P L E S OF
P L EA THE R MA N U FA C T UR E

dyed flesh 1 s preferred In dyeing in the pad dl e or drum the

skins a
.

re merely placed loose in the dye liquor so that the flesh e s -

are dyed equally with the gram sides P addle dyei ng has the
'

advantage of e ffecti ng a
-
.

considerable saving o f labour as com

pa red with the dye tray in which constant handling which often
lasts an hour or more is required It a
-

, ,

,
l So allows of almost e qual
.

FI G .
—
D y e in g in t h e Tr y a .
’

facil ity in exami nin g t h e c o l o ur of the skins which is very im

'

portant when dyeing to shade b ut it is less econo mical in dye,

stu ff as not onl y the flesh sides are dyed but a much larger
volum e of li quor i s used and a
,

s the dye bath can never be e n

,
tirely -

exhausted more dye is run away i n the use d liquor Drum

,
.

dyeing is much less expensive in this respect as the vol ume of

liquor m a a
,

y be very sma l l n d from the e

,
fficiency of the motion
the dyeing is very thorough and penetrates deeply into or through
the skin which in in a
,

,
n y cases is advantageous but it is di fficult ,

to dye to exact shade since the skins can only be examined b y

,

stopping and opening the drum Most dyes are more readil y .

fixed at high temperatures and in this respect the drum has an

advantage over all other methods a
.
,

s o n c é heated it r etains its

,

h eat with very little loss to the end of the operation whil e both ,
 D YE S A ND D YE I N G 59 1

in the paddl e and the dye tray the liquor is rapidly cooled and
-

special methods of maintaining the temperature complicate the

apparatus and require great care to avoid overheating It is
, .

usually best to work at the highest temperature which the goods

a
wi ll safely bear, and this varies to some extent with the class of
goods chrome tann ges and chamois leather being peculiar in
standing a
,

l most any temperature short of boiling With vegetable

tanned leather 50 C may be taken s a maximum but
°
.

cold wet skins may safely be introduced rapi dly into a liquor
a .

heated to
a
as they will cool it sufficiently
The Continent l method of dyeing in two trays may be men
t io n e d here as it produces very rapid and even dyeing with
.

, ,

considerable economy of dyest uff and the principle is capable of , l

application to other m ethods where a large number of skins have

to be dyed to the same colour A s generally carried out t wo .

trays are employed each about 4 feet long 1 8 inches wide and
, , ,

1 0 inches or a foot deep and these are usually made with a slop
'

’
,

ing bottom or propped up in such a way that the dye l iqu o r all
,
f

runs to the farther side of the tray A single pair of skins is

usu a
.

ll y dyed at once (inabout 6 litres ( 5 quarts) of liquor for sheep

and goat ) To begin with the first tray is fil led with a very weak
liquor and the second with one of about h a
.
,

,
l f strength The .

goods are entered in the first tray turned a few times and passed , ,

into the sec o nd the liquor in the first is run away and it is
a
,

refilled with one of the full strength to which the goods r e then ,

transferred and dye d to shade The second tray is much reduced .

in strength by the skins and now ser ves as the weak liquor for a
,

a
fresh pair which in its turn passes into that from which the goods
,

have been dyed out and then into a new liquor e ch pair of
, ,

goods thus passing through three baths o f which the last is of ,

ful l strength and which quickly brings up a full and even colour
, .

In the ordi nary English method the goods must for the sake of
‘

economy of dyestu ff be dyed out in a nearly e xhausted bath

, ,

which is a tedi ous operation the last stage of dyeing often taking
,

a time far longer than that required to bring the goods nearly up
to shade and even then failing to produce a good and full colour
, .

This evil may be l essened by adding the dyestuff in several Su c

c essiv e portion s as the bath becomes exhausted but cannot be

a
,

l together avoided with a single tray if any reasonable exhaustion

of the bath is to be attained A t first sight it seems a very slow .

process to dye the goods in single pairs but this is to a great ,

extent compensated by th e rapi dity with which they take o n

colour On the other hand the solutions must be of considerable
.
,

strength to avoid undue loss of time In the Continental system .

 59 2 P RI N C I P L ES OF L EA TH ER MA N UFA C TUR E

the dyes mostly of the coal tar series are used as strong solutions
,
-

, ,

and each new dye bath is made up by fill ing the tray wi th a
definite volume of hot water a
-

n d addi ng a measured quantity of

the dye solutio n -

The r e use of partially exh austed dye baths is generally limited

‘

- -

to cases where either single dyes or mixtures of very equal affinity

for the l e ather are employed since where dyes of unequ a l affinity
are employed one is m ore rapi dl y removed than the o ther a
,

nd
the shade of the dye bath is a
,

l tered Many dyes sold as single

-
.

colours are really mixtures 1 and alter in shade if successive

quantities of leather are dyed in their s olution s B asi c dyes a
,

re .

also apt to be precipitated by traces of t annin washed out of the

goods and thus rendered unfit for use a second time This may
,
.

be avoided by suit able preparation of the goods ( see p .

Much of the success of practical leather dyeing d ep en ds on

proper selection a n d preparation of the goods Sound uninj ured .

grain is a matter of first importance no satisfactory dyeing can

be expected on skins which t hrough carelessness i n soaks limes , ,

or bates are tainted by what is known as weak grain caused .

,

by destruction or inj ury of the delicat e hyaline layer which

forms the natura
.

l glaze and outer surface o f the skin ( p

'

For such goods acid are to b e preferred to basic dy es ,

the latter having an especial tendency to dye darker and deeper

where the grain is imperfect Goo d s of different tannages and
colours shoul d never be dyed together a s t h e y are cert a
.

'

in to ,

produce different shades in the same dye bath Tanne d skins -

.

which have been dried especially if they have been in stock for,

some time should be thoroughly softened by soaking in tepid

,

water and drumming a temperature of between 40 and 45 C ° °

being most adva

,

ntageous Skins such as calf of mixed or bark

‘

.
, ,
i

tannage must now be freed fro m all bloom by s c o urin g wit h brush
a
,

and if necessary with slate or stone but great c re is requisite to

avoid injury to the grain A little borax or other weak a
,

.l kaline
solution assists in removing bloom Fresh sumach tanned s kins .
-

a
merely require setting out with a brass or vulcanite sleeker but ,

those which h ve been long dried often dye more evenly and
readily if they are r e s um a che d

a
-

D ark coloured tann ges such as A ustralian bazils and East

I n dia sheep and goat tanned wit h c a ss ia a
-

, ,

bark are l ways im ‘

1 a
Su c h m ix t u r e s m y o ft e n b e d e t e c t e d b y p u t t in g d r o p o f t h e ir a
a
s o l u t io n o n b l o t t ing p p e r wh e n t h e d y e s f o r m d iff e r e n t l y c o l o u r e d r in g s
-

a a fi a a
,

c c o r d in g t o t h e ir m o r e o r l e s s r p id x t io n b
y t h e p p e r o r b y d u s t in g
a a a
,

t h e d r y d y e very t h in l y o n w e t b l o t t in g p p e r wh e n e c h p r t ic l e p r o d u c e s
-

aa
,

it s s e p r t e s p o t .
50 4 P RI N C I P L E S OF L EA TH ER MA N UFA C T UR E

no alterat ion in the colour Fo r browns yellows deep reds or

yell ow greens it i s a
.
, , ,

-
dvantageous to use titanium potassium -

lactate or o xalate ( 2 grm per litre ) which in combination with the

.
,

tannin produces a very permanent yellow coloration on which the

basic colours dye freely In many cases the titanium salt is best
.

applied after dyeing with one of the dyewoods ( Dreher) .

The basic colours usually require simple solution in hot water

before addi ng to the dye bath and are used in quantities of -

o 5 to 2 5 grm per li t re of dye bath accor d ng to their colouring

i
'

power which varies a g ood de a

-
.
,

,
l and to the depth of shade ,

required The solutions should not be boiled and some colours

'

a
.
,

r e inj ured by too high a temperature } Some colours dissolve

incompletely and requir e fil tration through a cotton cloth A s
,
.

basic colours are precipitated by calcium carbonate it is im ,

portant that temporary hard waters should be neutralised

with acetic or lactic acid till they faintly redden litmus
the case of colours which from their ttraction for the leather ,

fibre dye too rapi dl y and consequ ently unevenly better dyeing
and in
a
, , ,

is often obtained by the use of a small excess of acetic acid . ,

which also increases the solubility o f the colour To o much .

acid however will prevent the prop er exhaustion of the bath

, ,
.

Some few colours now little used require to be di ssolved in the

, ,

first instance in a li ttle methylated spirit and the ad di tion of '

spirit wil l often assist dyeing and staining where the leather is
slightly greasy though considerations of cost generall y prevent
,

its use So dium sulphate is not unfrequently added to dyeing

.

bath s to improve equality of dyeing ; and with some of t he ,

cotton dyes common salt is used to lessen their solubility and

facilitate the exhaustion of the dye bath -
.

A cid colours usually need the addi tion of acid to the dye
bath to liberate their colour acids and for this purpose sulphuric
acid is gen erally used in weight about equ a
,

l to that of the colour

used It s use is however obj ectionable in this case for the
.
, ,

same reasons as in bleaching since it is impossible by mere ,

washing to remove it entirely from the leather which it ulti ,

mately rots when concentrated by exposure to a dry atmosphere

,
a
or high temperature n d it is b e t t er to use formic acid to the '

extent of two or t hr ee t im es the weight of the dyestu ff So di um

'

acid sulphate ma
.

y also be used b u t is probably more obj ection

‘

able than an organic acid Many acid colours however dye

a
'

quite satisf ctorily from a neutr a

.
,

l bath The acid colours are .

used in somewhat similar quantities to the basic , but are generally

inferior in colouring power though they dye more evenl y e sp e ci , ,

ally o n defective grain and are often more permanent to light

, .
 D Y ES A ND D YEI N G 50 5

Mention has a l ready been made of the polygenetic or mordant

dyestuffs which are still used to some extent for dyeing glove
leathers and of which log wood is important in dyeing blacks
Fustic and B razil wo o d (p e a
.
,

ch wood) are not quite gone out of

'

- -

use among old fashioned dyers even for dyeing moroccos and -

ot her colou red leathers of vegetable tannage P each wood

'

-
.

”
with a tin mordant ( general ly a so called tin spirits made by -

dissolving tin in mixtures of hydrochloric and nitric acid) was

formerly much used in dyeing cheap crimso n s but is now quite ,

di splaced by the azo scarlets 1

The a c id tin solutions were -
.
-

frequently very injurious to the l eather .

Th e wood infusion rendered slightly alkaline with soda

ammonia or formerly with st a l e urine is usua
-

, ,

, ,
ll y dyed first on , ,

the leather and followed by the mordant stri ker

,
ferrous or
ferric solutions and potassium bichromate being used for dark
colours and tin salts or sometimes a
,

,
l um for the b ri ghter ones , , .

Th e mordant is sometimes added to the dye bath towards the -

end of the operation but is better used as a s eparate bath as it , ,

is apt to produce a precipitate of colour lake on the surface of

the skin which rubs o ff on friction In some cases a
-

,
nd especially .
,

in black dyeing the strong infusion of dye wood and the n e c e s ,

-

sary striker are successively applied by brushing instead of

in the dye tray
Logwood and B razil wood are both Ca
-
.

esalpinias closely allied

to divi divi Logwood is Cwsa lp im a Ca

-

mpechi ah u m ( see p
'
‘

It s colouring matter is h a
. .

e matoxylin a substance nearly all ied

to tannins and a
.

,
'

l most colourless ; which on oxidation gi ves

hmm a
,

t in which dyes di rectl y a y ellow brown only developing

other colours by the a
-

, ,

id of mordants Logwood chips are .

extracted by boili ng or heating under pressure for some time with

water and as h a ematin gives dark purplish red compounds with -

alkalies soda or st a,
l e urine is frequ ently added under the mis
taken belief that it produces a better extraction but it really ,

leads to waste of colouring matter by oxidation It is best to

extract with water a l one and add any necessary a
.

l kali to the ,

infusion before use On e to 2 lb of wood per gallon is frequently . .

employed in making t he infusion and as this proportion of water ,

is quite insuffic ient to properly extract the wood the residue ,

sho ul d be boiled with one or more further quantities which are ,

employed in turn for extracting fresh portions of wood Logwood .

1
Az o —
colours a ail y
re e s r edu c e d ad b l ah d b y m t a
n ll i m ad t h
e c e e c z c, n e

w r it e r once e x p e r ie n c e d con s id a
er bl t bl ef m gal a i d
ro u b lt e ro v n se o s

u se d in t h e fit t i n gs o f a pp co er bat h ad z i if d a
t a
nll h ld b p nc use s ou e ro

ai h ja
pa
,

t e ct ed b y v rn s or n .
50 6 P R I N C I P L ES OF L EA TH ER M A N UFA C T UR E

dyes best at high temperatures and especi a l ly in the case of ,

chrome leather with which a temperature o f 80 C may be safely

,
°
.

used The presence of a trace of a salt of lime is advantageous

.
,

and with very soft waters a little lime water or chalk may be -

added to the logwood liquor Logwood extracts be1 ng princi .

,

pally used for blacks with iron mordants are frequently adul
t er at ed w
,

ith tanning substances .

In blacking s ki n s th e strong infusion is rendered slightly

alka l ine with sodium carbonate or am monia and brushed u m ,

diluted o n the leather If employed as a bath a somewhat

' “

weaker infusion is used and the leather is frequently treated

’

first in an alkaline bath to which a sm a

,

l l quantity of po t assium
bichrom ate is often added The obj ect of the alkali is not only .

to assist in the formation of the colour lake by saturating the

acid set free from the iron s a
-

l t used as a st riker and thus to ,

prevent the colour from penetrating the leather too deeply but ,

at the sam e time to overcome the r esistance to wetting cau sed

by gr e a s e o r oil which the leathe r may cont a
i

.
in It is possible

a
.

that in some cases sulphonated oil soaps might be used with

advan tage A lk li must thus be u sed more freely when stu ffed
.

l eather is to be blacked but excess sho ul d be carefull y avoided , ,

as it easily renders the leath er tend er and brittle . The potassium

bichromate oxidises the h a ematoxylin or the ferrous salt sub ,
‘

sequently applied and forms a nearly black chro me logwood

a
-

a
lake Bichromates must be used with great caution s they
.
,

tender the grain and render it liable to g pe in subsequent

,

stretching
The iron solution is gener a
.

ll y either of ferrous sulphate of

”
perhaps 5 per cent strength or commercial iron li quor which .
,
-

is a pyrolignite or crude ace t ate of iron containing catechol ,

derivatives and other organic products fro m the distillation of

wood which act advantageously b oth as antiseptics and in
, ,

preventing the rapid oxidation which occurs when pure f errous

acetat e is used Iron liquor is genera l ly to be pr e ferred to
.
-

ferrous sulphate green vitriol as the sulphuric acid of the

latter unless complet ely neutra l ised by the a l kali employed
’

in preparation acts in t h e end disastrously on the leather Com

m e r c ia
.
,

l iron liquor is often adulterated with ferrous sulphate

-

which may be detected by its giving a precipitate with barium

chloride Great care should be taken not to use iron in excess
.

of the logwood or tannin present as it otherwise takes tannin ,

from the leather itself making it hard and liable to crack while , ,

any uncombined iron acts as a carrier of oxygen giving up its ,

oxygen to the colouring matter or tannin with which it is in

50 8 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E ‘

in a slightly damp o r sammed condition and the colour is ,

applied evenly with a softish brush in two or three coats the ,

leather being slightly dried after each A s a rule the more coats .
,

are applied the more even is the work but to save cost of labour
it is common on cheap goods to be content with two of which ,

the first is given preferably with a weaker solution to the dry , ,

leather Wh ere the leather is weak grained it is sometimes

advant a
-
.

geous to Size it first with a weak solution of gelatine gum ,

tragacanth or linseed mucilage and similar solutions are often, ,

used to fix the colour and give a higher gloss A weak solution

-

of the stearine glaze mentioned on p 49 4 is sometimes employed “

as a vehicle for the acid colours A cid yellows and browns ma

.

y .

also be di ssolved in the undiluted glaze where only a pale colour

is required or to heighten the colour o f leather already stained
,
.

A list of suitable colours for stai ning is given in A ppendix C ,

'

p 640 . .

I t rarely happens in leather dyeing that the r e qu1 re d colour

can be gi ven by the appli cation of a single dye most of the ,

shades now required bein g produced by mixtures It is there .

,

fore necessary to say a few words on the theory of colour

,

combinations .

White light is of course composed of a mixture of all the

spectrum colours and can be separated into them by the prism ,
.

I t is probable however that the eye is only capable of three

di stinct colour sensations and that a
, ,

l l the colours we perceive are -

represented b y the excitement of these in di fferent proportions

'

the act u a
,

l col our sensations being r e d blue green and violet 1 -

,
-

,
.

If we interpose a piece of yellow glass between the eye and white

light the violet and blue are absorbed and the remaining red ,

and green rays co mbine to produce the sensati on of yellow I f

, .

1
Th e sub e c t j of c olo ur is t o o co mpl c
i a
t d e to be a
d q a
t lye u e t r e t ed a
her e ad f f l l i f m a n ti or fu d t Ab er
y C l n or on re a
d a ers r e r e e rr e o ne
’
s o our

M a m t ad Mi t
,

e s ur e en L d n 89 Th i i w n x u re , on on , 1 1 s s no u

a a a a
.
,

f t or un t ly t f p i t b t th e ou l m o t b k m g
r n u er e re se ve r ore recen oo s, on

wh i h m a ta It m a
, ,

y b
c m ti d L ki h C bl
e 9 5 eny h w one uc es ons e, 1 1 o e ver ,

t t ha p im a a a
.
, ,

b ep i t d o n t w h il the t ou y l ti e e r ue r r c o o u r se n s ons re un

ad i l t ad b y m i t
-

a
,

q ti
ue s bly d bl on g re f l ig ht f ue -
r ee n , n v o e n x ur e o o

a a b p d d th
, , .

th l
e se ll th co oursl i l d i g whit o er c o o u r s, nc u n e, c n e ro uce e

p im a a d y l l w ad b l t h ff t b i g p
,

r y p ig m t r dy en s o r es re re e o n ue, e e ec e n ro

a by th a ad i t h l a
, ,

d uce d i th f m n d d it i
e f ol
or er ctt by se e on o c o u rs , n n e er

th i e r bt a ti M h
su f l i f ma
r ti
c ab bt a
on i d by th uc u se u n or on c n e o ne e u se

f a f a di a ab
.

o p k t p t p
oc e s y p i m fit t d i t
e c r o sc o e, o r e ve n o n or n r r s e n o ox

( g aig ab ) wit h a a w adb a

e c r d oxl it pa al l l w it h t h p i m n r ro c r o r s r e e r s

Dy d ma ial a mi d i a g d da
-

a a
. .

t th p p it de o t os e en yl igh t e er s re ex ne n oo

b y da t f a W l ba
.
,

dy l ti
e so u
-
i te t t b yl igh t
ons i f n h s l t i
-
u es or n ro n o e s c or e ec r c

l igh t Th t .
g t h l igh t t h a w t h lit whi h h l d b
e s ro n er d e e n rr o er e s c s ou e u se .
 D YE S A N D D Y E I N G 59 9

pure blue glass is used the red is absorbed and we have blue
as the resul t of the rem a
,

ining mi xture of green blue and violet

R e d glass absorbs the whole of the green and greenish blue a
, , .

ll ow
a
-

ing red yellow and much of the violet to p ss Thus if we com

,
.

bine blue and yellow glass only the green is allowed to pass and ,

similarly with red and blue glass gre en and blue is cut out and ,

only the violet remains Thus red yellow and blue are frequently
.
, ,

called the primary colours and by combining all three in equal

,

proportions all colours are cut out and black or grey results , .

The blue and violet which are stopp ed by yellow glass are those
colour s which would produce the sensation of violet blue and -

hence the latter is called the complementary colour of yellow ,

and so on with the rest It will be noted that all the colours of
coloured obj ects a
.

r e produced by absorption of a part of the light

and therefore coloured bodies are a

,

l ways darker than white ones ,

and where a colour is mixed with its complementary in suitable

proportion all colours are absorbed and black or grey is produced
,
.

Colours which are made by mi xing two p ri mary colours are

generally called secondary while the duller tints made by
the ad di tion to these of black or of a complementary Colour
which produces black are called tertiary
,
A n y prim ary colour .

is co mplementary to the secon d ary colour produced by mixing

t h e other two primaries and vi ce ver s a Th e following tabular
, .

arrangement shows at once the e ffect of colour mixing :

with B lack

Olive Sage , .

P urple ( Violet ) P uce Maroon

'

.
,

Theoretically colour may be obt a

,
ay
n ined by m1 x t ure of the
primaries and that this is possible to a great extent is sho wn in
,
”
the success of modern three colour printing by which pictures
“

are obt a
-

i n ed l n natural colours by the use of three primaries only

but l n practice few colours are q uite pure and if two very di fferent ,

colours are mixed it is di fficult to avoid the production of

,

tertiaries The most brilliant colours are generally produced

.

by dyeing with the nearest colour which can be obtained to that

required and sha di ng with another which is near but on the
, ,

other side of the desired tint .

Thus if we want to produce bright shades in dyeing we must

avoid the introduction of complemen t ary colours A bluish red .
-
 P R I N C I P L ES OF L EA TH ER MA N UFAC T UR E
“

51 9

mixed with a reddish blue will produce a brig ht shade of Violet -

but if we mix an orange red with a greenish blue we introduce - -

yell ow into the mixture and obtain a dull maroon or puce

a
, ,

ccording to the prop ortion of the other colours In a similar .

way the introduction of a blue dye will dul l a bright orange to

“

a bro wn and a little of a yellow dye will dull a b ri ght purple to

,

a maroo n This fact is f requently used in producing the quiet

.

shades of colour often required from the most brilliant dyes If ~

.

to a bright orange we add black or a blue dye which as its com

p l emen t a
,

r y produces black we convert it into a brown If , .

instead of blue we use green for dulling we give t hefi b ro wn a

‘

yellower shade since the green produces black at the expense of

the rea
,

l of the orange Violet similarly used gives a redder bro wn

.
,

since it produces black by combination with the yell o w This .

shading if small in amount is frequently done by direct mixture

, ,

of a suitable dye but if considerable it is generally better to top

, , _

one colour with another Thus a blue topped with a powerful

orange will pro duce a Hava
.

n na brown Fo r dark colours it .

is frequently convenient to produce a dark ground with som e

cheap dye such as logwood and iron or chrome and to top it
, ,
.

wi th a bright shade of the col our required In this way cheap .

dark blues and greens can be easily produced Fo r reds and .

browns mixtures of logwood and B razil wood or Brazil wood and

fustic ma
- -

, ,

y be used
, top p ed with coal tar c olours T anning ,
-
.
“

materials such as quebracho and mangrove extracts which give

, ,

bro wns with bichromate are also employed on cheap goods It

is a
.
,

l so frequentl y wise to dye with a basic colour and top with

an acid one o r vice ver saas in many cases the one fixes and
.
, ,

combines with the other and an increase of fastness is obtained ,

.

Morocco and many other coloured leathers are finished by

damping the surface of the dried leather with a very dilute '

seasoning of water milk and blood or albumen allo wing the

a
, , ,

leather to become quite or nearly dry and polishing b y frictio n , _

under a cylinder of agate glass or wood in the glazing m chine

1
, , .

Many leathers are also grained by printing from engraved or

electrotype rollers or by boarding , or a combination of the
two Boarding consists in pushing forward a fold in the
leather on a t a
.

b l e wit h a flat board roughed unde r neath o r l in e d

'

with cork in a way which is di fficult to describe but wh ich in

, ,

skilful hands wrinkl es or grains the skin in a regular pattern .

The colour of a dyed skin is much altered by finishing and ,

1
a
A g t e is b e st f o r afi a l gl a
n z b t h ad w d ( b o l ige, u r oo x or nu m v it ea
) g et s

b et t er t o t h e b o t t o m o f th g a i Gla i l
e apt t r n ss s e ss o se i e z in t h e
ahi li h i t a ab a
.

m c ne if it s h igh p o s k ff b y fi
s m y en o ne e er or c . r o run du m p p er .
 CHA PTER XX I X
E VA P OR A TI ON , H E A TI N G , A ND DR Y I N G

Q U ESTI ON S of evaporation wh ether for raising steam or for the

concentration of t a n n1 n g e x t r a
,

c t s and other solutions are of

*

considerable importance in the tanning industry a

,

nd as the ,

same natural laws which apply to these equally govern the

drying o f leather it is convenient to study the theory of the
,

whole subj ect in one chapter rather than to divide it and place,
-

each part in a di fferent portion of the book .

Th e modern conception of evaporation and vapour pressures

has been described on p 8 6 but it will b e necessary to r e
'

.
_ ,

capitulate a little It is a w ell known fact that most liquids

.
-

if left exposed in an open vessel gradually disappear by evapora ,

tion from the surface into the air even at ordinary temperatures ,
.

”
If the vessel is heated su ffi ciently the l iquid boils that is , ,

bubbles of vapour are formed within it and escape and the ,

a
evaporation is therefore much more rapid To avoid complica .

tio n let us first im gine a liquid sealed in a glass flask which con
tains no air but which is only parti a
, ,

,
l ly filled by the liquid It .

has been pointed out th at the motion of heat by which the

molecules of t he liquid are agitated enables some of them to
break away from the attraction by which liquid particles are held
together and pass into the form of gas or vapour which will fill ,

the empty part of the flask This evaporation will however

. .
, ,

soon reach a limit since the vapour canno t escape from the flask
, .

The flying m o lecules of vapour produce pressure by striking the

wa l ls of the flask while a proportion of them will s t ri ke t h e surface
,

of the liquid and again be caught and retained by its attraction

a
,

n d as the pressure rises t h e number of these necessar ily in

,

creases till a point is reach ed when as many fall back and are
retained ( or condensed as those which evaporate and t he
pressure will then rem a
,

i n constant The amount of the pressure .

will vary with the nature of the liquid and will be the greater ,

the more volatile it is or in other words the less the power of

, , ,

its internal attraction It will also increase with rising tempera

.

ture which by increasing the velocity of motion of the molecules

, , ,

renders their escape from the liqu id easier and their recapture
more di fficult It will not be at a
,

. l l affected by the volume of

51 2
 E VA P ORA TI ON ,
H EA TI N G ,
A ND DR YI N G 51 3

v apour or the size of the flask but so long as any liquid is present ,

it will depend merely upon the nature of the liquid and the '

temperature If the flask is large more o f the li quid will eva

p o rat e till the sa m
.
,

e pressure is reached If at the outset the .

flask is not empty b u t fil led wi th air it will make no di fference

to the pressure or qu antity Of the va
, ,

r in it which w i ll be
p o u
-

a If the se a
,

dded to that of the air whatever that may be l ing ,

.

of the flask is broken so that it is Open to the atmosphere air

and vapour will escape or air will pass in till the total pressure
is equ a
, ,

l to the atmospheri c pressure outside ( about 1 5 lb per .

square inch ) A s however the vapour in the flask is always

.
, ,

renewed by evaporation so th at the full vapour pressure of the

liquid is m a partial pressure ( as it is c a
-

i ntained the l led ) of

the a
,

ir in the flask will be less than that of the outer atmosphere

by the amount of the vap o ur pressure which makes up the -

difference Once this bal ance is attained evaporation will go

.
,

on very slowly in the flask as it can only replace the small ,

quantity of vapour which escapes : If however the vapour is , ,

removed by blowing fresh air into the flask it will rapi dl y be ,

replaced in t he old proportion by fresh evaporation Thus .

g00 ds in a close room will dry only very slowly even if the ,

temperature is high unless the moistened air is replaced by ,

drier air from the outside by some effective system of ventila

tion In absence of this evaporation only becomes rapid when
.
,

the temperat ure of the liquid is raised to its boiling point ,

that is when the vapour pressure becomes slightly in exc e ss of

,
-

that of the atmosphere so that the freshly formed vapour can ,

push out that already in the flask or chamber into the outer
air and at the same time bubbles can be formed in the interior
,

of the liquid by the escaping vapour As the vap our pressure .

-

of a liquid rises continuously with increasing temperat u re and ,

its boiling point is defined as that temperature at which it is

equ a l in pressure to the air ( or vapour) in contact with it it is ,

evident that the boiling point must entirely depend on the pres
sure Thus the boiling point of water in a boiler at a pressure
.

of 55 lb per square inch above the atmosphere is 1 50 C and in °

a parti a l vacuum equ a

. .
,

l to 5 8 inches of barometric pressure is -

onl y 60 C a fact which is made use of in the concentration

°
.
,

of extracts and other liquids at a low temperature in the vacuum

pan and in the Nance system of tannings ( p (A tmospheric .

pressure is taken at 3 0 inches or 7 60 millimeters of the barometer ,

7 lb per inch or 1 0 3 3 kilos per square centimeter )

'
1
or 1 4 -
.
,
.

1
Th e G e r m a n s p e l l in g of m e t r ic l a u n it s h ab s e en a
ll w o ed to rem ai n

fr o m t h e fi r st e d it io n , b oth t o a id vo e x t e n s iv e c o rr e c t io n ad n b ec a
u se

33
51 4 .
P RI N C I P L E S OF LEA THER MA N UFAC T UR E "

a piece of iron is placed over a powerful gas burner it will

If -

go on getting hotter till its temperature is nearly or quite equal “

to that of the gas fla me On the other hand a pan 0f water in -

.
, ,

the same con dition once it has reached its boiling point becomes , ,

no hotter till all the water is evaporated It is evident that the

whole available heat or energy of the gas fla
.

m e is consumed in -

c onverting the water into steam We might convert a propor .

tion of this energy into mechanical work by using the steam

in a steam engine ; but even without this work is actually ,

being done by the escaping steam in raising t h e weight of the

atmosphere and in overcoming the a
.

ttractive force wh ich holds

,

t he particles of water together in the li quid form I t is of course .

known to everyone that though energy may change its form

as from he a
,

t to work it cannot b e destroyed diminished or

a
-

, , ,
.

incre sed ; and therefore the wh ol e of the work performed in

converting the water into steam is again recovered as heat wh en
the steam is condensed Inthis connection a clear distinction
must b e m a d e between qu n tity of heat and temp er a a
.

tu r e which
’

in p opular language are often confused It is for instance .

,

obvious that if we mix a pound of water at boiling temperature

with another pound at freezing point the temperature is a l tered
to 50 C but the total qu a
°
. n tity of heat is unchanged
,
It is equally .

clear that no change in quantity of heat takes place when 1 lb

‘

of mercury at 1 0 0 is mixed with 1 lb of water at 0 though in

9 0

a
.
,

this case owing to the small cap city of mercury for heat the
, ,

common temperature woul d onl y be raised to about We

must therefore have some measure of quantity of heat apart
from the mere direct indications of the therm ometer and that ,

most generally used is the quantity of heat required to raise 1 kilo

a
of water 1 0 C ( kilogram c orie)
l 1
In England the heat required
°
.
-
.
"

to raise 1 lb of water 1 F is also in use as a unit The k calorie °

is equ a a
-
. . . .

l to 3 9 7 ( very approxim tely 4) lb X F or B T U

a
?

Fo r our purpose it may be taken that 1 00 k c lories of heat a

-
. . . .

re .
-

re quired to raise 1 kilo or litre of water from freezing to boiling

it is p h o n e t ic E n gl ish n d it s e e m s u n n e c e s s r y t oa dh e r e t o F r e n c h s p el l a a a
a a
,

in g wh e r e w e d o n o t d o p t t h e Fr e n c h p r o n u n c i t io n A p p e n d ix A )
a a a a a a
.

1
A gr m — c l o r ie o f o n e t h o u s n d t h p r t o f t h e b o v e is l s o in u s e f Or
-

so m e s c ie n t i c p u r p o s e s , b u t t h e kil o g r m —
fi c l o r ie o n l y i s u s e d i n the a a
f o ll o w in g p g e s a
at h a
.

2 T i
h s u n it c o m m o n l y k n o w n B T U B r it is h t he rm l u n it ,
‘

s e or

a qi d t a at it y f wa
. .
,

F i m
°
i e t h e qu ni lb t of he t
h re u re o r se 1 o er 1 s uc

a la t hat h a ad it i ap it y t h at it h a
. . . .
.
,

l i t i l
e ss c o n v e n e n ti l i n c cu on n e c or e, n s s

b l gal i d at h
ee n e it f h a ti g p w
se b y w h i h g am
s t be ld un o e n o er c s us e so

aa l ha
a w a d p t d im a
,

ad m a
i it w il l i
s nce l d d it i g whn vo v e l w ig h tn on c n e en e o ec e s

n e su r e s .
51 6 P R I N CI P L ES OF LEA TH ER *
MA N UFA C TUR E

highest temperature and lowest vacuum in the first effect

by the exhaust steam of the engine used for the vacuum p umps ,

while the steam from the first e ffect heats that of the next higher
concentration and s o on In the Y a , r ya n e vaporator p
( 40 8) . .

the boiling liquid is sprayed through coil tubes thus exposing an -

eno rmous surface to evap oration and the whole con centration
of a
,

ny given portion of liquid take s place as it passes through t h e

apparatus which does not even in multiple e ffects occupy more
, , ,

than four or five minutes and without the temperature of the ,

liquid ever rising above 60 or 7 0 C In the cas e of liquids like ° °

.
'

sugar and tannin solu tions which are liable to chemi cal change
-

from continued heating the shortness of the time is a very great ,

advantage The number o i e ffects which it is desirable to use

.

depends greatly on the cost of fuel as compared to the largely in

creased cost of the apparatus On e lb of coal employed in raising ‘

steam will evaporate 8 % lb in a single effect Ya r ya

. .

1 6 lb in a
'

n .
-

,
.

'

double effect 2 3 1 lb in a t riple 3 9 5 lb in a quadruple and 3 7 l b

-

,
.
,
.
,
.

in a quintuple e ffect apparatus but as a rule more than three

1 -

or four e ffects are not advisable ( see also p 40 7 )

Wh ere liquids are evaporated in the open a
.

.
ir at temperatures
below boiling it is advisable by some means to spread the liquid -

in a thin film so as to ex pose a large surface which must be

'

, _ ,

continuously removed by agitation so as to prevent the forma

tion of a skin An apparatus for this purpose is the Chen a
. li e r
evaporator ( fig which consists of steam heated copper discs
.
-

rotating in a t rough containing the liquid which is taken up by ,

buckets attached to the rims of the di scs and poure d over the ir
heated surfaces In other forms the liquid is a . llowed to trickle
over steam heated pipes or corrugated plates Such evaporators
-
.

shoul d be placed in a current of air so as to rapi dl y carry o ff

a
the vapour formed Their u se is very obj ectionable for l iquids .

like tannin liquors which are inj ured by oxid tion and they are
-

, ,

not nearly so economical as vacuum pans -

The drying of l ea
.

ther depends on the same laws as the evapora

tion of liquids but demands special consideration from its very
,

different conditions of temperature and supply of heat It is

important to remember that e va p orat io n c a
.

n n o t go on unless
'

the vapour pressure of the liquid to be evaporated is higher

-

than that of the vapour in contact with it and that air pressure -

,
-

1
Of c o u rse aim il as r eco n o my
“

wit h o u t v a
cuum a
m y be e ffe c t e d wit h
s o l u t io n s n o t a
in j u r e d b y t e m p e r t u r e b y wo r kin g t h e r st e ffe c t t fi a
h igh p r e s su r e a
n d t em p er t u r e nd a a
c o m in g d o wn t h r o u gh su c c e ss iv e

e ffe c t s t o b o il in g p o in t nd a a
t m o sp h er ic p r e ss u r e t h o u gh t h is is n o t s o ,

c o mm o n l y do n e .
 E VA P OR A TI ON ,
H EA TI N G , A ND DR YI N G 51 7

does not prevent evaporation so that if we sweep away the ,

stagnant vapour with dry air evaporation will go on as quickly

as in va
,

cu o except that the liquid cannot boil We must also

, .

bear in mind that evaporation consumes quite as much heat at

low temperatures as in a steam boiler and that this heat must
'

FIG . 1 1 0 . a
— Ch e n lie r E v p o r t o r a a ad Gl n ue Co o l e r s .

generally come from the surroun di ng air the tempera ture of ,

which it reduces .

The rapidity of evaporation and the quantity of moisture ,

which can be taken up by a given volume of air depends on the ,

vapour pressure which increases with temperature The relatio n

-

,
.

between the two and the weight of water in grams per cubic
,

meter which can be di ssolved in dry air is given in the following ,

table ( Grams per cubic meter is practically equivalent to

.

ounces per 1 00 0 cubic feet Vapour pressure rs gi ven l n m 1 lli .

-

meters of mercury of the barometer p 1 00 mm = 3 9 4 ,

. .
-

inches .

VA PO U R P R E SSU R E OF WA TE R
a —1 5 36
‘

Te m p er t u r e ,
°
C —
. 0 5 o 5 1 0 1 5 20 2 40
°
F . 1 4 23 32 41 50 59 68 77 86 95 1 04

P r e s su r e , mm 2 2 -

3
-
2 4 6
-
6 5 -

9
-
1 1 7 4
0
23 -

5 31
5 9 54 9
-

41
-

a
.

Gr m s p er cub m 2 4 3 4 49 9 3 1 2 8 1 7 2 22 8 30 1 39 2
- - - - - -

. .
51 8 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E ‘

is practic a
Air l ly never dry and in damp weather is frequently
“

saturated with moisture to the full extent corresponding to its

temperature In England the average quantity of moisture
.

contained in the air throughout the year is 8 2 per cent of the .

total possible and even in the driest summer weather it is never

,

less than 5 8 per cent So long as the water is in the form of “

vapour t he a ir r emains quite clear a

.

nd does not feel damp ln

fogs t he a i r is n ot only s aturated with moisture but contains

Of course when the a
,

a
small liquid particles floating in it 1
i r is .

re lly saturated with moisture it has no drying power whatever .

A s is ev ident from the table the amount of water which can

be di ssolved in a given volume of a
,

.
ir rapidly increases with
temperature A ir at 0 C is only capable of containing
.
°
.

grams per cubic meter or not much more than 2 0 per cent of ,
.

wh at it can contain at 2 5 C It hence rapi dl y increases in °

drying power as it is w armed and consequently the air in a

.

'

warm well ventilated drying room in win t er is generally much

-

drier and has greater capacity for absorbing moisture than the
,

open air in the d riest summer weather This is the principal

, .

cause of the tendency to harsh and irregular drying by the use

of artificial heat and may be remedied by a proper circulation
,

of the air by a fan without too frequent change wi th the colder “

air outside On the other hand the use of a little artificial heat
.
,

in damp summer weather when the air is saturated with moisture , ,

may be quite as necessary as in winter Th e amount of moist u re .

in the air is most easily ascertained by a device known as the

”
wet and dry bulb the rmometers This consists of t wo thermo .

meters mounted on a board one of which has the bulb covered

'
,
.

with muslin and kept moist by a lamp wi ck attached to it and

,
-

di pping in a vessel of water The temperature of the wet bulb .

is lowered by the heat consumed in evaporation and t h e di ffer ,

ence of its temperature from that of the dry bulb is proportionate

to the drying power of the air This may b e approximately
ca
.

l culated in grams per cubic meter by m ultiplying t he di fference

by 0 6 4 for Centigrade or 0 3 5 for Fa h renheit degrees and if -

deducted from the total capacity for moisture corresponding to

the temperature of the wet bulb as given in table p 5 1 7 will give
t he a ct ual moisture in gr ms contained in a cubic meter of air
_

but for practical purposes all that is necessary is to find b y

a ,
,
.
,

experienc e the temperature and di fference between the wet and

1
Th e a af g f l
re a so n m th t o ee s so u ch co l der a it th n s t h e r m o m et e r
t mp
e at i t ha
ert i wa
ure m i g it t
s, n r n o bo d y—
t mp a
t e er ure we h ave to
exp d th la t
en t h a t q i d t
e en
-
e re u re o c o n ver t t h e se l iqu id p at i
r cl e s in t o
v a
p ad i af t f g a
o ur, n l t m lt t h
n ro s s
o so o e e ic e .
 529 P RI N C I P L ES OF L E A TH ER MA N U FAC T U R E

may be dried out before the fats have time to take its place
This is generally best attain ed by the use of artificial heat a
.

nd ,

ventilation by circul ating the air by a fan without its too frequent
renewal especially in cold weather Frequently air which ha s

b een heated a
.
,

n d used for drying off finished goods and so ,

partially saturated with moisture may be used with advantage

— ,

for wet go ods or for other purposes where a more gentle drying
,

is re quired If the temperature is low outside the amount of

.
,

heat consumed in h eating cold air to the temperature require d

may be very considerable The weight of a cubic m eter of a ir s

at 0 C and atmospheri c pressure is 1 2 9 3 kilos a

o
°
nd its specific
he a
.
,

t at constan t pressure is o 2 3 7 5 of that of water Therefore to .

heat a cubic meter of air at ordinary pressure and temperature

1 C will require t he same amo unt of heat as that used to heat
°
.

o 3 0 7 kilo of water to the same extent or in other words 0 3 0 7 of

-

a k calorie .
1 -
If steam heating is used 1 kilo of good coal burnt
.
-

under the boiler sho ul d heat about 1 800 cubic meters 1 0 C o r °

'

.
, ,

1 lb should heat cubic feet 1 0 F assu ming that the °

. .
,

condensed water is not co oled below I OO C These seem large °

.

volumes but if we reflect that a 48 inch Blackman fan may

,
-

move cubic feet per minute we shall realise that the

a
,

cost of coal in heating ir is not inconsiderable

We must now consider the heat consumed by the actu a
.

l
evaporation of the water in the leath er The actu a
l evaporation
of water already r a
.

i sed to 1 00 C consu mes but °

.

the evaporation of water which has not previously been heated

so far consumes more heat and we may take that required at
“

ordinary temperatures as in ro und numb ers 600 k c a

,

l ories per .
-

kilo or 1 0 80 B T U per lb Disregarding small fractions this

,
. . . .
,

is equivalent to the cooling to the same t emperature of an

equal weight of steam in the heating pipes and this as we have , ,

seen demands about { 5 of its weight of coal for its production

from water a
,

l ready heated to I 00 C
°
.

Th e c o oling takes place in the first i n stance in the leather , , ,

the temperature of which is reduced like that of the wet bul b -

therm ometer and this 1 n its tu r n cools the air in co ntact wit h it
Thus in air drying without artifici a
, .

l heat the whole heat must

be supplied by the a
-

and the loss reduces its capacity for

'

n ,

1
F o r t h o s e wh o p r e f e r E n glish m e su r es room of 1 a a 0 fe e t cub e or

a ai a
,

1 00 0 c u b ic f e et or 28 1 2 c u b ic m e t e r s c o n t in s 8 0 4 3 o f
-
t f zi g r re e n

ad m a b am t p
p o in t n e n ro e er r e s su r e , ad q i n re u r es 1 9 B T U t a i th o r se e

t mp a a to a A t h t mp a
. . .

it
°
F 86 l i
°
e t er ure 1 or c or es i r se 1 C s t e e er ure

f a ad t a m wh a h a
.
, .

i th
r se s w igh t i b m e e o r eco es l e ss , k n es so e t l t t ess e o

ra i it A t 65 F o ly a
se b t
°
. n ou 1 8 B T U is
. . . r e qu ir e d .
 E VA P ORA TI ON ,
H EA TI N G ,
A ND D R YI N G 52 1

moisture greatly increasing the volume required This is not of

,
.

much consequence in open air drying Since even a light wind -

will supply air in enormous volume A moderate breeze of .

ten miles an hour moves about 1 5 feet or 4 5 meters per second .

When however the air must be moved by fans the power

, , ,

required becomes important The evaporation of 1 kilo of .

water at summer temperature will cool about 2 0 00 cubic meters ,

and that of 1 lb cubic feet of air 1 C .

°
.

In calculating the ventilating and heating power required in

fitting up drying rooms it is usually necessary to ascertain that
required under t h e most unfavourable circumstances and then
add a liber a
,

l margin to cover errors and accidents A s the .

cal culations are in consequence of the many varying con di tions

somewhat co m
, ,

plex it may be convenient to give as examples ,

"

the quantities of air and heat required to evaporate 1 kilo

( 2 20 5 lb ) of water under di fferent ordinary conditions and these
-

may serve as a b asis of c a

.
,

l c u lation of the drying power which

must be provided for di fferent tanneries
I n difi er en t Op en a
.
,

ir D ry ing — Air at 1 0 C ( 50 wet ° °

1

indicating a tot a
-
. .

bulb thermometer 7 C ( 44 3 l capacity for

° °

moisture of about 2 grm per cubic meter a

.

ir n o t to be cooled
‘

beyond 7 leaving a residual capacity for moisture

of 0 5 grm per cubic meter Each cubic meter will therefore
-
. .

take up 1 5 grm of moisture and as 1 kilo contains 1 0 00 grm

-
.
,
.
,

we have
1 00 0
666 c ub 1 c meters per kl l o re
qu1 r e d
-

to absorb m o 1 st u r e

9
~
888 cubic meters redu ce d 2 25
°
to furnish the
2 25 -

>
<o 3
600 calories required for evaporation Total air used 1 554 cubic .

meters or cubic feet 1

Dry ing with H ea

.

2 . t Outside air at 1 0 saturated with .

_ -
°

moisture heated t o 20 C ( 68 F ) acquires a capacity for 7 59 °

.
°
.

grm p e r cubic meter If we assume that a drying capacity of

. .

2 grm per meter is required to complete the dryi ng we have an

.
,

e ffective capacity of 5 9 grm -

.

1 00 0
2 1 7 0 cubic meters or . 60 0 0 cubic feet and to heat this ,

1 0C will require
°
. cal ories Evaporation of 1 kilo will con 51 0 .

sume 600 calories Total heat 1 1 1 0 calories

w a
.

D i it h H t —Outside air at as above heated °

3 ry g
n e 1 0 -
. .

to 2 5 C giving an e ffective capacity for moisture of 1 3 5 to

°
.

2 o = 1 1 5 grm per cubic meter

° -
. .

1
1 000 or 1 m .
3 =3 5 -

31 0 fe e t 3
52 2 P R I N C I P L ES OF L EA TH ER M A N UFA C TUR E

warm this
1 000
cub l c meters or cubic feet
’

87 307 0 . To
1 1 5
requires 1 ca l ories and 6 calories added for evaporation
°
3 00
1 5 9
gives a total o f 9 9 1 c a
,

l ories .

Compari ng 2 and 3 we see that the higher temperature is

more economical where it can be allowed than the lower , , ,

both in air and heat though this is partly compensated by ,

the greater loss of heat by cooling of the building etc which

it ent a
.
, ,

ils .

4 A i
. r at 0 C heat ed t o 20
°
requires
. about 9 7 cubic meters
°

or 3 43 0 cubic feet of air and a total of 1 1 80 calories , .

5 A i
. r at 0 C and h eated °
to 25 . C requires 6 3 cubic meters °
.

or 22 3 0 cubic feet and a total of 1 0 7 5 calories ,

.

C ( r
) equires 4 5 calories per c u b ic m e t e r
°
6 A i
.r at — 1
5 5 F
°
. .

_
'

to raise it to 0 C and acquires a capacity for drying of about

°
.
,

2 grm per meter . .

We will apply these figures to a drying room arranged with

a screw fan with a cent ral division or two floors so that the air
-

, ,

can be either ci rculated or replaced with fresh air from the out
“

side a t will ( see fig Such a room with 1 0 0 feet of length

.
.

clear of space required for fans air passages and heating pipes , , ,

and 20 feet by 8 feet in section should hang about 800 medium ,

butts weighing say 1 2 % kilos ( 2 7 lb ) each and when wet from the
a
.
, ,

yard containing the same weight of w ter A 48 inch Bl ackman .

-

fan under these con di tions wo u ld probably move say

cubic feet ( 565 cubic meters) of a i r per minute at the cost of
2 or 2 & horse power This in a room o f the sect ion named would
-

.
, ,

g i ve an average velocity of 1 2 5 feet per minute or rather under

I % miles an hour ; n o t a t a l l too much to keep the air freely

°

circulating among closely hung leather If we assume that these

b utts are to be dried in a week ( practic a
.

lly minutes) un der

a
the con ditions of No 2 the kilos of water they contain
.
,

will require cubic meters of air or bout 1 7 0 cubic ,

meters per minute or about Tit—6 of the air must be fresh every time
'
,

it passes through the fan On e kilo of water requiring 1 1 1 0

'

calories must be evaporated per minute .

U nder the con di tions of No 4 only 9 7 cubic meters of air .

per minute woul d be required or about g might be circulated ,

.

without change but the total heat required would be about the -

same 1 1 80 c a
,

U nder t h e c o n dit io n s of No s 5 and 6 some

'

,
l ories . .

1 6 2 0 calories per minute would be employed I t is har dl y nec es .

sary to provide for the full amount of heat required by No 6

a
.
,

since in this country such con di tions occur but seldom and never
for more than a few days at a t ime n d during such a
,

period ,
-
524 P R I N C I P L E S OF L EA TH ER M A N UFA C T UR E

but di fficult to estimate If we considerthe drying room a

. l ready
described the total area of the walls and ceiling is about 400 0
,
"

feet and to maintain its temperature 30 F above the atmosphere °

at 1 2 calories per square foot would require 480 0 c a

.
,

l ories per
hour or 80 calories per minute a very sm a l l am
,
ount compared
to that consumed in drying .

The fol lowing table calculated from data given by Bo x will

give some idea of the amou nt of s team or hot water piping
required for heating The sizes given are for t he 1 n t e r n a
-

l
diameter of the pipe allowance being m a
.

, d e fo r the increased
heating surface of pipes of ordi nary thickness Small pipes are .

co n siderably more e ffective in proportion to their su rface than

large ones and for high pressure heating 1 12 o r 2 inch wrought
,
- -

iron pipes are to be recommended as in many ways preferable

to cast iron The gilled or ribbed pipes now often used are a
. l so
advantageous as giving a greatly increased heating surface .

The temperature of the air to be heated is understood to b e

60 F
°
.at lower te mperatures t he qu a
n t it y O f heat given o ff by
'

the pipes would be greater and at higher temperatures less the

, ,

amount being approximately prop ortional to the di fference of

temperature between the air and the hot pipes It is also im .

HE Ar GI VE N B Y STEA M -
PIPES

K .
-
cal ories per hour per
foot run of Pipe .

portant to note that the table refers to steam pipes in still air -

and that if placed in a powerful draught ( as im mediately before

or behind the fan ) their heating e ffect may be at least doubled .

This has not been consider ed in the following calcul ations .

A pplying t hese figures to the est imate of 1 1 1 0 calories per

minute required for drying in our b uildin g a n d assuming 8 0 , _
 E VA P OR A TI ON , H EA TI N G A ND D R YI N G 52 5

calories p e r minute for the loss of heat through the walls we have
a tot a calories per hour a
,

l of about n d to obtain this

would require 7 3 6 feet of 4 inch pi pe a
,

F (heated by
°
t 220 -

exhaust steam ) or 7 0 0 feet of 2 inch pipe heated to 3 0 0 F by

°
-

, .

steam at 5 2 lb pressure . .

I f We adopt the estimate of 1 620 calo ries of No s 5 and 6 we .

Shall require 1 0 5 0 and 1 00 0 feet of the two pipes respectively and ,

this covers approximately the worst condi t ion s We mus t how .

,

ever re memb er that these estimates are made for continuous

'

dr ying during the t went y four hours and that if the fan and steam
a
-

re only applied during a portion o f this tim e the Su p p l y b o t h

'

of air and steam must be proportionately increas ed or the time ,

of drying correspon dingly lengthened .

It is very desirable however that the fan should be driven by

a small separate engine the steam for which W ill only forma
, , ,

sm a a
,

l l p roportio n of th t required for heating and of which the

Whole of the h ea
,

t will be recovered si nce even that utili sed in ,

a
driving the fan will again be converted into heat by the friction
of t he air and w ill therefore cost nothing This arr ngement

a
, .

will enable the drying to proceed so long as the necessary st eam

is maintaine d which in bad we ther can easily be done by the
,

night watchman It may also be pointe d out that during a great

.
,

a
part of the year the goo ds can be dried to a sammed con
, ,

dition Without he t or in t he open air or in the case of dressing ,

leather a considerable part of the water can be removed by .

pressing or squeezing e ffecting a further economy , .

It must be left to the reader to apply the same calculation

to other sorts of leather than sole but it may be pointed out
that the essenti a
,

l p oint as regards heating and ventilation is

, ,

the weight o f water to be evapo rated in a given time and that ,

‘

the actual size and shape of the dryi ng room is unimportant so

long a
a
s adequate heating and circulation of the air between

the leather is secured ; n d these remarks also apply to the

particular form of fan or o t her ven t il a t io n employed and to r ,

the means o f heating A s the quantity of heat consumed is very

.

considerable it is well to look out for sources of waste heat which

,

can be employed or for means by which the heat of the fuel can be
,

more directly and completely utilised than it is in raising steam .

Thus a large amount of heat can sometimes be obtained by pass

ing air through pip s or economisers fitted in a chimney flu e ; 1

or gilled stoves or c a e a
-

l o r ife r s may be used 1 11 a separ te chamber

‘‘

to directly heat th e air which 1 5 drawn m by the fan .

1
Th e s e p ip e s sh o u l d b e p r o vid e d w it h s c r p e r s t o r e m o v e a so o t , ai s n
’
fi
G r e e n s e c o n o m is e r , o r t h e ir e f c ie n c y w il l b e m u c h d im in ish e d .
52 6 P R I N C I P L ES OF L EA TH E R MA N UFA C T UR E

Figs . and 1 1 2 furnished by the James Ke ith and Blackman

1 1 1 ,

Co Lt d give a good idea of the c onstruction of screw fans of

. .
,
-

which there are now many di fferent patterns and the general ,

principle of arrangement of fan drying rooms the air in this case

-

b e ing circulated in opposite di rections on two floors and the ,

am ount of change being regulated by the shutters at A etc ,

.

The grou ping of pipes at the ends of the two floors which it shows

FI G . 1 1 I — Bl akm aF a
c n n .

is in genera l a good arrangement but the length between them ,

should not be too great or the drying will be unequal in differen t

,

parts of the room Sometimes this is convenient thus if most

of the heat be supplied to the a
.

ir coming fresh from the inlet

“

of the upp er floor the damper and colder air of the lower room
,

can be continuously used for drying wet goods from the yard ,

and the upper reserved for drying o ff the finished leather A .

disadvantage of this plan is that open air drying can seldom be -

utilised except in an elevated buil di ng ; and even when it is '

adopt ed means should be provided for heating the lower room

,

in cold weather In place of two floors it is obvious that a

.
‘

single floor may be di vi ded into two compartments by a longi

t u di n a
l partition Wh atever pipes are grouped at the ends of
.

the building it is advisable to arrange su fficient to prevent

,

frost against the walls or in the old fashioned way on the floors
, ,
-
52 8 P R I N C I P L ES OF L EA TH ER M A N UFA C T UR E

removes t he risk of accident from wet leather falling on the hot

pipes The latticed space should be open at the e n d facing the
.

'

air current so as to receive a portion of the draught which will ,

become heated and ascend its place being taken by damp and
c old a
,

ir from the leather to be r e warmed Water vap o ur in -

.
-

itself is lighter than air b ut the contraction produced by the ,

cooling o f evaporation more than compensates this and the ’

damp air is therefore heavier than the dry The arrangement

,
__
.

of ho t pipes near the ceiling of a drying room which has been ,

borrowed from some A meri can tanneries is wrong in principle , ,

unless the air is forced in at the upper part of the room or the
upper fl oor is latticed and only cts in other oa ,

is thoroughly mixed and circulated by mechanical ven tilators

s e s whe n the air a
,

while pipes near the floor will continue to produce a certain

amount of circulation of the air even when the fan is not running ,
.

In protecting pipes by lattices care should be taken not to

confine them too closely or their heating e ffect will be seriousl y
diminish ed In fan drying leather is p r efer a
,

b l y h u n g edgeways
'

to the current of air so a

-
.
,

s to allow of its free and uniform passage

,

between In the case of sole leather the butts or bends are

.

conveniently suspended by S hooks of brass or iron wire to hooks -

or nails fixed in the joist s If gangways between the leather

must be left in the direction of the dr ught they should be closed a ,

at intervals in the length o f the room by curtains or shutters so ,

as to deflect the air current into t he leather

-
.

Screw fans like the Blackman can be used either to suck or to

-

blow the air though the former is preferable where it can be

,

arranged b ecause it produces a more uniform current in the room

,
.

On the blowing side the air issues with considerable velocity in a

s ort of c o ne but little coming thro u gh the centre of the fan while
that near the edges spreads rapi dl y from its centrifuga
, ,

l motion . .

This is rather advantageous where the fan blows int o an open

room but involves waste of power where it disch rges into narrow
,
a
and square airways The ends of t he vanes o f the Blackman may
.

be turned in at the rim of the fan to prevent this tangential dis

charge but it is probable that where a fan 1 5 to bl o w into a room it
,

would be more advantageous to put it on the Inner side of the wall ,

and without curved ends to the vanes so as to di stribute the air as ,

wi dely as possible A somewhat similar result would be attained

.

with a Blackman by placing it in a p osition the reverse of that '

for which it is intended and running it also the reverse way but
, ,

its efficiency mi ght possibly be lessened .

Screw fans are good for moving large volumes of air at com
pa ra a
-

t iv e l y low vel o cities n d against little or no resistance but ,

 E VA P OR A TI ON ,
H EA TI N G ,
A ND D R YI N G 52 9

they are quite unsuitable for forcing air against high resistance or
through narrow channels and for this purpose cent rifugal fans like
,

the Capel ( fig 1 1 3 ) are much more suitable and mechanically

.
,

more e fficient In any case there is much loss of power in forcing

.

FI G . I 1 3
— C
. a aa
p e l Ce n t r if u g l F n .

a
air through narrow airways and if a screw fan must be employed
,
-

for the p urpose the channel sho ul d be as large in section s the

,

area of the fan and all sharp angles in its course should be
,

avoided There is great loss of power where a current of air or

.

water has to pass suddenly either from a wider to a narrower

channel or the reverse and in both cases the resistance is
, ,

diminished by making the enlargement or contraction gradual or

bell mouthed
-
Thus a pipe conveying water at a given head
.

34
 P R I N C I P L ES OF LEA TH ER M A N U F A C TUR E
‘

53 9 .

into or out of a cistern will discharge a much larger quantity if

the ends are bell mouthed than if it terminates abru ptly Fo r -
.

the same reasons air su ffers considerable resistance if it has to ,

‘

pass suddenly into or out of a larger space such as a drying ,

room and unn ecessary partitions and other abrupt changes of

,

dimension in the current should be avoided Curves should also

take t he p l a
.

c e of angles as much as possible

'

Syst ems in which air is drawn or forced over systems of heat

in g pipes by a centrifu gal fan and th en distribute d through
comparatively sm a
,

l l airways am o ng the leather which is to be

dried are in some cases convenient and advantageous A mong
”

.
,

a
th ese may be mention ed the Sturtevant and the Seagrave ,

B evingto n There can be no v lid patent on the general prin

c ip l e of heating by distributing air in this wa
.

y but only on the ,

particular arrangement o r appliances used in the special case

Centrifu gal fans should be considerably larger in dia
.

'

m e t e r than
in axial length those with long vanes of small radi us b ein g
,

wasteful in power from the i nsufficient supply of air to t he c e n t r e _

_
.

There is also no reason wh y in some cas e s centrifugal fans should ,

-

not be substitut ed for screw fans in drying on the system which I

first described especially in cases where the a
-

i r has to encounter
,

considerable resistance as ; for instance in traversin g a fil ter to , ,

remove dust On e of the best fil ters for this p urpose is a table of

.

wire gauze or fin e netting covered to a dep th of 3 or 4 inches with

-

loose wool H air or cheaper fibrous materials may b e sub

'

stituted f o r the wool b u t are less e ffi cient The air must of ,
“

course be sucked downwards through the gauze Wh en the wool

becomes dirty it may be washed if possible in a wool or h a
.

ir
washing machine and again spread on the table in a damp
,

condition as it will quic kly be dried by the current of a

,

,
ir Flannel .

is also useful where the wool hi ter is impracticable but requires -

frequent washing .

A part from wind natural ventilation is seldom to be relied , _

on for drying on any considerable scale Heated air is of .

,

course lighter than cold and this is the cause of chimney

, ,

draught but to get a good circulation in this way a high shaft

,

and high temperature is require d Nevertheless in o n e of it s .

,

best f orms the method has been a good deal used in Am erica
”
in the so called turret dryer a building of seven or eight
- -

stories in height constructed of wood with latticed floors and

heated by steam piping at the bottom Where the a
, ,

ir is admitted
-

,
.

The method is not likely to be much used in this country as , ,

apart from the questions of cost of buil di ng fir e ris k and trouble , ,

of raising and lowering the leather a good draught will o nly be ,

 53 2 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

frost but during use a vacuum is frequently formed by the

,
’

sudden c ondensation of the steam into which the water is shot ,

like the liqui d in a water hammer producing violent and ,

noisy concussions and in some cases even fracture of the pipes

,

o r l o o sen in g of their j oints

\
If high pressure steam is used a .
-

very small supply pipe will feed a considerable system of heating

-

p 1 p e s or radiators but with exhaust steam great pains should

,

be taken to have pipes of ample size to avoid back pressure on

'
-

the engines In b o t h cases it is often convenient to arrange the

.
.

pipes not as a continuou s line in which drainage is generally

, ,

di fficult but in parallels like the bars of a gridiron

,
With high .

pressure steam there ne e d be no fear if the pipes are kept clear

of air by all o wing a little escape through small a
,

i r taps of the -

a
,

steam failing to find its way to all parts o f the pipe as a vacuum ,

is produced by condensation in proportion to the he t given off

With exhaust steam no steam trap is desirable but any steam
.

not conden sed should escape freely into the open _air or a chimney
( after sepa r a t ing condensed water ) and it is well to render
.
the ,

resis t ance in all the pipes of a gridiron approximately equal

which ma
,

y be done by admitting steam at one corner and

allowing it to escape at the opposite ( diagonal ) one In the
a
.

arrangement of st eam pipes in p rallels the practicability of -

'

repair to one pipe or joint wit h o u t i n t er ferin g wit h the others

“

must always be considered If screwed wrought iron pipes are

‘

used each parallel must be provided wi th a bolted flange or ,

running socket to permit of unscrewing The di fficulty of

accurately adjusting the lengths of the severa
.
,

l parallels must be
considered especially with flanged metal pipes and also ”their
, ,

motion by expansion when hot which amounts to 1 or 2 parts ,

per 1 000 of length accor di ng to the tem peratures of steam and

a ir . Expansion j oints with stu ffing boxes are costly and trouble
some and apt to leak and may in many cases be avoided by suit
,

able arrangement o f the pipes Thus instead of having the pipes .

rigi dl y fixed at both ends one end of the system may be left free

a
to move each pipe being separately returned to an exit pipe at
,

the s me end but lower in level than the supply or a single exit
,

pipe may be thus returned its expansion and contraction bein g ,

practically the same as that of the heating pipes In moderate .

lengths of wrought iron pipe su fficient relief may often be obtained

-

from the fle x u re of the pip e if in some part of its course it is carried

at right angles to its general direction which is often necessary ,

for other reasons If pipes are laid in long lengths the l oose end
.
,

sh ould be supported on rollers or short pieces of pipe so as to ,

avoid moving the supports or straining the pip e in expansion .

 E VA P OR A TI ON ,
H EA TI N G ,
A ND DR YI N G 53 3

It is useless to attempt to regulate the temperature of low

pressure steam pipes by turning do wn the steam since so long
-

, ,

as the pipe is supplied with sufficient steam to fil l it its tempera ,

ture cannot be less than and even with high pressure pipes
the power of regu lation by a
-

l tering the steam pressure is very -

limited It is far better to arrange the pipes or radiators in

.

groups from som e of which the steam can be t urned o ff entirely

,

when less heat is needed It must not be forgotten that if thes e .

discharge into a com mon steam trap it will be necessary to turn -

o ff their exits as well as their steam supply or steam will come ,

back into t hem from the other pipes and probably prevent the ,

escape of conde nsed water In many cases it is more convenient .

to give the several sections independent exits or steam traps -

.

Many good steam traps are now on the market depending

either on the expansio n and contraction of met a
-

l s or on floats in ,

a closed box which open a valve as the water accumulates

, .

Traps o i the latter class with closed copper bah s are to be avoided ,

as the ball is sure eventually to become filled with water Several

t rap s ha
.

ve been devised in which an open vessel is used as a float

'

which is always kep t empty by the di scharge of the water through

a pipe dipping into it
Th e condensed water from steam pipes is rarely sui t a
.

ble for -

use in the tannery from the di ssolved and suspended iron oxide
,

which it contains from which it can only be freed by boiling

,

and fil tering or treat ment with precipitants ( p I t s most

app ropriate use is gener a
.

a
l ly return to the boiler Systems were .

formerly in vogue by which it was llowed to run back to the

boiler a s it condensed but these could only answer when the
pressure in t he pipes was equ a
, .

l to that in the boiler which is '

rarely the case It must gener a

,

l ly be forced in by the feed

.

pump or inj ector .

H o t water has often been advocat ed in preference to steam

,

for heating but is more costly as it requires a separate boiler

, ,

a
and much larger pipe surface for the same effect It s only -
.

important advantage is that the pipes m intain their heat for

some time even when the fire has gone down While steam pipes ,
-

cool at once if steam is allowed to go down in the boiler In .

any considerabl e tannery however this will seldom or never b e , ,

the case since if a go od pressure of steam is up at nigh t when

,

the fires are banked up the boiler will in itself contain a large ,

reserve o f heat and of course working pressure will be required

'

, , ,

before the engines can start in the morning H o t water systems .

-

require careful planning to obtain reliable and uniform circulation .

A heating system is in use in which water at high pressure

534 P R I N C I P L E S OF L EA TH ER MA N UFA C TUR E

and temperature much above boiling point is circulated by a

pump in thick wrought iron pipes of very sm a l l intern a
l di ameter
-

In the only case which came under the wr iter s observation it

’

was not very successful ,and if the pipes become choked from any
cause they are extremely di fficult to clear In ordinary hot
,
.

W ater systems without forced circulation the higher the heating

pipes are above t he boiler the better wi ll be the flow .

Among other leather drying appliances the aut omatic

-

dryer of Mr A NA Ma
,

rr of Leeds must be mentioned

. This .

consists of a long chamber I n which air warmed in side chambers , ,

MARRPATENT LEATHERSAMMlNC aYN M

DR l c
N
AC HlNE
C R O S S S E C T I O .

ép ee d a
‘
o

FI G . 1 1 4 .

and with arrangements by which the proportion of fresh air to

that already used can be reg ulated is circulated From end to , .

end of the drying chamber pass en dl ess chains sl owly m oved by

wormgear which carry the hides suspended from laths which
a
, ,

are picked up automatically at the entrance n d dropped at

,

the exit the heat and air circulation being so regulated that
,

they com e out dried at the farther end The writer has seen . \

Only one of these appliances in action which was drying chrome ,

tanned s t o c k ve r y satisfactorily b u t was rather too rapid for

'

vegetable tannages a defect which could easily be reme di ed

,

by a longer chamber and less intensi v e drying The apparatus .

is shown in figs 1 1 4 1 1 5 and 1 1 6 .

, , .

A nother arrangement which ful fil s the same purpose very

satisfactorily though less automatically is to suspend the goods
, ,

from laths which rest on overhead bearers passing from end to

end of a long drying room through which warmed air is blown
or sucked by a screw fan The goods are entered at the cool or
-
.
53 6 P RI N C I P L E S OF L EA THER M A N UFA C T UR E

and damper and carri es it down regularly below it ,

warm

air rising through wet leather is a

pt to g et chilled and form
 E VA P OR A TI ON , H EA TI N G , A N D D R YI N G 537

irregular do wnward currents It is necessary that the air as

.

it escapes from the pipes should be distributed and this

is sometimes done by sm a
,

l l free running fans over circul ar

-

apertures in the tubes driven by the escaping air '

Small .

perforations in the tubes will of course ful fil the same purpose ,

and a simple and adj ustable device would seem to be a circular

metal plate supported over ( or under) a round aperture in
.

the tube by a screwed central bolt on which its position could

be fixed by two check— nuts The possibility of adjustment is
.

somewhat important for unless both the size of the tubes and
, ,

the power of the fan is very ample the pressure will fal l o ff toward
,

the farther end of the system and the goods there will get in
,

s u ffic ie n t air
. Centrifugal fans are essential as screw fans will ,
-

not give su fficient pressure to overcome the friction in the com

pa rat ive l y small tubes and fo r reasons which have been a
.

, ,
l ready
explained it is necessary to provide means for regulating the
,

a a
proportion of fresh air to that which has been previously passed
over the leather On e of the gr e a
. t d van t g es o f the S urtevant
t
principle is its easy applicability to mo st existing buildings .
 C HAPTER XXX
CON S TR UC TI ON A N D M A I N TE NA N CE OF TA N N E R I ES
AS few architects have Speci a l ly studied the construction of
tanneries and in most cases much of the arrangement depends
,

on the knowledge of the tanner himself a short chapter on the

subj ect will not be out o f p l a
,

ce . .

In the selection of a site a clay or loamy soil is to be pre

ferred to a gravelly or sandy one as lessening t he liability t o ,

leakage and waste of liquor Perhaps however the first con

sideration of a
.
, , .

ll is the possibility of drainage and disp osal of

e ffluent waste liquors and washing waters since it is now rarely ,

possi ble to run these without previ ous treatment into a river or
stream Some in fo rm a
, ,

t io n is given in Chapter XXX I on the

'

methods o f partial purification which a

. .

r e available to the tanner

but these a re a a
_ ,

l ways costl y n d troublesome and the possibility

o f runni ng direct into a sewerage system or a tid a
,

l river is of
great advantage Under the Public H ealth A c t authorities a
. re -

b o und to receive manufacturing e ffluents into their sewers if the

latter are o f s ufficient capacity and the e ffluents not such as
either to damage the sewers or interfe re wi th the processes of
purification adopted by the authority This A c t is in many
di stricts practic a
.

l ly superseded by special legislation but tanners ’

e ffluents are genera

— ,

l ly received into sewers if freed from solid

matter When mixed with other se wa
.
g e t h e y do n o t interfe re
'

with irrigation or bacterial treatment 1

In selecting a site within .

a sewered district regard must be had to the possibility of

causing a nuisance to the neighbourhood by foul smells R e a
,

l ly .

injurious smells should not be caused by a properly conducted

tannery but it is difficult to avoid odour and a single ba dl y
, ,

disposed neighbour may cause infinite trouble and exp ense

.
.

Traditional rights are not to be depended on as a defence as ,

obj ectors may claim that a change of process or of the

arrangement of the tannery is not covered even if it is really a
,

,
n ,

improvement .

1
a
P e r h p s in t his r e s p ec t a ia l l im
rsen c e l iqu o r s aa
re n e x c e p t io n , but
a
-

t he u se o f a
r s e n ic s u l p h i d e c a w b di p e ns e d wit h s u b s t it u t in g c c um
l i
ad ai m
n no e s

a am i
,

s u l p h yd r t e or x t u r e o f s u l p h i d e o f so dium n c lc u . chl o rid e .

 P R I N C I P L ES OF LEA TH ER M A N UF A C T UR E
“

540

A hap ter on the construction and maintenance of tanneries

c

and leather works woul d be incomplete if it did not refer to the

very important question of Fire Insurance 1
To an extent this
ma
.

y be regarded as a fixed charge against any business very

‘

much in the same way as local and imperial rates It is not .

,

however to be lost sight of that to some considerable extent the

,

amount of insurance premium is regulated by the insured him

self If a m a
. n conducts his business i n unsuitable and badly -

constructed buil di ngs if attention is not paid to some of the

elementary hazards conn ected with a fire outbreak he must not ,

blame the insurance companies for the demand of what he 00 n —

siders an excessive premium If this f aulty construction and .

imperfect equipment of buildings pertain to any considerabl e

extent throughout a given t rade where the process is more or
less hazardous it is futile to appe a l to insurance companies
, ,

which after all are merely commercial and not charitable

, ,

institutions for a reduction in the rates The only standard to

, .

guide the company is the loss ratio and given a high loss ratio -

,
-

there must be a corresponding premium paid

There is however— thanks to modern s c I e n c e — amethod
.

available whereby the gr eat bulk of fires may be checked in

th eir inception an appliance automatic in its operation and of
,

proved efficiency This appliance is known as the sprinkler . .

A system of water pipes is fixed under the ceilin gs of the building

-

to be protected to which are attached sprinkling j ets at suitable

,
-

intervals each of which is closed by a valve held in place by a

,

j oint of fusible metal which gives way if the temperature ri ses ,

beyond a given point Water under su fficient pressure must .

of course be available There are two or three recognised

a
.

p tterns approved by the Fire Offices Commit tee after patient

investigation and practical test These appliances have n o w .
_

been at work for many years in this country On e of the firs t

.
.
-

trades to recognise their utility was that of the cotton spinner -

.

At one time serious fires in the cotton trade were of frequent

occurrence No w— owing to t he efficient fire appliances— while
.

fires may be as frequent in their inception as formerl y they are ,

stopped at such a stage as to prevent any considerable loss .

Th e consequence has been that the cotton spinner at one time

the o wner of a highly rated risk a
-

n d one which few companies -

cared to insure is now in the position of having his business

,

eagerly sought for and large discounts o ffered him o ff the charges
,

he was once called upon to pay .

1
W it h reg ad t fi
r o re in su r a nce, I a
m m u c h in d e b t e d t o Mr A W a
B in
al a ma
. .

of Le e d s fo r v bl iu e n fo r ti on .
 M A I N TEN A NC E OF TA N N E R I E S 54 1

More important still is the consideration to him that his

business is not so hable to be interfered with or stopped as the
result o f fire There are it i s estimated at the presen t moment
.
, ,

no less a proportion than 9 0 per cent of the cotton spinners

whose premises are protected by sprinkler inst a
-
.

l lations .

Other hazardous risks such as corn millers wooll en and worsted

’

manufacturer s saw miller s engineers are adopting these a

-

,
’ ’ ’

p
p l ia
-

, , ,

n c es freely
. and it is a matter of surprise that so very few
,

tanneries or currying shops have done the same The c o n se .

qu e n c e is that the l oss ratio in tannery risks still retains its

-

unenviable notoriety ; the rates for fire insurance have risen

considerabl y and as a resul t the tanners profits are correspond
,
’

in gl y less Considering the extent and importance of many of

a
.

the tannery risks throughout Great Britain one can only express ,

surprise that these appliances have been so little dopted There .

is of course ri sk of damage by water which should be covered by ,

the policy .

Th e construction of a new tanne ry demands serious attention

fr Om a n ins uran c e standpoint The boiler house should be a .
-

detached building the grin di ng of bark and myrobalans should

be conducted in buildings isolated from the general works in
fact no better advice could be given to a tanner either in the .

construction of new premises or the rearrangement and r e

modelling o f old than to consult an experienced insurance man
whether o ffic ia
, ,

l or broker as to the best mean s of constructing ,

and arranging to secure the most favourable terms .

A nother point which sho u ld be provided for and which is often ,

overlooked is the feasibility of future extension without Serious

,

changes of arrangement It may be taken as a probability of

the future even if it be not already a fact that sm a
.

,
l l tanneries ,

cannot be made to pay and that if a business succeeds its , ,

extension will prove desirable and in an ill planned yard this -

may involve either entire reconstruction of a very expensive and

.

inconvenient sort or the separation of new departments so as to

, ,

involve serious increase of carrying A good arrangement is .

that of a long front building serving to connect the whole behind ,

which the various departments are erected at right angles leaving ,

room for extension backwards as required .

A s regards the carrying of goods if the various soaks limes , , ,

bates and han dl ers are well arranged it is har dl y necessary to

, ,

do more than draw the goods from one pit into the next through
out the whole of the process To and from the layers the goods .

must generally be carried or wheeled In the sheds if it be a .

,

sole leather tannery the butts shoul d first come into turrets or ,
5 42 PR I N C IP LE S OF L EA TH ER MA N UFA C TUR E ’

open sheds for the rough drying then into a room sheltered ,

from draughts to temper for striking The striking machines or .

beams shoul d be in an adj oining room or immediat ely below ; ,

then a small shed space for drying before roll ing next the roller
-

room and then the warm stove for drying o ff If two of the
latter can be provided to b e use d a lternately it will a
.

l low the
goods to be aired o ff without taking do wn and they may then be ,

immediately handed or lowered into the warehouse without fear

of over drying which is sometimes di fficul t to avoid where leath er
must be t aken direct out of the hot drying roo m The sa
-

me .

principles are easily applie d in yards for lighter leathers .

To lessen loss of power in t ransmission the engine sho uld be

near the centre of the m a in range of buil di ngs with perhaps the ,

grinding machinery on one si de and the leather finishing on '

the other but this would b e rather liable to i n crease the fire
risk A very good plan wo ul d be to have the engine house
.
-

in the centre as suggested but separated from the buildings o n

each si de by brick gables a
,

n d with the boiler house behin d it

,
-

and under a separate roof say of corrugated iron If it be ,

.

impossible to have t he engine near its work it is in most cases

b e t t e n t o employ separate high pressure engines which m a
,

y be
-

a
within a glass partition and will work all day with scarcely any
,

attention The loss of power in carrying ste m for moderate

.

distances through su fficiently large and well — clothed pipes is

much smaller than that of long lines of shafting The writer .

has kno wn cases where full y half the in dicated power of the
engi ne was consumed in friction of the engine sh fting and , a
belts High —pressure engines are as a rule to be preferred to
.

condensing for tannery use since the waste steam can generall y ,

be employed for heating and both the first cost and that of
maintenance are sm a
,

l ler Wh ere much fuel is used it is quite

.
,

worth while to have the cylinders i ndicated o ccasionally both ,

running light and driving the machinery mu ch information is

gained in this way as to the power spent on the various machines ,

and very frequently large economy is e ffected by proper adj ust

ment of the va l ves To work econ omically an engine sho ul d
be of ample power for all it ha
.

s to do and adj usted to its work ; ,

not by loweri ng the pressure of steam or by checking it at t h e “

throttle valve but by s e tting the slide valves to cut o ff as early

-

,
-

in the stroke as may be A s t o how early this is possible an

.

indicator diagram will at once give information If the whole

-

of t he waste steam can be used pro fitably for heating purposes

economy in the working of the engine is of little consequence ,

but otherwise it is very inj udicious for the sake of a little savi ng
, , ,
5 44 P RI N C I P L ES OF L EA TH ER M A N UFA C T UR E

revolutions and a I z inch one at 3 0 0 Of course the higher it s

,
-
.

speed the more power any gi ven shaft will transmit b u t increased ,

friction and wear and tear soon limit this advantage The .

velocity of a belt in feet per minute is obtained by multipl yi ng

the number of revolutions per minute by the girth of the pulley
in feet or by its diameter mul tiplied by or more accurately , ,

3 1 41 6
-
.

shoul d always be of ample breadth for the power

Pulle ys
they have to transmit and it is more economic a l both in p ower ,

and cost to use broad si ngle belting than the same strength in
double If the pulley will not take a belt broa
,

. d enough for the

work it has to do a second belt may b e made to run on the top
,

of the first as suggested by Mr J Tullis and will do its share

, .
,

of the work B elts should be washed occasionally with soap

and tepid water and oiled with castor or n e a
.

t s fo o t oil but if of
sufficient b r e a
, ,

dt h sh o ul d not require the use of rosin or adhesive

, ,

materials to make them grip the pul ley Chrome leather belts .
- ~

should be kept t ho r o u ghl y o il e d They have a much greater .

adh esion than vegetable tannages and this is increased by oiling

Good chrome b elting is much stro nger than bark t a a
.
,

nn ed nd
'

is una ffected by damp or steam but generally stretches some ,

what more Makers of machines often err in constructing their

driving pulleys too sm a l l both in breadth an d d ia
.

'

m e t er Very .

thin or soft belts will not run satisfactorily on flanged pulleys ,

as the edges turn up and the belt often becomes crooked This ,
.

troubl e is often due to pulleys not being in proper alignment as ,

the belt then t ends constantly to run against the rigger to one
side Pulleys should always be s lightly higher in the centre than
.

at the edges as the belt tends to run on the highest diameter

,
.

The horse power which a bel t is capable of transmitting

“

obviously varies extremely with circu m stances but may be

a
,

approximately calculated by the form ul a '

66ooo
v
where ais the
area of contact of the belt with the smallest pulley and 7) its ,

velocity in feet per minute Another rule is that at a velocity .

,

of 1 0 00 feet per minute each inch of breadth of belt shoul d

transmit z é horse power on met a l pul leys or 5 on wooden ones o n
which the adhesion is greater A dhesion may a
-

, ,

l so be increase d
by covering t he pulleys with leather or in dia
.

r u b b e r but in the ,

latter case oily belts cannot be used H oles are s ometimes drill ed
in bro a d pull eys to a
.

l low of rapid escape of air B oth rul es

’

assume that the belt is of ample strength On e horse power .

-

would be transmitted b y a b elt running 1 0 00 feet per minute

with a pull of 3 3 lb A good single belt should not break with
.
 MA I N TEN A N C E OF TA N N E R I E S 5 45

much less stress than 1 0 00 lb per i nch of breadth and should

’

.
,

not be given more than one tenth as much as a working stress

The following table gives the experiment a
-
.

l breaking stresses
and extensions of some leathers It may be noted that I square .

’
'

inch sectional area is equal to a belt 4 inches wide by inch

'

thick and that kil os p er

,
per inch .

B R E A KI N G STR E S SES OF LE A TH E R 1

B elting leather layer system

,

Durio sys t em
Well tanned chrome leather
-

Over tanned chrome leather

S t u ffed a
-

l um e d leather
Al u m e d rawhide

Good English tanned b elting leather breaks a t from 45 00 to

5 5 0 0 lb per square inch section a
-

. l area .

Over tann e d leathers are less tough ( though they stretch less )
-

whether of vegetable or miner a

,

l tannage than those somewhat ,

lightly tanned and the tensile strength of leather varies con

s id er a
,

b l y with the part of the hide from which it is taken that ,

from approximately over the kidneys being the strongest Even .

thick and tough leather is easily torn if a cut or nick is once

started and all holes used in j ointing belts should be carefully
,

rounded Glucose and the us e of acid in bleaching both lessen

.

the toughness of bel t s and they may also be rendered tender by

,

the heat evolved in slipping on a pul ley .

Countershafting and high speed machinery such as di sin t e

gr a t o r s striking machines of the Pries t m a
-

n type etc should run

without materi a l j ar or vibration If this occurs it is gener a
.
, , ,

lly .
,

a sign that the rotating part is not equally balanced In this .

case the shaft or spindle must be taken out of its bearin gs and
supported on exactly horizontal st raight edges on which it will -

roll till the heaviest part is downwards and weight must then ,

be taken o ff or added till it will lie in any position In this way

the writer has had to a
.

dd fully 2 lb of iron nuts to balance the .

drum of a striki ng machine before equilibrium was secured and

a most troublesome vi bration prevented The exact alignment
of bearings is very important and a sh a
.

ft running in bearings
,

out of line will ul timately break Of course all machinery sho u ld

.
.

be supported as soli dl y as possible and if circumstances permit ,

1
G erb e r , 1 9 00 , p .
73 .
5 46 PR I N C I PLE S OF L EA TH ER M A N UFA C T UR E

most machines are better on a ground floor In placing bark .

mills however it is frequently convenient to fix them at a hi gher

, ,

level so that the ground materi al may be sent down shoots by

,

its own weight to the required places A n alternative and .

,

perhaps bet t er plan is to set the mill on the ground over a pit
, ,

and to raise the ground material with a bucket elevator This

may b e done successfully by letting the materi a
-

l fall directly from

the mill into the bu ckets but otherwise it must be thrown in
with a shovel as buckets will not pick up ground bark even from
a hopper and in a ny case such eleva
, ,

tors are apt to be trouble

some the tanning material getting be t ween the pul leys and the
,

belt and causing the latter to break or c ome o ff In a grinding

,
.

plan t designed by the writer the unground material was fil led

on the basement floor into a n iron barrow which was whe eled

a
-

into an iron sling working between upright guide rails like a hoist
'
-
.

On pulling brake line the barrow was raised to the top of the _

building and its contents were tipped into a large hopper after
, ,

which the barrow righted itself and descended for another load , .

In the bottom of the hopper was a sli di ng sho ver which forced ,

the material on to vibrating screens by which it was guided eith er

into a disintegrator or crusher rolls a
,

t pleasure B oth these

-
.

discharged through iron sp outs into large hoppers on t h e outside

of a bri c k gable from which powder y materials like myrobalans
,

and valonia co ul d be run direct into barrows or trucks It is .

very desirable that such hoppers shoul d be s eparated from the

main buil ding by a fireproof partition Fires may occur from hard
substances getting into disintegrators along with t h e b a
.

r k etc

and if this occur with a dry a n d dusty tanning m a t t e ria

.
l
, ,

l it is not ,

unlikely that it may result in an explosion such as sometimes

happens in flour mills in which the fire is rapidly conveyed along
,

spouts and into chambers filled wit h dusty air Insurance eo m f

pa
.

n ies generally charge an extra rate for di sintegrators and it ,

is very desirable to keep the mill house structurally apart from -

other buil di ngs either b y actual separation or by the introduction

,

of brick gables di viding the 1 00fS On the whole however mills ’

.
, ,

of the co ffee mill type are probably quite as dangerous as disin

t egr a
-

t o rs since if they become partially choked the heat caused

, ,

by frictio n is very great .

In A merica the fire risk from mills is often lessened or pre

vented by the introduction o f a j et of steam into the chamber or
'

spout by which the mill discharges but this is only permissible ,

if the tanning material is conveyed at once to the leaches o r ‘

a
yard
The use of chain con veyors for h ndl ing tanning material
-

,
548 P R I N C IPLE S OF L EA TH ER MA N UFA C T UR E
durable some of the original pits at Lowlights Tannery con
structed in 1 7 65 having been in use till 1 88 9 Lo a
.
, ,

m mix e d
with water to the consistence of thin mortar may a
.
, ,

l so be em
ployed t he pits being fil led up with water to keep them steady
, , ,

at the same rate as the loam is run in On e of the best materials

‘

for pit sides are the large Y orkshire fla

.

g s t o n es Where these .

are n o t attainable very durable pits may be made of brick either

, _ ,

built with Lias lime and poi nted with Portland cement or built ,

entirely wi th the latter Common lime cannot be u sed as it

”

spoils both liquors a

.
,

n d leath er and even cements with too large

2 3
'

7
'
o

FI G .
— Mr C E P
. . ak r
’
e r s c o n s t r u c t io n o f L im e -

p it s .

a percentage of l irrie are unsatisfactory Brick and common .

mortar are however suitable for lime pits and for these Mr
, ,
-

C E Parker s plan of constructing the bottom of cement t he

’

ends and sloping hearth of brick a

. .
,

n d the sides of 3 inch planks ,

-

bolted together is also very satisfactory ( fig Most of these .

methods are now however superseded by reinforced c oncrete

, , .

Th e writer has const ructed wooden pits in two ways In

‘

the one case after making the excavation beams were laid in a
, ,

well pud dled bed of clay ; on these a floor of strong tongued

-

and grooved deals was laid and on this the pits were constructed
‘

of similar wood to the floor and puddl ed rou nd with clay In , .

the second case the pits were built like large boxes above gr ound ,

and when finished lowered on to a bed of clay prepared for th em ~

,

and then pud dl ed both around and between It may have been .
“

due to defective workmanship in the first case but those made ,

on the last named plan which is that adopted from very e arly
-

,
'
 MA I N TENA N C E OF TA NN E R I E S 549

times cert a inly proved the tightest a

'

, nd most satisfactory .

Mr Schultz describes a plan as the B uffalo method in which a ,

floor is laid as just described and grooves cut with a plane for ,

the reception of the sides which are formed of perpendicular

a
pl nks each end and side being fin a
,

,
l ly tightened up by the
insertion of a wedge plan k Owing to the perpendicul ar .

position of the side planks such pits wo uld be di fficult to repair

in the common case of decay at the top .

If bri cks be used great care must be taken that the cement
,

is not merely laid so as to fil l the j oints towards the two surfaces

of t he wall as is the habit of modern bricklayers but actually
floated into a
, ,

ll the j oints so as to make the wall a solid mass ,

or leaks can har dl y be avoided Hard—pressed bricks are best .

,

and shoul d be tested as to whether they di scolour liquor ‘

.

Cement pits are very good and though not particularly cheap in
materi a
-

l which must be of the best are readily made by in

,
’
,
.

t e ll ige n t labourers under good supervision The first step is .

to lay a level floor of good concrete in which glazed pipes for ,

-

emptying the pits may be embedded care being also taken

that a
,
’

l l j oint s in t hes e are thoroughly tight since future repairs ,

are impossible The next step is to make frames the exact

.

length and breadth of the pits required and perhaps 1 5 inches ,

deep These are arranged on the floor where the pits are to be
.
,

and the intervening spaces are filled with concrete of perhaps

one of cement to three or four of crushed stone or brick R ough .

stones and bricks may also be bedded 1 n the concrete as the work
goes on to help to fill up A fter t he fir st layer has set the frames
.
,

may be raised and a second ad ded and so on The work is

genera
.
,

l ly finished by floating over it whil e still damp a little , ,

pure cement to give a smooth surface B efore using the cement

should be tried on a small sc a
.
,

l e to be sure that it does not di s

colour leather o r liquors and the pits should always be seasoned
,

with old or cheap liquor before actual use .

If possible both leaches and han dl er pits should b e provided

,
-

wi th plugs and underground pipes communicating with a liquor

wel l some feet below their levels Glazed fir e cl a
y is very .

suitable for both pipes and plug holes which should be in the
pit co rners If fire c l a
-

y blocks for plug holes cannot be obtained

-

-
.
,

they may be cast in good cement t he wooden mo ul d being soaked ,

with hot paraffin wax to prevent adh esion Means must be pro .

vide d for the ready clearing of the pipes when choked with
tanning materials A good plan is to let each line of pipes end
.

in a liquor well large enough for a man to go down A s it is

“

a
-
.

l most impossible to mak e plugs fit without occasional leakage ,

5 50 P R I N C I P L ES OF L EA TH ER MA N UFA C T URE

it is no t well to run pits with very di fferent strength s of liquors

to one well but the layers han dl ers and di fferent sets of le ches a
a
, , ,

should each have t heir o wn so as to avoid mixture A good . .

me ns of clearing pipes co nsists in a series o f iron rods 3 to 4 feet

l ong connected by hooks fitting int o double eyes as show n in
, ,

fig 1 1 8 It is o b vious that in a narrow pipe or drain these

. .

cannot bec ome disconnected .

Th e o rdinary canes of t h e
chimney sweep are also useful -

P ipes may often be forced out

by fitting a strong delivery hose
a
-

of a ste m pump into one of -

the plug holes -

.

It is as Schultz points out , ,

of questio n able advantage to

lay wooden troughs under the
F I G 1 1 8 — Cl e a
. n in g R o d J o i t
.
'

a l leys for suppl ing liquor to

y
n .

each p it since it is almost im ,

possible to preserve them from decay but t he sam e obj ection ,

would not apply to gla z ed pi pes j ointed with pit ch or cemented

Between concrete pits the alleys wo u l d p r o b a
.
.

'

b l y also be c on
_

crete .A very fine tar — macadam ; such as is often used for .

footpaths , seems also suitable for a l eys and is easier to take

l
up and make good fo r repairs of pi pes than cement A good
,

a
.

and cheap pl n 1 n practice is to let the liquor pump or a raised -

liquor—cistern discharge into a large and quite horizontal trough

raised 6 or 7 feet above the level of the yard a
,
-

n d provi ded with

plug holes at intervals from which the liqu o r c a

, ,

n be run into the

“
-

various pits by short spouts or sail— cloth ho se In place of .

plugs in the raised trough a simple and conveni ent valve devised
by the writer may be advantageously employed A lead weight .

i s made by casting in a hemispherical pressed steel basin of about

5 inches diameter and 2 inches deep l n the centre a loop of strong ,

brass wire with turned up lower ends being suspende d in the

middle so as to become fix e d i n the lead To prevent adhesion .

t he tin must be previously burned o ff and the basi n well black

leaded This weight forms the valve whi ch rests in u s e o n a
6 in ch washer of good in dia
.
,

-
r u bb e r with a 4 inch hole which i s -

h eld by a wood block or brass flange against the bottom of the ‘

trough through whieh a 5 inch hole is cut The valve is ra1 sed
,
-
.

by a lever or cord and is absolutely water tight in use It is

,
-
.

shown in section in fig 9 1 ( see p . .

a
I t is very advantageous in practi ce i nstead of pumping direct ,

into the pits to ha v e one or more t nks into which liquor can
,
5 52 PRI N C I PLE S OF L EA TH ER MA N UFA C T U R E

however will stand a good deal of heat Double acting force

pumps ha
.
,

Ve practically superseded t h e older sin gle acting -

double or tripl e pumps Instead of direct driving with a steam

cylinder it is sometim es advantageous to dr ive by belt but a
.

t ,

least one steam pump should be provide d so that pumping can

-

be done when the main engine is not running and the speed of ,

the pump can be regulated to the work which is impossible in a

'

belt driven pump Steam pumps are some t imes very useful
.
-

as fir e — e n g in e s .

Cen t rifugal pumps are very suitable for tannery work where
the liquor i s drawn from a well but are not well adapt ed for use ,
—
with suction pipes If the form with vert ical s pindle is adopted
-
.
,

which is sunk below the liquor in the well t he pump fil ls itself ,

and needs no foot —valve but unless the well is very large or
a
, ,

s o me convenient me ns is devised of withdrawing the pump ,

repair or cleaning is di fficult If the h orizontal p at t ern is use d

which is a
.
,

bove the ground rep air cleaning and driving is m uch

easier but a
, , ,

foo t —valve is necess ary,which may itself give trouble

a
, ,

n d s o m e c o nvenient means such as a pipe from a raised tank ,

'

should be provided for filling the pump with liquor as unlike , ,

sucti o n pumps centrifugals will not start unless full al though

they raise very large quantit ies when r u n n l n g a
, ,

n d fro m their ,

s t eady flo w will deliver much more through a given pipe than

an ordinary reciprocating pump with the same p ower In .

s el ecting the pump care sho ul d b e taken that the pattern allows _

r eady access not o nly to the foo t valve but to the b ody of the -

, ,

pump Some of the more m o dern rotary pumps may pro ve

.

suitable .

It is seldom satisfact ory to use win db o r es or strainers to

prevent tanning materi al getting into a pump s they spee dily , a
b ecome choked and it will be found better after taking such “

precautions a
-

s are possible to h ave th e pump and valve of ample,

size and suitable construction to pass what comes with the liquor
Th e writer has kn o wn a
.

mop head pumped and delivered through -

-

a 3 inch hose without stoppage by a Tangye fly wheel steam

a
- -

pump with br ss clack valves such as have been alluded to

-

Pulsometers ha ve not in the experience of the writer proved

s atisfactory in t a
, ,

warming and diluting the liquor con

'

nn e r ies

s u m in g much mor e steam than a

_ .
, ,

pump o f the same power ,

and becoming easily choked Fo r the same reasons steam j et .

,
-

water raisers are not to be recommended except where raising

-

is to be co m bined with heating as in some leaching devices ,

B ut little alteration has bee n made in the foregoing chapter

 M AI N TEN A N C E OF TA N N ER I E S 5 53
"

since it was written in 1 9 0 3 but it may be in place to conclude ,

with a few words as to the tendencies recently observable The .

use of reinforced concrete not only in general construction but ,

in the making of pits has co nsiderably increased, partly due to

,

the di fficul ty of building in bri ck since it is possible to do much ,

of the concrete work with the semi skill ed labour general ly -

available about a tannery and with the aid of the j oiners and ,
’

fitters shops with which modern tanneries are generally provided

’

_
.

Fo r the const ruction o f pits it is probably really the most satis

'

factory material and for lime and water pits requires no further
,
-

finishing but for liquor pits should be coated with boiled oil
,
-

with pitch or with some sort of varnish though some cements

, ,

withstand the action of ordinary tanning liquors quite well

without Fo r chrome liquors protection by some varnish is
.

essential and cement on the whole is probably less satisfactory

,

than wood or what is still better slate, ,

.

In roofing for tan houses the weavi ng shed construction with

-

lights to the north has still much t o r e c o m m e n d it but fo r lime "

,

houses the ligh t wooden latticed girder and curved roof has very
much taken its place as it has the advantage of giving very large
,

spans without the obstruction of pillars On e of the finest .

lime houses which the writer has seen is that of Messrs Walker
-

at the R osehill Tanneries at Bolton not only on account of its

size but fro m the admirable rrangement of the machines
,

fir st the lime pits with suspension and agitation with comp ressed
-
a ,

air then a row of unhairing machines with pits behind them to

,

receive the hair next a row of fle shin g machines with pneumatic

'

rolls and fin a
,

,
ll y a wi de space for sorting and rounding so tha t ,

the hides proceed direct from the limes to the rounding table .

Fo r floo ri ng for most purposes about a tannery good concrete

is quite satisfactory but it is a good de a l attacked by acid chrome
liquors and genuine asph a
,

,
l t or the fine tarmac often used for
footpaths would probably be more durable .

Fo r leather drying the use of wooden lou v r e boarded build

ings has become a

-

l most obsolete and brick structures with ,

pivoted windo ws have largely taken their place while drying

with artifici a
,

l heat and fan ventilation is almost universal .

D etails of the methods most in use will be found in Chapter

XXV II I The use of fir e proof reinforced concrete floors fo r
.
-

upper stories is increasing Compressed air is coming much .

into use both for agitating and for moving liquors Mechanically
,
.

it is not very economical as much heat is lost at the compressor , ,

which must be water j acketed and the compressed air cools the
-

liquors in expanding which is sometimes advantageous and ,

554 P R I N C I P L E S OF L EA TH E R M A N UFA C T UR E

sometimes the reverse and it costs as much m echanic a

, l power to
force air to the bottom of a liquor as to raise the same volume of
water the same height but once the somewhat expen sive com
pressor is inst a
,

ll ed its c onvenience is so great that this dis

,

advantage is probably ful ly compensated Fo r stirring of

suspension limes the a
.

i r is simply allowed t o escape from per

fo r a t e d tubes at the bottom of the pit of which the bottom should

,

be so curved as to pro m ote a good circulation of the lime and

liquor and the only t r o ub l e which sometimes occurs is t he ten
,
x

d en c y of the lime sludg e which must settle towards the air

,

pi pes to choke them when the air is not flowing Fo r this reason
‘

it i s probably best to have t he openings directed do a a

.
,

r ds Fo r
t h e stirring of tanning liquors the o x id a t io n h a
.

s been pointed

out as a disadvantage but unless the liquors are alkaline the

, ,

l o ss 1 s not likely to be important With ch rome liquors no

.

oxidation takes place but if used for hypo liquors in the two
,

bath process there may be loss of sulphurous acid Fo r stirring .

loose skins compressed air is not so satisfactory as the paddl e

The m
.
,

oving of liquors by compressed air is done by the air

”
lift the liquor being allowed to flow down into a well some little
,

dep th below the bottom of the pit and the air being made to
,

bubble up through an open wh en it will carry the

'

liquor u p with it to some h eight above the surface of that in the

pit This has the great advantage over pumps that there are
no valves a
.

nd no wearing parts Th e method has long been

.

used in the United States for raising water fr o m d e ep wells where

the installation of a pump would be di fficult .
5 5 6 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

though they weaken the hair do not seem to a ffect it s commercial

va
,

l ue
Fl es hings a
.

nd Glu e s tufi — The various scrap s of fat and -

flesh containing som e actual hide substance are usually worked

, ,

up for glue though if they cannot be sold for a fair price it will
“

pay to boil them in order to recover the fat they contain B efore
“

boiling the fle shin gs are treated with sulphurous sulphur ic or

, , ,

hydro chloric acid su fficient to neu tralise the lime present The ,
.

boiling shoul d be carried on very gently so as to allow the fat ,

to rise without emulsifyi ng with the gelatinous matter Open .

steam may be used but in this case the size formed will have
'

little value ; on the other hand if the fle shin gs are carefully ,

delimed with sulphurous acid and a wooden vat with a copper

steam coil be employed really good size may be obt a i ned and , ,

the slight trace o f bisulphite which it may contain will prevent

it s putrefaction Except under special conditions it will not pay
t o ma ke glue on a small sc a l e in England as its va
.

l ue depends
'

much on its appearance and the necessary plant is somewhat

In some places however size can be sold to a dva
,

exp ensive . n , ,

tage Fig 1 1 9 shows a glue boiling plant -

Material for glue must be in a neutr a

. . .

l condit i on In dried .

glue stu ff this is secured by the carbonation of the lime in drying

-

but wet fleshin gs or glue pieces must be fr eed from lime by

’

treatment with acid preferably sulphurous and then from excess , ,

of acid by thorough washing which may be shortened by the ,

use of a little soda in t he last wash water so that t he material ,

is neutr al to methyl orange or Congo red but must not redden ,

phenolphthalein In place of using sulphurous acid goods may .

be carbonated b y blowing carbonic acid (the fumes of a coke.

stove or even washed furnace gases) through them in water til l

,
-

they no longer redden phenolphthalein and this metho d is

particularly advantageous with ma
,

a
tter containing rancid fats
with oxidised acids which from their ready emulsification r e ,

particul arly apt to render the glue turbid The skimmed fat .

is also improved but the scutch or undissolved residue must ,

be treated with acid to recover the fatty acids present as lime

soaps The writer has in this way made a bright glue from se l
. a
fle shin gs which usuall y give one turbid and nearly black
’

.
,

Skin glues are generally boiled in open vats such as are shown
-

in the illustration These may be of iron or copper or of woo d

‘

.
_ ,

like the leaches used in tan extraction ( p and like them .

, ,

they are furnished with a copper heater or boiling coil and with ,

,
”
a perforated false bottom usually of iron or copper to support , ,

the material The steam for heat ing is supplied by a vertical

.
WA S TE P R OD U C TS A N D TH E I R D I SP OSA L 557

pipe in the centre which is surrounded by a wooden casing or

,

eye passing through t he false bottom so that when the liquor

boils it rises through the casing a
,

n d flows over the top of the vat ,

passing do wn through the gl u e st u ff If dry material is to be

~

boiled the va
.

t is usually fitted with a curb in which the ,

spetches can be piled and sink do wn gradually as they soften

,
.

Fo r material in which the lime has been neutralised and rendered

FI G 1 I — G l u e B o il in
.
9,
g .

insoluble by carbonation iron vats are quite suitable but if acid ,

deliming even with sulphurous acid is practised wood is better

, , , ,

because the iron ( and even copper) is slightly attacked and

darkens the glue After boiling for six or eight hours as much
.

of the fat as possible is skimmed o ff and the liquor is run into a

,

tank where it is allowed to cool somewhat and a further portion

, ,

of fat separates The material is boiled a second time w ith a

.

further quantity of water and for common glues this size is

usually used to fil l the v a
t for boiling a
,

z
s e c o n d lot of glue material
’

a
.

A prefer ble method is to evaporate at once for a somewhat

inferior glue or to add it to the strong size for evaporation ( see
below) Some alum or a
,

. l umina sulphate is frequently added to

the size at this stage to harden the j elly and raise its melting point .
 5 58 P R I N C I P L ES OF L EATH E R MA N UF A C T UR E
~

separati on of the fat by skimm

"

A fter ing the clear size is ru n ,

o ff from the re s idual matter into wooden or galvanised ir o n c o o l ‘

ing troughs about 5 feet l o n g b y 9 inches deep and 1 5 i nches wide '

in which it is allowed to set ( fig 1 1 0 p Great care is r e .

-

,
-

quired that both size and coolers are quite sweet and free from
_

putrefaction the coolers being frequently washed with sul

,

p hur o u s acid s olution or fresh milk of lime The j elly is cut out
“

of the cool ers in blocks and sliced into cakes of appropriate thick ,

ness by means of a s eries of frames like slate frames Which fit -

over the block of glue and between which a wire or thin blade
stretched on a s a
,

w frame is inserted to cut the glue into sheets

-

or now more commonl y by a machine with a seri es of parallel

a
bla des against which the glue block is pushe d The sheets are -
.

afterwards sep rat ed by girls and laid to dry on nets on which

When dry the cake s m a
,

they are frequently turned y be

washed with w arm w
.

ater to rem o ve any adhering dirt whi ch in ,

smoky districts quite spoils their appearance but this causes ,

so me loss of weight and in many cases it pays b etter to dry in a

'

a
,

stove until quite hard th en grind in a disintegrator and sell s

' '

size powder , in which appearance counts fo r little if t he colour

-
“

and strength of the size are good .

A rtificial heat cannot be used in drying t he soft glue on t he

nets and in hot and especially in thundery weather it some
,
«
, ,

tim es melt s and runs through the nets not only Wasting the ,

material but making a mess di fficul t to clean up and bacterial

,

tr0ubles ofte n occur probably increasing the tendency to melt , ,

and causing bubbles i n the interior of the cakes Fo r this and .

other reasons the process j ust describe d has been largely super
se d e d and the settled or fil tered size is run direct to an evaporator

of the Y a r ya
,

n or Climbing Film type and c o n c en

t ra t e d till it will set to a firm cake when run on glass plat es
—
a
previously w xed or rubbed with o x gall to prevent its adhesion
a
-
.

Vacuum i s not strictly n ecess ry as the very brief heating to ,

boiling temperature does not noticeably in j ure the glue The .

cakes when set are stripped o ff the plates and dried on nets which ,

are often in frames on wheels which are passed th rough a ,

tunnel through which warm air is circulated entering at the

farther end w hen the p rtially dried glue can stand a higher
,
a ,

temperature
Fa
.

t
. The fat whether obtained in t he manufacture of glue
-

or by boiling the fle shin gs and shavings for its recovery alone is ,

skimmed from the surface o f the heated liquor and should

afterwards be freed fro mgelatinous matter by washing it with
_ ,

hot water in a tub and running off the upper layer after allowing
"

,
 L EA TH ER MA N UFA C T UR E
'

5 60 P R I N C I P L E S OF

a ai g a
B te s h -
very valuable as sizing materi a
vn s re ls They .
.

shou ld be well washed in water or with a very dilute solution of ,

sulphurous acid and are th en laid out in thin layers to dry They
may a
.
,

l so be partially dried by pressing between latticed boards

in a screw or hydraul ic press and are th en best fin ished as ,

cakes On the manufacture of sulphurous acid compare p 24

a pith or intern a
.

a
H om s re usuall y kept until t he sloug
bone c n be knocked out having become loosened through
drying and putrefaction If kept dry practically no longer
l

.
,
,

time i s required and the smell and other annoyances incidental

,

to storing i n a damp place are avoided The sloughs may be .

removed at once by steaming but the horns are somewhat

damaged by this treatment The sloughs are princip a
,

l ly ground .

for bone meal but some are boiled for glue either without
-

,
“

preparation or aft er decalcifying with dilute hydrochloric

'
'

acid
The ac t u a
.

l horn itself which is quite I ncapable of making ‘ “

glue is used chiefly in the manufacture of combs buttons and

, _ , ,

similar articles The value of horns is to a considerable extent

dependent on their size s m a
.

ll h o rn s being unprofitable to work ,

up for the articles above mentioned

Sp en t To m —Th e tan as it is obtained from the le a
.

ches after
extractio n has naturally no va
e
-

l ue for the tanner e xcept as a

, ,

fuel Spent tan cannot be profitably sold as manure as its

worth in this respect is extremely sm a
.
.
,

ll In those places where

”

white lead is still made by the Dutch process oak bark is used ,
-

to cover up the earthen pots and commands a good price It

is however essenti a l that o a
.
,

k bark o nl y shoul d b e used as

many other tanning materi a
-

, , ,

l s give o ff products which injure the

colour of the white lead The quantities of tan used for hot
b eds and for deadening the noise of traffic in the streets a
.

re so

small that they are o f no practical account in the di spos a

, ,

l of
this product Spent tan is not nearly as go o d a
,

s wood for the

‘

manufacture of paper though spent mimosa bark has been used ,

for brown paper with some success An attempt to distil it .

,

and thereby obtain pyroligneous acid and wood spirit did not -

result in any commercial success On the Continent fin e ground .

-

tan is usually pressed into briquettes for u se as domesti c fuel

but it wo uld be hard t o obt a
,

i n a marke t for these in England

On t he whole in spite of its low heating v a
.

,
l ue spent tan is ,

best utilised as a fuel Fo r this purpose Specially constructed .

furnaces are necessary on account of the dampness of the tan

and its low calorific v alue, which varies however with the
particul ar materials thus while oak bark and va l o n ia a
, ,

r e only
'

-
WA S TE P R OD U C TS A N D TH EI R D I S P OS A L 5 61

poor fuels hemlock and myrobalans are much better on account

,

of the resins and lignine they contain .

Th e first successful furnaces for raising steam with wet tan

were introduced in the United States and consisted of a large ,
‘

arched combustion chamber with abundant grate area and with -

four or six fe e d holes in the fire —brick top which formed a floor
-

on which the spent tan was laid and where to some extent it ,

was dried b y the waste heat The flames and furnace gases
were conducted under the boilers the flue being very large a
-
.

nd ,
’

deep so as to collect the light ash which was drawn in great

quantities from t he furnace and the gases were then returned ,

As t

FI G . 1 20 .
— H ux h m a ad B n r o wn s
’
Fu r n a ce .

w
through the tubes of the boiler after ards passing down the ,

sides and g oing to the chi mney The wet fuel partially dried . ,

on the firi ng floor was fe d in through the firi ng holes alternately ,

a
,

so that only a part of the gr te space was covered at once with -

a
.

wet fuel which was spee di ly ignited by the heat from other parts
,

Th e large
'

1
of the furnace and especially from the v ul ted arch
,
.

grate area was a necessity not only on this account but because
-
,

of the light weight of the fuel and its low calorific power which ,

involve d the need of burning a large volume Fig 1 20 represents

a
. .

a furn ce of similar principle constructed by Messrs Huxh am

and B rown s Furnaces of t his t yp e are the author b elieves
. . , _
,

still largely in use —in the United States but in Germany step -

,
‘

grates sloping from t he furnace doors towards the back are -

now preferred In these the combustible mat erial rests upon

.

the flat surfaces of the grate while the air enters by the spaces ,

between the steps without the fuel being able to fall through .

1 D tail d d a
e e nd pa
w in g s a
"
i
t cru l a a g iv e i J ak o S h ul t z s
r rs re n n c s n c
’

ii uf a
t her M a
Lea e tm e f a
i n t he U n i te d S t te s , N e w Y o r k , 1 87 6 .
5 62 P R I N C I P L ES OF L EA TH ER MA N UFA C T URE

Fig .
represen ts the furnace on this pri n ciple constructed by the
1 21

Mo e n u s Co 0f Frankfort
The essenti a
. .

l conditions which are to be observed in the

proper burning of the tan are a sufficiently large grate area a
.
-

correct and su ffi cient supply of air and a combustion chamber -

a
,

of very high temperature It is consequently not possibl e to

.
'

burn t n very successfully an ordinary Lancashire or Cornish

FI G . 1 21 .
— Mo e n u s -
a
St e p gr t e F u r n a
ce .

boiler sinc e not only the grate Space is too li mited but the
,
-

water of the boiler prevents the upper part of the furnace from
attaining a high tem perature and it is therefore di fficult to get
,

the damp tan rapidly into vigorous combustion The difficulty .

may to some extent be overcome by mixing the tan with a

proportion of coal ; and by closing the ash pit and employin g a -

forced draught unless the chimney is a very powerful one In

,
. .

this way large quantities of tan may be burnt but without ‘

effecting any great saving of coal The heating power of the t a

,

n
.

is improved by the partial removal of its water by pressing and ,

this is almost essential where a special furnace is not employed .

The answer to the question as to whether tan should be used

as fuel in the wet state in which it is obtained from the leaches ,
5 64
-

PR I N C I P L ES OF L EA TH ER MA N UFA CT UR E

other sim ilar bo di es will only permit comparati vely pure waters
to be turned i nt o public streams or watercourses

a
.

Various methods of e ffecting the ne cessary p urification of

the wast e liquors from tanneries have been proposed t di fferen t
times and have been used with —varying degrees of success
,
[
.

These methods may be divided into t hree heads : precipitation ,

a
followed b y filtration or sedimentation ; land treatment ; and
- -

bacterial purific tion .

The first of thes e depends on the power of certain substances .

,

such as alumina and oxid e of iron to carry down organic matter ,

'

with them if precipitated in solutions containing it The method

‘

a
.

usually consists in adding a sufficient quantity o f lime to render _

'

the waste liquid slightly alkaline n d then treating it with

some crude s a l t of aluminium or of iron or vi ce ver s a By this
,

.
,

means a p recipitate of aluminium or iron hydrate is formed which ,

encloses within itself a considerable proportion of the organi c

matter of the liquid and after settling to the bottom of the ,

a
precipitation —tank is drawn o ff as sludge V arious chemicals
“

a a
.

”
re sold under fancy n mes such as l u m in o ferric ferro ,
-

zone e t c and have a co mposition not very dissimilar to that of

crude sul phates of iron or alumina In so me cases b y products
.
, ,

-
.
,

such as the acid liquors used in preparing iron articles for

galvanizing can be used with advantage
, .

In the case of the waste liquors from a tannery the use of

a
,

these chemicals m y often be avoided or reduced if suffi cient

care be taken in r e gu l a
t in g t h e proportion of the various liquids
'

'

which are to b e mixed together and run into the se ttling tank -
.

A s tanning matter combines with lime and dissolved hide sub -

stance to form a heavy bro wn insoluble precipitate it is clear ,

that if care be taken to have rather more wast e lime liquor mixed
with the waste tan liquors than is necessary to throw a ll t he t a
-

-
n /

out of solution a very considerable amount of purification of the

,

effluent will have taken place without any cost whatever to the
tanner Hence if the proportion of w ste lime is small in com
.
, a
pariso n to that of the tanning liquors an extra addition of lime ,

may be necessary in order to precipitate the tannin .

The precipitation or settling tanks are usually square or rect -

angul ar vessels or pits the size of which varies with the quantity
,

of liquid to be treated but of which the depth rarely exceeds 6 ,

feet They may be divided into two classes— the intermitten t

.

and the continuous In the former class the tank is fil led with
.

the mixed waste liquids taking care that such a su ffi ciency of ,

lime is present that the mixture is fairly alkaline to ph enol

phth al ein paper and is then allowed to rest until the susp ended
,
WA S TE P R OD UC TS A N D TH EI R D I SP OSA L 565

matter has settled down to the bottom of the tank when the
cle a
,

r or almost clear upper liquid is drawn o ff the remainder

some means must a
, , ,

being the sludge ‘‘

l so be employed t o pre
vent the passage o f scum and floating matters In the case of the
a
.

intermi ttent process it is advis ble to have two tanks one of ,

which is being fil led while the other one is set tling or being
emptied With the continuous process the liquids are run into
the tank in the proportions c a
.

l c ul ated to give a maximum amount

of purification as described above but as they enter very slowly
, ,

the un di ssolved matter soon settles and consequently the liquid ,

may be continuously run out at the farther end of the tank .

This p lan though it does n o t yield such good results in the hands
,

of unskilled workmen is yet useful in many cases as o n y one

,

tank 1 5 ab solutely necessary It is desirable that in runni ng o ff

' l .
,

the tanks the e ffluent should be taken as near the surface as

pos sible by means of a hinged pipe attached to a float or some
’

equiva l ent device and care is required as the tank gets low to
, , ,

avoid the escape of any of the sludge .

Fo r continuous settling the tanks are usually long and some

what sh a l low rectangul ar p onds into which the previously well ,
~

mixed preci pitating liquid flows through a wooden trough fixed

across one end and as long as the breadth of the tank and per
fo r a
,

t e d with holes to allow t he uniform and quiet influx of the

liquid which finally escapes by a similar trough crossing the
,

opposite end of the tank In front of the exit trough a scum .

-

board must be placed which is a simple plank dippi ng slightly ,

below the sur f ace of the liquid so as to prevent any oil scum or
other flo ating matter from passing out of the tank a
, , ,

l ong with
the clear effluent Whether the interm ittent or continuous
.

system is employed the effluent should in most cases be after

wards passed through a bacteri a
,

l fil t er bed or treated by land -

filtration before it is allowed t o flow into a stream er river

, ,
.

Tann ery e ffluents are usually received into sewers without further
treatment than mixing and settling to remove solid matter
and many authorities are satisfied with the remova
,

l of merely
such coarse suspended matters as might choke the s ewers Where .

c ontinuous precipitat ion tanks are use d they must be emptie d at

frequent interva
-

l s and the sludge run on to cinder fil t e r s to part

with most of its water These fil ters are conveniently placed a
-

. t
a lower level than the settl ing tanks and it is generally necessary -

to return the e ffluent from them for further precipitation and

settling Several types of continuous settling tank with upward
.
-

flow have been devised by Mr Candy and others which are very ,

suitable for use where space is limited but otherwise less costly ,
5 66 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E
“

constructions are often sufficient Apart from the question .

o i obtaining an e ffluent su fficiently good to satisfy the sanitary

authority the treatment of the slu dge is one of the greatest

,

diffic ul ties in the purification of effluents It is usually very .

bulky easily putrescible and therefore di fficult to dry ; it is

, ,

of little value for manure and if allowed to remain long wet ,

its smell is very o ffensive Chloride of li me is probab ly the best .

disinfectant .

I t has been mentioned that in most cases the liquid and in ,

e very case the sludge In ust be freed from solid undissolve d ,

'
'

matter by fil tration This may take place through Open fil ters .

or through fil t e r presses The open filters generally c onsist of

-
.

a pit with an exit at the bottom for the fil tered liquid This .

pit is filled with either stones and sand with clinker ashes or , , ,

coke Most tanners use c linker and ashes as they do not cost
anything ; and the materi a
.
,

l shoul d be so arranged that while

the lowest layers are very coarse the surface of the fil t e r b e d ,
-

shoul d be of the finest material As soon as this has become

covered with so t hic k a
.

l ayer of solid matter that the fil tration

x

p roceeds too slowly the top surface of the fil ter may be removed
,

with a rake ( taking care to remove as little of the ashes or sand

a s possible ) and burnt or dried and used as manure In some
ca Ses filt er presses are used which a
.
, ,

-
r e compo sed of grooved or

perforated plates with cloth s between them through which the

l iquid is forced by pressure The solid matter remains behind .

in the form of a comparatively dry cake The fil t er cake .

-

dried if desired is sold as manure for which it is in many ways

’

.
, ,

very suitable though its value as a fertiliser is not great

, .

Although they work much mor e rapidly than do the open fil ters ,

the cloths so soon become rotten and have to be replaced that ,

t h e open ash fil t e r is on t h e W
-
hole the most convenient for the
tanner s use ; It will be readily understood that apparat us of
’

this kind though very efficient on a small scale is quit e out of

, , _

the question wh en many thousand gallons of liquid have to be

”
fil tered daily and so can only be effectively applied to
,
sludge .

No system of chemical precipitation has as yet pro ved entirely

satisfactory Undoubt edl y a great de a
,

. l of purification is e ffect ed
by this means but in most cases the purified liquid is s t ill
,

too impure to be turned into a stream though for various reasons ,

this is often permitted by the authorities .

A great advance was made in the purificati o n of e ffluents

-

when manufacturers were compelled by law to allow the e ffluent

from the precipitation tank to fil ter through land set apart for -

that purpose In this case certain hardy cereals were sown on

.
 '

5 68 P RI N C I P L ES OF L EA TH ER M A N UF A C T UR E

and light or any serious escape of smell The liquid to be .

_

purified is allowed to flow very slowly through a tank or series

of tanks of this description entering about a foot below the ,

surface through a distributing trough at o n e end and flowing

o ut similarly at the o ther at such a rate as to change the con ,

tents o f the tank about once in twenty four hours and when -

t he tank is in working order the liquid is much puri fied by the

’

process and m os t of t he solid organic matter has become

‘

a
,

liquefied and disappe rs It not unfrequently happ ens especially.

,

wh ere the septic tank treatment is not very prolonged that

a
-

the liquid which esc pes has a stronger and more o ffensive odour
than it had on entering the tank It is n e vertheless really
pur er t ha
.

the increased smell being due to the volatile

'

n b e fo r e x

, ‘

products of the partially decomposed organic matter and by ,

passing the liquid through an open coke — fil t e r t he smell will be

e ffectu al ly removed In all cases it must be bo i ne in mind that
as septic tanks and bacteri a
.

l fil ters depend for their e fficiency

on the organisms they cont in time must be all owed for these a
to develop and accumul ate before good results a a
,

re obt ined and

for this about six weeks use is generally necessary after which ’
-

they will continue to act for an indefinite period until they

beco m e choked by sand and I norganic matter .

It must not be supposed that t h e action i n the septic tan

a
k is
wholly an erobic ; and with weak sewage most of the organic ,

matter may under f avourable circumstances be converted into

ni t rates a n d carbonic acid by this means only but generall y a
much more c o mp l e t e p u rific a
“

t io n is e ffected by the subsequent

'

”
use of b acterial fil ters These in their simplest form consist
.

of tanks of about 4 feet deep fil led with coke broken bricks o r , , ,

'

clinkers and fitted with drain pipes at the bottom by which

, ,

they can be easily emptied _ These tanks often known as .

,

Contact beds are fil led with the sewage or septic tank e ffluent
-

,
-

which is allowe d to remain on them two hours , and the tank is

a
then emptied and all owed a rest of six hours for oxidation and
,
,

aer tion duri ng which considerable heat is developed which pro

motes the bacterial activity In most cases the sewage requires .
,

two such treatments the last of ten through a bed with finer
,

coke in order to be completely freed from putrescible matter

,
-
.

I n place of the intermittent process as applied on the contact ,

beds continuous aerobic fil tration is often employed the b e d

b eing so construct ed as to a
, ,

li o w of free adm ission of air at the

bottom and sides and the liqui d to be puri fied being distributed
,
'

on the surface by a sprinkler or some similar device and allowed ,

to trickle through the bed The continuous process seems likely .

WA S TE P R OD UC TS A N D . TH EI R D I SP OSA L 5 69

to supersede the intermittent one as the beds are not only capable ,

of treating a much larger quantity of sewage in proportion to

their area but are also less liable to choke About six weeks is
,
.

required with either contact beds or continuous fil ters before

,
-

the m aterial they contain becomes coated with the necessary -

bacterial layer and they get into full working order The resul ts .

as regards the effluent are perfectly satisfactory and the gr eat ,

di fficul ty and cost consists in the slow but inevitabl e choking of

the beds which involves the replacement of the porous material
,
.

This is considerably delayed by the use of a settled or precipitated

sewage and in this respect beside its bacteriolo gi ca
,
l function , ,

the septic tank serves a useful purpose in settling insoluble matter ,

which is much more ch eaply removed from it than from the fil t e r

beds It will be obvious that ordinary settling tanks if deep
.
-
-

, ,

ful fil many of the functions of the septic tank and both lead to ,

the production of a much more uniform liquid from the different

e ffluents which the tanner produces which is important in the ,

subsequent bacterial purification A go o d deal o f interesting

‘

.
_
_

information on these subj ects will be found in a paper by Mr W H

a
. .

”1
H arrison on the B a cteri ologic l Treatme nt of Sewage .

There are a good many patents in connection with the various

methods of sewage purification and some caution is necessary ,

to avoid their infri ngement though of course the general prin ,

c ip l e s of settling and fil tration and the destruction of organic ,

matter by bacterial action are open to all ,

.

As a general rul e the waste liquors from a tanyard or leather

dye works are exceedingly impure They con tain the organic
-
.

m atter (in a state of great putrefaction ) from the soaks bates and , ,

puers other o rganic matter also more or less p u t re fie d fro m the ,

.

tan pits ; the lime liquors with their large p r o p o r t io n o f lime

'

and of dissolved protein and in addition the various dyes a

-

,
nd

other chemicals which may have been used in the conversion of

the raw hide into the finished leather and hence their e fficient
purification has presented di fficul ties which do not occur in most
other trades .

The di fferent waste liquids are best run into a capacious tank
and after being thoroughly mixed up together r e all owed to
,

settle for some hours By this means the greater part of the
»
,
a ,

tanning m atter will combine with the lime also present to form
a heavy bro wn insoluble substance some of the dye and other
,

organic matter will become entangled in this and thus be remove d ,

from the liquid The clear liquid is next run o ff into a bacterial
filter (preferably a septic tank foll owed by a
.

n open c oke fil t er ) ,
-

1
j o ur n S oc
. . Che m I n d ” 1 9 00 , p 5 1
.
,
. 1 .
 P R I N C I P L E S OF LEA TH ER MA N UF A C T URE
’

57 0

and then into the nearest stream If the tannery is near to a

town and the corpora
.

, tion sewers can be utilised it is probable ,

a
that a filter made of spent tan may be substituted as this material ,

will not only remove ll excess of lime from the liquid but will ,

also fix much of the colouring matter ( Koenig) The tan aft er

-

.
,

bein g used for this pur pose contains so much lime in its pores ,

a
that it is said to be useful as manure
In t nneries where large quantities o f disinfectants such as
“

mercuric chloride carbolic acid etc are used it is necessary that .

.

, , , ,

the mixed liquids shall Contain so much lime as to make them

distinctly alka
a
l ine In this way most of t h e disinfectants will
.

be either precipitated or rendered in ctive Wh ere arsenic is .

used in the limes it may be a dvisable to add a little ferrous

sulphate ( green vitriol or copperas) in Order that the rsenic a
may form an insoluble compound with the iron and so be re moved ,

along with the sludge : The ink produced by the action of t he

iron salt on the tan liquors will b e completely removed by the
bacterial fil ter .

The problem of the utilisation of leather scrap shavings -

, ,

m o isin gs and flu ffin g dust is a very diffit

,
one Although .

leather contains considerable quantities of nitrogen its value as

a
,

a manure is negli gi ble since it takes at le st years to decay in

,
“

the soil or to produce any useful e ffect It is easily pulverised .

by scalding with steam or boiling water dryi ng and grin di ng , , ,

but even the fine powder is almost imperishable Probably .

better r esults would be obtained by treating it with strong and ,

if possible hot sulphuric acid and incorporating it in super

,
~

phosphate mixtures but j udging by the time it takes fo r solution

'

in Kjel da
, ,

hl in g even this would not be very e ffective

,
It would .

also be decomposed by heat and alkalies but in this case it would ,

be di fficult to prevent the escape of the ammonia formed Prob _

.

ably the best treatment is destructive distillation and recovery

of ammonia from the escaping gases In some experiments On .

c ondemned army boo t s 5 1 3 lb of ammonium sulphate was

recovered from a ton The residual charcoal would a
.

. l so have
decolorising and deodo rising power and there would be a go od ,

deal of combustible gas .

Pulped leather has been used in mixture with vegetable fibre

for making leather board but app arently the less proportio n
-

,
_

of leather the better the result It see ms curious however that .

, ,

some satisfactory way cannot be found of c o mpacting pul ped

leather into sti ffeners heels and various articles of that sort for
, ,

s hoe manufacture .

A suggestion has been patent ed b y S Bro ugh ( 1 9 1 0 ) for the .

 CHA PTER XXX II
CON CL U S I ON

IT may be well in concluding this book to sum up shortly the

most important of the a dvances which have been made since the
publication of the first edition of 1 9 03 some Of which h ave been ,

already discussed while others are here alluded to for the first
tim e in these page s ; and perhaps also to a
: .

l low myself a few

words of suggestion as to the Opportunities for progress in the
near future 1

A mong the most important of the practical gains which a

.

re
also of scientific importance may b e mentioned Dr St ia sn y s
’

discovery of a new class of syn thetic tanning matters the

2
,

syntans which can be produced s o cheaply as to have already

,

found extensive use in the tannery From the scientific side

these tans of comparatively simple constitution o ffer a
.

n opp or
-

, ,

t u n it y for the investigatio n of the relation of constitution to

tanning e ffect which may throw much light not only on the
nature of t he vegetable tanning process but on the causes of the ,

quality we call astringency .

Less important are the di scoveries of the e ffect of hydroxy

3 ~

acids such as tartaric which by forming c omple x ions with ,

chromium renders possible the removal of chro me from chrome

tanned leather by R ochelle s a
.
.

l t ( so di um potassium -

and explains the effect of some of the products which occasional ly

occur in chrome liquors reduced by organic matter producin g
'

purple liquors which will not tan ; and the production of con
c en t r at e d chrome liquors by the direct reduction o f strong
solutions of sodium bichromate with sulphurous acid 4
.

A n interesting new departure is also the vacuum tanning

process of Mr Nance All previous attempts to introduce tan
into leather by the same use of vacuum a
.

s is so successful in

creasoting ti m ber ( a nd there were many ) had failed because the

1
A p o r t io n o f t hi s c h p t e r is t k e n f r o m a a
l e c t u r e g iv e n b y t h e wr it e r a
a
'

to a a
t h e Co n f er e n c e o f t h e L e t h e r]Tr d e F e d e r t io n s t t h e L e t h e r s e l l e r s
’
a a
H ll a 7 t h No v e m b er
1 1 9 20
a
, .

2
G er P t 2625 5 8
. .
,
1 9 1 1 .

S OC Che m I n d 30
3
j ou rrt 1 9 1 6 p 2

a
. . .
, , . .

fo m
4
. R oy S OC . . o f A r ts , 6 6, 1 9 1 8, p p .
7 47 , 776 .

57 2
 C ON CL USI ON 57 3

pores of the hide are filled with incompressible water instead of

with air and it was not until Nance used a vacuum so high that
,

the water actually b o iled in the pores of the hide at a temp erature
of only 7 0 or 80 F that t he wat er co ul d b e expelled and the
° 0
.

entry of tan liquor made possible -

.

A new departure in drum tannages is t he use of viscous colloids -

such as tragasol 1 and starch paste 2 as vehicles for the tanning

extract w
,

a
hich all ow it to be used in concentrated form without
,
-

hardening the surface or dr wing the grain and p robably them a ,

selves contribute to filling the leather .

Of more scientific interest though p erhaps of less immediate

,
,

commercial importance are Professor Meunier s investigations on 3

,
’

tannage with various chemical substan ces and especiall y with ,

quinone which gives one of the most perfect and resistant leathers
,

known though its price precludes it at present from any extended

,

use Quinone is a derivative of benzol a ring of six carbon atoms

.
, ,

to each carbon of which in benzol its elf an atom of hydrogen is , ,

attached In phenol ( ordinary carbolic acid ) the place of one

.
“

of these hydrogens is taken by an OH or hydroxyl group and ,

the substitutio nof a second OH gives as might be expected three

di hydroxy phenols a
.
, ,

-
l ike in composition but di ffering in pro
-

, ,
_

p e rt ies and in the place of the second OH on the ring

, Taking .

the OH of common phenol as in the noon position the two o clock ’

position gives catech ol the source of a

,

l l the catechol tannins ,

the four o cl o ok is resorcin present in the dyestu ff orcin and the

’

six o clock is hydroquinone the common photo gr aphic developer

’

,
.

If hydroquinone be oxidised b y exposure to the air or otherwise -

the H s of the two hydroxyls combine with the O to form water

’

and the spare links of the deserted O s j oin hands across the ring
“ ’

and form quinone Such a structure is naturally littl e stable .

,

and in presence of hydrogen easily reverts to hydroqui none .

In a 1 per cent solution of quinone pelt becomes first rose .

,
s

coloured then violet and finally brown and is converted into

, , ,

a soft tough leather which will stand boiling and washing with
soap or even with dilute acids or alkalies and which dyes readily ,

with acid basic and mordant dyes Meunier found hydroquinone

, ,
.

in the used liquor thus proving that the skin had not merely ,

combined with quinone but with oxygen A similar tannage ,

.

can al so be produced by hydroquinone but more slowly and

only in presence of a
, ,

ir The oxidation of the hide substance is of .

-

1
aa
G u m Tr g so l S u p p l y Co Lt d H o o t o n n e r Ch e s t e r a
a a a a
. . .
, ,

2
A T u r n b u l l n d B C r m ic h e l E n g P t 1 0 1 4 7 0 1 9 1 7
a
. . . . .
, ,

3
Co ll 7 , 1 9 0 8 p 1 9 5
.
, I b id 8 , 1 9 0 9 p p 5 8 3 1 9
, .G er . .
, , .
, . . P t . 20 69 5 7 .

1 9 09 .
 57 4 P RI N C I P L ES OF LEA TH ER -
MA N UFA C T UR E
so me t heo re t ic a
l impo tance Meunier concludes that the quinone
r .

combines with the ami no groups of the skin to which apparently -

acids and vegetable tannins also attach themselves

Meunier pursued his researches wi t h other phenols a
.

n d p h en o l
'

derivatives such as pyrogallol and gallic acid and found that

, ,

most of them wo ul d tan if exposed to the oxidising action of the

air and still more rapi dl y when in a slightl y alkaline condition
, ,

which p romotes oxidation Gall ic acid with access of air

“

r endered gel atine insoluble 1 n three days while gallotannic acid

failed to do s o i n t w
,

enty six days In a closed vessel but rapi dl y -

did so when air was admitted This seems to show that air has .

som e function in tannage which has not been generally recognised ,

though whether t he skin or the tannin or both must be oxidised , ,

is not yet clear It may however be pointed out that if tannin

will not tan gelatine in va
.
, ,

cu o it will certainly tan skin and the ,

reason may possibly be that while the tannin permeates the hide
and penetrates the extremely fine fibres it is not able to penetrate ,

gelatine in the mass but only tans the surface wh ile the ins o lubili
, ,

sation of the i n terior is due to the oxidat ion of the gallic acid
which is always present in commercial tannin or is formed by its
decomposition In experiments on t he diffusion of tannins in
.

gelatine j elly it has been found that this is apparently the case .

Meunier s statement that gallic aci d tans more rapidly 1 n alkaline

’

solution is noteworthy and shows that its mode of action is ,

ra dically di fferent from that of the tannins which will only tan ,

in an acid medium The gallic acid is however probably

absorbed as a
.
, ,

n acid though it only exerts its t anning e ffect when

'

oxidised The work throws an important and rather unexpected

sidelight on the vexed question o f the va
.

l ue of the phenolic non

’

tans such as gallic acid which are present in all tanning materials
, ,
.

Though partially absorbed by hide po wder in the ordinary

a
-

analytical process they certainly do n o t tan n d Wilson 1 has

, ,

shown that they can be removed from it by Washing but it is ,

clear that if exposed to the air in drying they will become fixed
by oxidation producing an actual tanni ng and adding to the
, ,

weight and solidity of the leather These facts will have to be “

consi dered in a
.

n y r e vis io n of the analytical method The ideal

‘

analytic al method of t h e fu t u r e should give much more det a

.

'

i led
information as to the constituents of the tan but wil l conse quently ,

cost more in execution for which users will have to pay and the, ,

present process imperfect as it avowedl y is has become of such

, ,

commercial importance that no changes even for the better , ,

can be lightly undertaken .

1
jo u rn . . a
A m e r Le ther Che m A s s o c . .
,
1 9 20, p . 29 5 .
 57 6 P R I N C I P L ES OF L EA THER MA N UFA C T UR E

and affi nity for water Placed in strong solutions up to 80 per .

,

cent water flowed freely from the skin under the osmotic pressure
.
,

of the solution which seemed scarcely to penetrate it and in a

'

few hours left it in a state when after putting out with the
sleeker o r even wiping with a cloth it co uld be dried rapidly
, ,

in the air and after staking formed a soft white leath er which
,

was permanent so long as dry but returned rapidly to pelt when ,

soaked in water A s very little potassium carbonate is actually

“

absorbed there is a commerci a

.

l possibility of using this process

,
.

as a substitute for pickling .

A nother interesting set of experiments were made b y repeating

‘

similar experiments in duplicate with potassium carbonate and

a
,

dding to one set 3 c c per litre of commercial formaldehyde '

a
. .

solution Where the potassium carbon te solutions were of

.

less than 1 0 per cent the le ather of both series dried hard and
'

horny a
.

nd more concentrated ones w ere necessary for good

,

result s In each series the skin was equally leathered but while
those with the carbon a
.
_ ,

te alone returned to pelt on soaking those ,

with formaldehyde when re dried were as soft as before Meunier -

.

concludes from this that t he function of the sodium carbonate in

the Payne and Pullman process is merely that of dehydration and ,

not that of an alkali I am not myself quite convinced on this .

point since their patent specifies Only 1 9 to 2 8 per cent of sodium

,
-
.

carbo nate which is less dehydrating than the potassium salt and
, ,

in Meunier s experi ments Would be quite insufficient to produce

’

a soft leather while I can say from my own observation that

“

Pullman s skins were perf ectly leathered in the drum It is

’
.
.
,

however certai n that satisfactory formaldehyde leather can be

produced in the presence of other salts which are n o t a l ka
,

l ie n
‘

Meunier s opinion of form a

.

l dehyde as a tanning agent is not a

’

very high one He states that it slowly evaporates on exposure

to air leavi ng the leather hard and brittle a
.

,
nd that it can be
removed by continued treatment with hot water being in th t
respect very inferior to his quinone tannage We have f ound at
.
[
,

.
,
a
Leeds that formaldehyde can be quantitatively recovered from
leather by hydrochloric acid so weak as decinorm a l
In connection with what has been s a
.

i d on new tannages it is ,

perhaps worth while to mention the accidental discovery of o n e

in which I had a part I had noticed in the laboratory the power .

ful dehydrating e ffect of saturated solutions of ammonium

sulphate which easily produce a white leather like Meunier s
,
’

and I communicated this to Mr Seymour Jones thinking it -

might be useful in some cases where the use of acid in pickling

is obj ectionable He tried it on a practical scale but used .
,
 C ON CL US I ON 57 7

commercial ammonium sulphate which contains traces of tarry ,

phenolic products and found to his disappointment that the

,

leather was permanent and would not return to pelt It is quite

, .

possible that by the choice of suitable tar products a leather might -

‘

might be m
.

ade of commercial value .

Leaving Professor Meunier I must turn to the work of some ,

other chemists It was noticed by Liip p o Cramer 1 that colloidal

.
-

silver peroxide precipitated in the gelatine fil m of photographic

plates rendered it insoluble in hot water and that it had the sam e ,

e ffect on gum arabic and star ch More recently Dr Eri ch A

-
. .

So mm e rho ff discovered that co lloidal precipitates such as ,

hydroxides , sulphides phosphates and silicates of the h eavy

,
-

metals when drummed into pelt rapi dl y produced complete

, ,

tannage and what is much more surprising that ultramarine ,

, , ,

a fine and quite insoluble powder had a rapid tanning effect ,

.

I t has long been known that leather could be formed by the

precipitation of such bodies in or on the fibre Phosphate leathers
have been c ommercially produced , and the p yro t a n process
owes at least part of its e fficacy to a similar e ffect Leathers .

have also been made not o nly by chrome and alumina but by
, ,

other metals producing basic salts hydrolysed by the skin and

the two bath chrome leather owes its superior softness to that
-

o f basic tannag e to the sulph ur deposited on the fibre Prob

'

a
.

bly almost any colloidal precipitate is c apable o f producing

leather
Instances of this sort might be multipli ed almost a
.

d infin itu m
but enough has been s a
,

id to show that no single theory of tan

a
nage can embr c e all possible cases and that in most commercial ,

processes more than one of these actions is involved .

The investigations of H R Procter and his collaborators. .

,

amplified by many others and especially by Dr J Loeb have

,
.
,

been su fficiently described in other parts of this book and need

not be discussed here but it has much e mphasised the importance
,

o f extended investigation of the region lying between ordinary

'

alkalinity and acidity roughly that between the rea ctions of

,

phenolphthalein and of methyl orange in leather chemistry , ,

since within it he the isoelectric points of gelatin and hide

fib r e on the one side of which these bodies act as acids and on
’

.
,

the other as bases and which is therefore the turning p o in t in

,
.

the r eactions involved in tannage (p It is obvious that .

this region cannot be investigated by the ordinary methods of

titration since it is mostly a question of the actual hydrion
,

concentration and true acidity and not of the total con ,

1
Co l l 7 ,
1 9 08, p . 24 .
57 8 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

centration of unionised acids and quite di fferent means must ‘

therefore be adopted The most satisfactory of these meth ods

is the electrometric in which the actu a
.

l acidity at the moment

is determined by t he el e c t ric potential of a vo l t a
,

ic cell in which
'

the po sitive element is a platinum plate saturated with hydrogen ,

but this method involves an elaborate apparatus and delicate

manipulation which is not suited to the ordinary work of the
tanners laboratory It is therefore of great practical importance
’
.

that the in ve n t io mo f the comparator (A p p D) has brought .

an approximat e det ermination within the range of ordinary

laboratory work and at least made a great forward step i n the
,

determination of the swelli ng power of tanning liquors I t s .

e ffect 1 r1 the control of li ming and bating I S not likely to be less

than that with regard to the actu a
_

l tanning since the depleting ,

e ffect of deliming is dependent on the cl oseness of the approach

to the isoelectric point and the swelling power of limes on the
concentration of ionised OH jus t as that of li qu o rs is on that
.

of H+ .

While it is still hard to say whether tannage is in the mam a

”
chemical or a physical process the wo rk o f the last twenty ,

a
years has much emphasised the impo rtance of t he study of the
colloid st te o f m a t t e r and especial ly of the electric cha rges of
the colloid particles on which their chemic a
,

l acti on d epends
and which usually ch a
,

nge in sign at their isoelectric point We ’

a
.
.

are still in ignorance o f the ex ct position of many of these -

isoelectric points and their determinat io n is a necessary work of

,

the future 1
More information as to the dispersity or size of
the particles under di fferent conditions of t emperature a
.

nd

dilution is a l so urgently required and in some important ,

cases as in that of chrome liquors we do not yet kno w with

, , .
,

certainty whether we are dealing with molecular or coll oi dal

solutions .

The valuable work of J T Wood on the bacteriology of bates . .

,

puers and drenches was largely completed before t he first edition

, ,

but since that time he has added largely to our knowledge of the
enzymes concerned in these processes n d the trypsin bates have ,
a
increasingly taken the place of those containing active bacteria ;
and it is not likely that these will again come into use though we
'

may have to resort to bacteria for the production of the necessary

Th e ba cteriology and ferments of lim es a
-

enzymes ( p . nd
liquors is however still to a large extent unexplored and it is to ,

1
Th e is o e l e c t r ic p o in t o f gel a
t in is P H = 4 7
'

ad n th ta of hid e —fi b r e

pp a
a a a a
,

e rs to b e p r c t ic l l y t h e s me . Se e E . C . P o rt er ,

1 921 , p . 2 59 .
 A P P EN D IC ES

A PP END I X A

TH E D E CI M A L S YS TE M

TH E metrical system of weights and measures and the Centigrade

thermometer scale have been generally used thro ughout the book
as more international and scientific than the complicated systems
still unfortunately in use in this country It s much greater .

convenience in calculation and the fact that it must ultimately

'

come into use throughout the civilised world and is already the ,

only system in use in scientific laboratories also make its com ,

prehension imperative It has the advantage of being based

.

on a single measure of length the meter from which all other

measures of area a
, ,

n d capacity are derived so that instead of ,

having to learn separat e tables for each of these it is easy to ,

pass by a mental calculation of squaring or cubing from o ne set

of dimension s to another Thus the cubic decimeter is the liter
.
,

and a cubic meter is 1 0 00 liters and the liter of water weighs a

“

kilogram and the cubic meter a m

,

,
etrical ton or 2 2 0 4 6 English -

lbs and if we know the specific gravit y of a b ody its weight in

.
,
“

kilograms is at once apparent Thus a stone of Sp Gr 3 0 and

'

-
. . .

I meter cube is at once seen to weigh 3 metrical tons and for ,

most aqueous liquids the weight does not vary seriously from
I kilo for each liter .

The following table gives the figures re quired for reduct i on

from the English to the metrical system or vice vers a : ,

I meter 3 9 3 7 inches
-
.

I millimeter o o o 3 9 3 7 inch -

I liter 0 2 2 0 2 gallon -
.

I cub cm water = 1 5 43 2 grains -

. . .

I cub met er
.
3 5 3 1 7 cub ft
-
. .

I foot o 3 o 4 8 meter _
-
.

I inch millimeters .

I gallon 4 5 41 liters
-
.

I grain 64 8 milligrams .

I OOO cub ft 2 6 3 I 4 cub meters

. .
-
. .

A ctual reduction is however generally unnecessary if the

, ,

5 80
 TH E D E C I MA L S Y S TE M 5 8 1

question be treated as one of proportion Thus asolution of . .

I g ram per liter is of the same strength as one of I lb per I o o .

gallons ( 1 00 0 and very approximately as one of I oz avoir , .

dupois p e r cubic foot ( I cubic foot weighs 9 9 7 1 In the case

of pits it is often simplest to measure them directly with a meter
,

rul e ; len gth breadth and depth m easured in decimeters and

, , ,

multiplied together giving the contents in liters and in the case

of water the weight in kilograms The c a
, , ,

pacity of a rectangular
tank is l en gt h x b re a
.
,

dt h x d e p t h that of a cylindr ical one 1 s ,

( half diameter ) -
or a p proximately by

a
the Imperial gallon is 2 7 7 2 7 4 cubic inches and that of water -

weighs exactly I o lb t 62 Fa The A merican g a

,

hr l lon is t he
°
. .

o l d English wine gallon and contains only 2 3 1 cubic inches

1
.
,

The Centigrade or Celsius thermometer di vides the di fference

between the freezing and the boiling points of water into 1 0 0 0

Th e foll o wing table gi ves the points at which its scale agre es
without fractions with that of F ahrenheit

C OMPA RI SON OF CE NTIG R ADE A ND FA H RE NH EIT DE G R EES

° ° ° ° °
C C F
° ° ° ° °
C F F C C F C F
°
F
°
. . . . . . . . . . . .

— 20 o 68 6o 80
4 32 20 40 1 04 1 40 1 76 1 00 21 2
~
1 5 5 5 41 25 77 45 1 1 3 65 49 1 85 1 85 1 05 22 1
— 86
1 0 I4 1 0 50 3o 50 1 22 7 0 I 58 90 I 04 1 1 0 230

5 23 1 5 59 35 95 55 1 31 7 5 1 67 95 20 3 1 1 5 239

1
ai d p i p d i 7
Th e vo r g ai u ad t h
o s 43 7 5 g a
oun m s 000 r ns n e ounce r s

y a d a g a ad t h
-

p th a
.

’
Th t e ro i p nd i f 57 6 o i ec r es
(i oun s o 0 r n s, n e o un ce n

wh i h all p
c i m ta l a w ig h d ) i 4 8 g a
r e c o us i b t th
e fl id
s re e e s 0 r n s, u e u o u n ce

f wa i ly 4 3 7 5 g a h mi t y t h M h ’
t i I l it k il
“
o er s on r ns n c e s r e o r s er o

a a
-

f wa d i pla f th t
.

°
o t t 5 C ) i g
er ll y I l it
s f kil
en er us e n ce o e ru e er o I o

a
.

°
t 4 C .
 A P P END I X B

OR I GI N A L P A P ER S ON TH E GE LA T I N E E Q UI LI B R I UM

As most readers dislike ( a nd shirk ) mathematics and it is yet im ,

possible thoroughly to understand a mathemati cal subj ect without

it , it ha s seemed best to print two of t h e most important origin a l
papers in full rather than burden the text with a long mathe
ma t ic a
,

l explanation The selection has been made on several

.

grounds The first paper was originally published in German

.
,

a
and t hough it has since appeared in English in the
there are many readers to whom it is not readi ly ccessible It
contains a mass of experiment a
.

l work much of which has been ,

utili sed in subsequent papers and for a ful l understanding of

any question it is important to know something of its historica
,
'

l
development and it is indeed the wa n t o f this which leads many ~

unscientific people to c omp lain of t he changeableness of scientific

views when with more knowledge they wo ul d realise that the
newer View is simply the logica
, , ,

l and necessary outcome of the

older in the light of wider knowledge Though t his first paper .

left much of the problem unsolved it is interesting to its writer ,

to see how much of the later solution is suggested ; and the final
answer was only rendered possible b y the important papers of -

Professor Donnan on membrane equilibri a which were ,

published in the same year A curious proof of the scient ifi c .

foundation of the theory is found in the determinations of acid

fixed which are gi ven in Tables III and IV and shown in fig
and which produced a pecul iar curve which a
.

t the ti m
. .

1 23 , e _

seemed inexplicable The explanation coul d not be given til l

1 9 1 4 when an equation to the curve was published in the Tr a
.

ms
of the C hemi ca
, .

l Society p 3 2 5 and its exact paral lelism wi th the

,
.
,

experimental results was most striking The rather important

paper ( Tra
.

m s Chem Soc p 3 1 3 ) in which this appeared is not

here reprinted as it is pretty readily accessible and a
. . . .
,

, l though , ,

it marked a great advance at the time the theo ry has been con
s ider a
,

b l y amplified and perfected in the paper of 1 9 1 6 b y Procter

and Wilson which is given
, .

A list of some of the more important papers on the acid

gelatine equilibrium are given
58 4 P RI N C I P L ES OF L EA TH E R M A N UEA C T UR E

even saturated solution of common salt has no dehydrating e ffect

without the preliminary acid treatment the e ffect is at first sight
striking a
,

n d unaccountable .

Th e swelling action is complicated in skin by its anatomical

structure which allows it to absorb liquids not m erely by colloidal
,

swelling but capillarily in the interstices between the fibres and

, ,

it was ob vious that no quantitative study could be made unless

means were devised to separate t he two e ffects Fortunately .
,

however gelatine b ehaves in a manner at l east qualitativel y

,

identical with hide fib r e and the very close chemical relationship

-

between the two j ustifies the assumption that t he sam e chemical

a ffinities are involved while from the absence of structure , _

capillary absorption is excluded Comparative experiment con .

firmed this anticipated identity of behaviour and as the e x p eri

ments were only intended as a preliminary invest igation ordinary ,

commercial thin sheet gelatine was selected as a material For .

the same reason and to avoid complicating the work slight

, ,

variations of laboratory temperature and other secondary dis ,

t u r b in g causes such as adhering moisture were neglected and a , ,

method of experiment adopted which was capable of c ompara

tively rapid execution Sheets of thin French gelatine of the.

purest kind were cut air dry to portions of about 1 gram in

weight and soaked in the requisite solutions th eir ga
-

, , _

i n in weight
'

, ,

determined after draining as far as possible from adhering

moisture and both the gelatine and the residual solution an a
a
l ysed
as reg rds acid and salt and the Whole c a
,

l culated to ash free,

-

gelatine dried at and to mill igram molecules per gram The -

.

air dry gelatine in the earlier experiments contained 1 6 0 7 per

-

cent of moisture which as it was kept in a stoppered bottle was

.
, , ,

practically constant and 1 1 9 per cent of ash consisting mainly .

“

of lime with traces of sulphites and phosphates It was no .

,

doubt a bone gelatine Fo r all the e arlier experimental work the

-

same sample of gelatine was used but for so me later series of

.
,

determinations other gelatines were employed of the same

character but not actually of the same parcel This may account .

for some variations between different series of experiments while

any single series ga
,

ve as a rule very consistent curves .

The S welling f
o a
Gel tin e in Wa
ter

The extent to which a gelatine will swell in cold water at a

given temperat ure is to a great extent a specific quality of the
particular sample influenced by the proportion of partially
hydrolysed gelatine products which are a
,

l ways present in the

-
 P A P ER S ON GEL A TI N E E Q UI L I B RI U M 585

commercial article These indeed cannot wholly be avoided since

.
,

the y are formed to some extent whenever the gelatine j elly is

heated so as to melt it and they are unquestionably the main
a
,

cause of those variations in ch racter which have been attributed

to what has been called the Vorgeschichl e ( previous history)
of the j elly Traces of soluble electrolytes al so affect it osmo
.

ticall y and perhaps chemically

, That gelatine and other .

gelatinising substances do not swell to infinity and become

colloid solutions like gum and dextrine is due to the solid but
elastic structure which is formed at setting the cohesion of which
fin a
,

l ly balances the attraction of the gelatine for water Under .

these circumstances it seemed not improbable that the swelling

maximum of any given j elly would be influenced by the volume
of its structure at the moment of setting and this is prove d to
be the case by the following experiment
Solutions cont a
.

ining approximately 5 1 0 and 2 0 per cent of , ,

.

air dried gelatine were cast in glass tubes on wire spirals for
-

convenience of handling and were then dried for some days in a

,

current of dry air weighed and allowed to soak in water at

, ,

laboratory temperature and weighed at int ervals Taking the

,
.

weight of actual dry gelatine as unity the amounts of water ,

absorbed were as follows

TA BLE I —A B S O RPTI ON
. BY G ELATI NE
1 0 20
per cent per cent . .

D ried in air O I ‘

A fter soa king 2 4 hours

a
A fter so king 7 2 hours
A fter soaking 9 6 hours
A fter soaking 1 2 0 hours
A fter soaking 1 44 hours
A fter soaking 1 68 hours
In ori gi nal j elly

As will be seen from the figures the original setting volume has
,

considerable influence on the maximum swelling but is evidently ,

not the sole determining caus e .

A c ti o n of A l cohol on a
Gel tin e j elly
It is well known that the swelling of gelatine j elly can be
reduced by treatment with alcoholic solutions and with absolute ,

alcohol it becomes a hard and apparently dry mass A s there .

is no reason to suppose any chemical action of alcohol on gelati ne ,

5 86 P RI N C I P L ES OF I EA TH E R M A N UFA CTUR E

which on soaking in water returns to its origin a l j elly condition

“

the case seems a favourable one for the study of the e ffect of
purely physical forces on j ellies Gel atine is practically quite .

insoluble i n cold al cohol either pure or dilute and conversely

even quite weak j ellies are semi permeable to a
, ,

l cohol i n solution -
.

Alcohol placed m a porous cell lined with gelatine and immersed ,

in water develo p s a considerable osmotic pressure and masses

of gelatine j elly dehydrated by a
, ,

l coh ol absorb scarcely any of

the latter
In order to ge t some idea of the e ffect of a
.

l cohol upon swell

ing weighed portions of a i r dried thin sheet gelatine were im
m ers e d m a series of mixtures Of a
-

l cohol and water for twenty four -

hours and again for twenty four hours l n renewed portions of the
,
-

same solutions This length of time had been found Sufficient 1 1 1

previous experiments to establish practica
.

l equilibrium The .

portions were then drained and weighed to determine the swell

in g the gravity of residu a l a
l cohol t aken and its percentage
a
, ,

calcul ted by the ordi nary tables , and the pieces d isso lved in hot
water and distilled to a volume of 2 5 c c of distill ate of which
the gravity was taken to determine a
. .
, ,

l cohol in the gelatine Onl y .

in the case of the 1 00 per cent alcohol did the gravity of the
di stillate fall so low as 0 9 9 9 a
.

n d in this case only to 0 9 9 7 9 , ,

so that any alcohol found may very well have been that merely
a dhering to the surface of the gelatine a n d more exact methods ,

of experiment must be adop ted before conclusive evidence of any

solubility of a l cohol in gelatine j ell y can be obtained tho ugh it , ,

seems possible that when the gelatine is nearly dehydrated some ,

alcohol 1 5 absorbed
A second series of experiments were a
.

l so made in a simi lar

'

way in which the gelatine was swollen l n wat er for twenty four
,
-

hours before treatment with the alcohol ic solutions The resul ts

which are given below a re a
.

l most precisely similar to those of the

,

fir st series except that in the 9 0 per cent and 1 00 per cent

a
. .
,

l cohol complete equili brium does not appear to have been

reached No eviden ce of penetration of the a
-

. l cohol into the j elly

was obtained the gravities of the di still ate ran ging from 0 999 6
,

to 1 0 0 0 The equilibrium appears to be completely reversible

. .

a
Table II gives the weight of swollen gelatine obtained from
.

I gram of dry It will be o bserved th t the curve is quite a

.

regul ar one The weight of the gelatine from absolute al cohol

is slightly less than its weight a
.

i r dried
It 1 5 of course impossible to c a l culate theoretic a
-
.

l ly the os motic
pressures of a l cohol in such concentrated solutions as were here
used but the curve is such as would be expected from osmotic
,
5 88 P RI N C I P L E S OF L EA TH ER MA N UFA C T UR E "

pressure acting on a material with a certain elastic rigidity of its .

own and there seems no reaso n to invoke oth er forces Prob .

ably if the osmotic pressures of the alcoholic solutions were

independently determined such experiments might furnish a,

means to calculate the elasticity of the j elly Neglecting any

a
.

small attraction of the alcohol for the gelatine the equilibrium ,

is prob bly
Cohesive attraction o f jell y ~

= attraction of gelatine for water

Attraction of a l cohol fo r wa
.

te
‘

Thi s is of course merely an inverse way of stating the osmotic

View since osmotic pressures are pa
,
rtial kinetic pressures ,

and may be exp r e ssed as minus internal pressures of the

solvent j ust as in a mixture of air and water vapour at atmo -

spheric pressure the pressure of air in the mixture is lowered by

that of the water vapour which is e qul va
-
l en t to a minus atmo
,

spheric pressure .

A lcohol though it precipitates hot gelatine solutions when

,

added i n large quantity can be mixed i n moderate proportio ns

,

without causi ng separation and the mass sets to an apparently,

homogeneous j elly which if alcohol is insoluble in j elly must

, , ,

really consist of alcohol water solution of such concentration

as corresponds to the equilibrium just di scussed enclosed as a
-

n ,

e mul sion in a j elly medium Such an emulsion should swell .

more in water t han a plain j elly since not only will the j elly
absorb a
,

ll the water necessary for its maximum swelling but ,

the alcoholic emulsion globules will become di luted and exert

'

an outward pressure on the j elly mass On the other hand if .

,

the action of the alcohol were a chemical one lessening the ,

absorptive power of the gelatine the swelling should be reduced ,

'

whether the alcohol were introduced from without o r we re

a
, ,

already present in the mixture Exp e rim en t ll y it was found '

that of two somewhat concentrated j ellies Of equ a

.
,

l strength
“

one made with water alone and one with a mixture of water ,

and alcohol the latter swelled much the more thus confirmin g
, ,

the emulsion character of alcoholic j ellies It is almost certain .

that such j ellies would sh o w microscopically the cell ular strue

_

ture which has been attributed by B ut s chli and van B e mm e l en

to j ellies in general .

The A c tion o f A cids on Gel tin ea

It is well known that gelatigenous fibre is swollen by all dilute
acids which are su fficientl y ionised a
l though very feeble acids ,
 P A P ERS ON GEL A TI N E E Q UI L I B R I UM 58 9
such as boric carbonic and sulphydric have little or no swelling
, ,

e ffect and the same is true of many of the weaker organic aci ds
, .

Gelatine l s similarly a ffected A gelatine which absorbs seven

.

or eight times its weight of pure water may absorb over fifty times
its weight of very dilute hydrochloric acid Fo r the most d e a .

tailed experimental work hydrochloric acid was c hosen as a ,

highly ionised and typ ical monobasic acid which could be easily
estimated both acidimetric a
,

l ly and by silver nitrate A further .

reason for the selection was that although in the commercial

pickling process a l ready mentioned sulphuric acid is used in con
ju nction with exc ess of com mon salt yet the acid principally ,

active must necessarily be hydrochloric ; and as a satisfactory

pickling can be produced by this and salt a l one nothing could be ,

gained as regards principle by complicating the equilibrium with

t h e presence of sulphu ri c acid and sulphates
Th e gener a
.

l method of experiment was similar to that which

has been already described Pieces of air dried sheet gelatine of
.
-

about 1 gram in weight of which the content in dry ash —free

.

gelatin e was known were soaked in solutions of acid of known

,

volume and concentration for forty eight hours which was found
-

a su fficient time to produce a steady equilibrium The volume .

and strength of the residual solution was determined acidi metri

cally with standard KOH solution and phenolphthalein the ,

s well in g o f the j elly was measured by weighing after draining

'

and it was subsequently melted and the absorbed acid similarly

titrated it having been proved by preliminary experiments that
,

the whole of the acid present could be thus determined and that ,

no di fference l n result was cause d by melting the gelatine An y .

slight variations from this procedure are noted in connection

with special series of experi ments
In an early series of experiments it w a
.

‘
s found that though the

whole of the acid present in the j elly wa s estimated using phenol

phthalein as indicator yet only a portion was determined when

methyl Orange was used a
,

l though to free hydrochloric acid both

,

indicators are equally sensitive It is therefore clear that in the

j elly a portion of acid is combined either chemic a a
.

l ly or by dso r p
tion in such a way that it is less ionised as regards H ions than
the rem a a
-

i nder which behaves s if merely dissolved in the j elly ,

”

and of course varies with the degree of swelling In order to .

get rid of the complication thus in troduced it was assumed as a ,

first approximation that the absorbed volume of liquid was of

the same concentration as that of the surrounding acid solution ,

and that the excess which was always found on the titration with
phenolphthalein was fixed or more closely combined with the
59 0 P R I N C I P L ES OF L EA TH ER MA N U FA C T UR E “

gelatine : This fixed cid proved to h e usu a ll y somewhat a

lower but roughly approximate in quantity to that estimated by
phenolphth a l ein but not by methyl orange and obviously re

a
,

presents the excess o f acid absorbed by the gelatine though it ,

does not accurately determine what portion is ttached to the

gelatine and what to the absorbed water and it will be shown ,

later that the quantity of acid really fixed by the gelatine is

greater than that so de termined Still it a ffords a ready means of
a
.

c omparing the char cter of the absorption and as such 1 s g1 ve n , ,

in the tables .

Table II I represents the results of more t han one series of

experi ments the R oman nu mer a
.

l s of the first col umn i ndi cating

,

the series These experiments were m ade in 1 8 9 9 and 1 9 0 0 on

.

one sample of French gelatin e the titrations being done mostly ,

by Mr P aget Table I V repres ents experiments made more

. .

recently with slight variations of method suggested by experien ce

, ,

on another sample of gelatine of a Slightly more acid character ,

and with apparently a greater solid c ohesion as the maximal ,

-

s welling is in all cases less though the character of the curves

a n d the positio n o f the maxima in g ener a
,

l show good agreement

with the earlier results Especially in the lower concentrations .
.

of Table IV some ambiguity is caused by the acidity of the

.

gelatine consisting mainly of bi sulphites which amounted to

0 2 8 2 mgr mols per gram as in di cated by phenolphth a
, ,

.
-
lein but
.
,

did not a ffect methyl orange and of which at least a portion ,

di ffused into the outer solution and a ffected its molecular acidity
'

as determined by phenolphthalein but could h a a

,

r dl h v e much
y ,
”
influence on the acid fixed D eterminations of the strengt h .

of the outer solution by methyl orange which certainly represent ,

the whole of the acid present as HCl are therefore given with
correspon di ng calcul ations of fixed Haci d a
, ,

n d of the acid

absorbed 1 n the gelatine a

,

s determined by t h e two indicators .

In reference to this work attention must be drawn to a paper 1

by Dr Wolfgang Ostwald on the swell ing of gelatine in which ,

he gi ves c urves for the swelling of gelatine plates in acids and

al kalies of di fferent concentrations In both cases he shows the .
’

existence of a maximum such as has j ust been described but he

a
,

l so observed a minimum with very di lute solutions of which the

Ostwa
,

present writer has found no trace 2

l d himself ascribes .

1
W0 O st w l d a Ub e er d e n E in fl u s s vo n S a
uren und A lk l ie n a af u d ie
G la
.
,

”
u el l u n g der ti A rc hi v f lir d i e g es P hy s i o l og ie B d 8 Bonn,
Q e ne, 1 0 1 9 05
m m ha i a
. . . .
,

2
T his m 1 n 1 b e e n fo u n d t th is o e l e c t r ic p o in t P H = 4 7 ,
“

u s s n ce e °

a a
.

or N /5 o o o o b u t , c o ul d no t well b e d e t ect ed b y t h e m e n s o f t it r t io n
u se d .
(H R P ) . . .
 “

59 2 P R I N C I P L ES OF L EA TH ER M A N UFA C TUR E

this tentatively to the originally acid reaction of the gelati ne ,

and in this he is prob ably correct as the acidity is usually due to ,

bisulphites which are acid to strong bases and basic to strong

,

acids and of which neutralisation in either sense would

probably diminish the o ri gl n a
,

l swelling in water The plates .

FI G 1 23 a
( T b l e s I II ad
n am g
— Ab s c is s e
; r -
m o l s H Cl in g rrn s o l u t io n
I
'

a Ta a
. . . . .
.

O r d in t es r e su l t s fr o m bl I I I e .
,
= r e s u1 t s fr o m T b l e IV .

he emp loyed were much thicker ( 3 to 4 mm as compared to about ~

.

0 2 5 mm ) than those used in the present research so that it is

. ,

doubtful if real equilibrium was reached ‘

.

Table V gives the results of a ser ies o f experiments intende d

.

to test the reversibility of the equilibri um gelatine acid water - -

Th e gelatine was swollen for forty eight hours in a solution which -

when equilibrium was reached was of 0 2 2 5 3 mols per mil con , .

centration and th en for twenty four hours in solutions of varied

,
-
 P A P ERS ON GEL A TI N E E Q UI L I B R I UM 593

O
mm m v H
0 o T

a
m
.

a
H
w m mw N m o m
o o
mm
c
w w
v
fi o
wE m S o
w
0 H 0
m H N o w o
.

mfi u N
3
H H n o o o
E
u
o m o
fi N
l o u w w w x e m w o mw u N w
fi oo nH fi R H ao
. .

é 0 o o o
.

fi x O m O 0 0 0 0 0 0 0 0 0 o 0 o
E
.

H o o
w H
N
n »
E H
H N

3 H%
.

fi
.

m
a
w
0 Q

—2
o
8fi n w m m wm m
_

K
o

u ao $ N m i
n 0 £8 o H N 0
m8
0

m w m o m m 0
h
k 0
3 o
u b m 5 w m
9 o
1 w w w w n o v m
- H
H
M E e c
m 3 8 o 0 é 0 é o 0 0 o o 0 o o b 0 0 0 0
0
d
w n
a
S8 e
m fi

m m m w w
HN in o
h

$ $
o H
m£
o 0
S
“
4
N
w w v
i
0
8
4 o
oH H H H H ? mm 5 5 m0 m
H
.

o 0
. .

0 0 H H H H H 0 0 0 0 o 0 0 b

m m H 0 m N m w N N v
$
o H 0 0 o
u o o 0 H w H o o N m o
6 wm
o n
N m N o 5 v 0 p w H n v n m H
mm N N N N H H H 0 0 0 0 0 0 0 0

m m w© mo w mw
v v
N
o 3 m
o w ©
N
N w
m
¢
H
0
N o m H
H u H
9 o
0 o o 0
N H H H H o o o o 0
.
0
.
o o 0
.

o 0 0 0 0 0 0 o o o 0 0 o o 0

N mm m N m mm w o o o
ao
3
o H
o mw u w n 0 n
o
H o o o o H
m o m v N m N N H o o
a
u 0 o
v am m m
n . N N N H HHHHHH

m
o m
s w w
H
N
H
.

H
e

H
N
o
O
H
Ku
0
N
m
N
N
m N w
HNe m H N m H o w
w H o 0 N mw 0 fi
m Hc
H m m
H © w
NN m w m m m m m m m m N
0
.
w o
n
. . .

mH .
a
. .
N
H
.

N N m mo H H m
$ o H N O mm N
H m m o N m N N H H
.

o
e N
N .
o N m m
H H H o m 6
o 0
v
o
H
0
.
H
0
.
H
0
.
0
0
.
0
0 .
0
0
.

0 o 0 0 0 0 0 0 o 0 0 0 0 0 0

H N m Si H N m fl mO h oo Ch O H
S
l n xo 1\ oo Q
' -

H H
59 4 P RI N C I P L E S OF L EA TH ER MA N U FA C T UR E

(lesser) concentrati on latter time does not se em to have The

'

been quite sufficient for equilibrium to be again attained but there ,

is no reason to suppose the absorption as other than completely

reversible The lowness of the fixed acid as calculated by
.
“

deducting the calculated acid o f the solution absorbed is some -

what remarkable and it is Unfortunate t hat in this series no ,

parall el determinations were made with methyl orange Several

"

possible explanations may be suggested but it see m s best t o defer ,

discussion for further experimental investigation The portions

which were only t r e a
.
.

t ed fo r forty eight ho urs in one solution are

'

norm a
-

l in respect of fixed acid .

Although no exact quantitative result can be expected from the

somewhat crude method of experiment it is evident that graphic ,

plotting of Tables I I I and IV fig 1 2 3 represents the curves of a . .

,
.
,

regular equilibrium the figures being fairly consis tent for any one
t 1 0n s a
series of de t e rmin a
,

n d the errors of experiment not greater

'

than may be expected considering the influence of various u n ,

determined factors such as the cohesive elasticity o f the j elly

and the extremely small f orces involved in considerable cha
, ,

nges
of volume near the swell ing maximum The approximately .

horizontal course of the fixed acid line after a certain con ,

centration of acid is reached s t ro n gi y suggests the idea of a ,

definite though h ydrolysing chemical compound rather than a

a
,

merely physical one n d the determinations of fixed acid ,

by the di fference of reaction of phenolphthalein and methyl

a
orange prove a decided change of concentration of the H ion at '

or near that p rticul ar point The Occurrence of a very marked

maximum of the swelling volume ( S) is s t rikin g a
.

n d this follows , ,

naturally from the combination of the two regular curves of

total acid per gram of gelatine ( a ) and of fix e d acid ( f) “
'

since by the mode of calculation S L

— _F
, it being the concen tra
x

tion of the external so l u t 1 o n gi ven l n column a .

As regards other acids only a limited amount of work has ,

been do ne With weak acids like acetic and lactic no definite

.
,

1
maximum of swelling has be e n observed the absorption of liquid ,

increasing with the concentration till solution of the j elly begins

.
.

With formic acid a maximum occurs at a concentration of about

0 0 7 gram mols per liter but it is less marked and the rise to it
-
.
, ,

1
It h ab s e en s in c e o b se r v e d by Mr A t ki n 1 9 20 , p 1 8 7 )
a a
ll aid a
t a aa
.

t h t t h is o c cur s wit h P c s H of 2 4 o f t h e ex tern l c i d w hic h

c o r r e sp o n d s v ery cl o s e l y wit h t h e PH =3 '

0 a
o f t h e g e l ti n i ts e lf f o u n d b
y
Lo e b b u t t h is H co n c en t r a
ti on w a
s not a
r e c h e d wi t h t h e v er
y we k a
aid
,

c s .
(H . R . P .
)
59 6 P RI N C I P L ES OF L EA TH ER MA N UFA C T UR E

is much more gradu a l than in the case of hydr ochlori c acid .

Owing to the fact that no repression of swelling t akes place

with the weaker a c1 d s ; a greater tot al swel ling can be obtained
by concentrating the s olutions with acetic and probably with lactic
acid than with hydrochloric though it is evidently accompanied ,

with greater solution and possibly by structural changes of the ,

gelatine .

As regards the fixation of acid the methyl orange method 1 s

inapplicable to any but the stron gest acids but ca
,

l culating the
absorbed solution as of e qu a l strength to the extern a
,

l figures for

a
,

the excess absorption are obt ained which for acetic acid of
-

m e di um concentrations are somewhat l o w er and for l ct ic and ,

formic about the same or slightly higher than those for hydro
chlo ric At the higher concentrations the tot a l absorbed acid
s so l a
.
,

’
rge that experimental error makes the determination of

a
fixed acid irregular and u nreliable and from the l owe st con
cen t ra t io ns the va
,

l ue rises to a fixed aver ge much more gradually

than in the case of strong ac ids .

As regards sulphuric acid but few determinations have been ,

made but these show that it produces a maximum swelling e ffect

at a low concentration of which the va
,

l ue has not yet been deter

mined and the apparently fixed aci d i s also somewhat larger
,
.

No experiments have yet be en made on the determination of

fixed acid by methyl orange but a s the change of colour of

this in di cator is gradu a

,

l it is evi dent that determination by mere ,

a
titration is so mewhat rough and it is proposed to investigate the ,

subj ect further by the actual de termin tion o f ionisation constants -

.

The following tables V I to IX give the results of the work . .

which has already been done on acids o t her t han hvdro chl o ric .

Table X ( XX I X 1 —3 ) gives a few deter m

. inations on sheep
.

a
skin and shows that a maximum exists the weaker solution swel l “

ing more th n the stronger and the acid fixed is very similar
in amount to that fixed by gel a tl ne The skin was un wo o ll e d in
the customary way freed from lime and dried at 80 C a
.

nd
°
.
, , ,

soaked in water till soft before use , .

A ttention must here be drawn to a research pub lished by

St ia sn y on the absorption of water and acid by hide powder and
’

o x hide
1
by quite di fferent methods to that adopt ed by the writer
From the data given it would be diffi cult or impossible to c a
-
.

t he acid fixed but the occurrence of a m ximum of swel ling in t h e

,

weaker solutions is in both cases very clearly marked The

l culate
a .

1
St i ay sn U eb er a
ti
neg Ad p tive so r on, 11 n d d ie B e st im m u n g der
Sa a
uf H a
,

”
Sc hwe l l wir k u n g vo n urentp l u u ve r u n d B l o ss e Ger b er 1 9 09 ,
ad C ll g i
, ,

pp . 1 83 e t s eq , . n o e u m, 1 9 09 , pp .
3 02 c i s e q.
 P A P ER S ON GEL A TI N E E Q UI L I B R I U M 59 7

H
e
um mm
mm o
e
.
o n o
.
w
Hm S
m e . .
am m
b o
.
o 0
.
H
0

.
m m m
m3 w
o
.
o
. .
. .

o 0 0 0 0 0 o N 0 0 0 0 0
l +

H
H .

O
<
H
0
fi
o
2E
5 w w
a
.

n o u o “ N v
E
0
2 E i w
vo
m
a
0 H u N N u u 0 N o
H 2
n
o N m m m m m m

a
? 0 w w 0
0
?
o H o n
NHo m N
.

h v h e
.

0
8- m H 0 9 ro “
o
H
H

4
.

m
A 8
H
sw 5
n
o n
H ” 0

3
5 A
n
,n
M
6 0 H H
d
o Q c
£ fi fl
a
.

fi
6 o
0
E fi
H o
m mw
3 H

a
w
.

E
0

m
. H E
w H
S 0 m m o
3
0 0 m N H m N C

a
i
H
H o m m H v 2 m w © H o H H
0 w w m N
H
0 H
fi m w 0 o 0 0
8 E fl n e H
.
o o o 0 m N H o 0 0
o
. . . . . .

-
o. 0 o o 0 0 H 0 0 o 0 0
H
9 H m
w
2 00
o i

H t mo H N 00 v mm
 *
59 8 P RI N C I P L E S OF LEA TH ER MA N UF A CT UR E

w v w
w H N m m Ho
v m o w w
. .
e
.
v
e
. .

o 0 0 0 0 0

E EN
a
0
wC E
a Ha
0
i m
n N H 0

a
E
v o o o n

H m m
a
.

n
H E
m H
i 9 m m m $
t o H 0 n “ 4

m m
? fl
m
0
H

0 E
H E
w w
.

m H H5 0 0 H
0 H 0 H H
0 H R $ 9 0 H 0 0

a
8 e
E oEE
0 0 H 0
H -
0 . . . .

H
m 5 0 0 0 0
.

a
H H o
w0 0 0
m
Q 2 0
0
0

H N M ?

H v mo m
60 0 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E”

results with hide powder and o x hide showed considerable d iver

gence which St ia sn y a
- -

,
t t rib u t es t o di fference in texture but which ,

perhaps may have been partly due to the time given having been
insu fficient to establish complete equilibrium .

On e of t he most st ri kin geffects of the pickl ing process which

gave ri se to the investigation is the extraordinary d ehydration
produced by the action of strong solutions o f c o m mo n salt on
the acidified skin fibre a nd a
«
_

l so on the acidified gelatine and

acidified gelatine is a
,

l so precipitated by it as a coherent mass from

its warm solutions No such e ffect is produced by common s a lt
al one on neutra
.

l fibre or gelatine the e ffect even o f saturated ‘

solutions being somewhat to increase the swelling— agelati ne

,
’

absorbing about eight times i t s weight o f water b eing capable of

taking up about eleven of saturated common sal t solution and a ,

larger quantity of one of medium dilution Th e results of a .

series of exp eriments are given in Table X I Some other sal t s .

,

however and notably ammonium sul phate and some other sul
“

p ha
,

t e s are well known to exercise a powerful dehydrating e ffect

,

on Swollen gelatine or skin and even to precipitate gelatine from

,

strong warm solutions as a coherent mass The discussion of

these actions of neutra l sa
.

l ts must be d eferred till the e ffects

of salts in acidified solutions has been more fully considered ,
.

It may be pointed out however that the e ffe ct is most n otice

, ,

able in the case of sulphates of weak bases such as ammonium ,

and zinc .

It is unimportant whether the gelatine or skin fib re is first

swollen by acid and then submitted to t he action of Sa
-

l t solution ,

or the proceeding is r e i erse d since similar effects are pro duced

f

by the addition of a suitable quantity of acid to the a

,

l ready salted

a ca
,

alth ough commerci a

a
gelatine and an e ffective pickling may be pro duced by adding
l c ulated quantity of cid to skins placed i n a strong brine
l ly the method 1 8 more costly The quantity .
,

of acid which is most e ffective is larger t han that re quired to

produce a maximum swelling since the presence of salt enables ,

the skin or gelatine to fix a larger quantity of acid than it can

do in an equ a l ly dilute acid solution without s a
,

lt In presence .

of su fficient salt however the necessary quantity of acid may be

( and commercially usu a
, ,

l ly is ) largely exceeded without mu ch

1 n t e r fe r in g with the result though large excess is undesirable
, ,

and in dilute salt solutions diminishes the dehydration Some .

instances of the action of aci di fied salt solutions on skin are given
in Table X ( XXX and XXX I and the results of much e x p eri
. . .

mental work o n gelatine I n presence of hydrochloric acid and salt

in di fferent proportions in Tables X I I and X III . .
 P A P E R S ON GEL A TI N E E Q UI L I B RI U M 60 1

Comparing the resul ts with those of Tables Il I t 0 V which gi ve

°

. .

the resul t s with hydrochl oric acid alone it will be noted that
the tot a
,

l acid absorbed by I grm gelatine is lower the con

‘

.
,

traction of vo lume caused by the salt expelling acid as well as -

U)

8 8
8 Q g

a
H 00 CO N N
?
“ “
‘
-
l J '

85
-

22 8 - 0 t
o 11
51 0 0
5w 0 0 0 0 0

a
z e
(n
9
5
o
”

N 00 N H
l\ c 0
? H

0 0 0
H H H

0 0 0 0
00 00 0 l\
O 00 00
x
9
M H 0

water but on the other hand the acid fi xed as calculated by

deducting from the tot a
, , ,

l absorbed acid that contained in a

volume of solution equ al to that absorbed is in all cases higher
than with hydrochlo ri c acid a
,

l one This does not necessarily .

60 2 P R I N CI P L E S OF LE A TH ER M A N UEA C T UR E
.

m 0 0 N H 0 0 0 0 0 0 N 0 0 0 0
0 H 50 0 H 0 0 0 N 0 0 0 N 0 0 0 H H
0 o
85
H
0 H 0 0 N H H N 0 0 0 0 0 N 0
H
fl
3
. . . . .

0 0
.
0

2 5 2 ofl
0 0 0 H H H 0 0 0 0 0 0 0
fi 0
o
w 5
g 0 0

0 N 0 0 0 0 0 H 0 0 0 0 0 H
0 O 0 H 0 0 N 0 0 0 0 H 0 0
N N H 0 0 0 N N H H H 0 0
I
H
. . . . .

0 H H H H 0 H H H H H H 0

0 0 H 0 H H 0 0
0 0 0 0 0 0 0 H
0 0 0 0 0 0 .
0 0
0 0 0 0 0 0 0 0 0

E
0 H h
9 0
.

3 H
H
0 H
m 0 0 0 0 0 0 0 0 0 0 0
8
H
0 H 5 0 G 0
0 0 0 N 0 H 0 N 0 0
-
5 b 0 0 0 0 0 0 0 0 0 0

m H 2
0
. .

O
E
.
3
.

n
H 0 0 0 0 0 0 H H
i m0
0
O

H 0 0 H 0 0 0 0 0 0 0 0 H 0 0
0 0 0 0 0 0 H H 0 0 0 0 0 0 N
0 0 0 0 N 0 0 0 N N
.
N
.
N 0 0 0
. . . .
. .

H H H H H H N
,

H H H H H H H 0

H 0 0 0 0 0 0 0 0 0 N 0
0 0 0 0 0 0 0 N 0 0 0 H 0
N 0 H 0 0 0 H H N 0 0 0 .
0
H
. . . .

H N 0 0 N 0 H H H H H N
H

0 0 0 0 0 0 H 0 0 H 0H 0
N 0 0 0 0 0 0 0 0 0 0 H 0
0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0
.
0 0 0 0 0 0 0 0 0 0 0 0

N 0 0 0 H 0 0 N 0 0 0 H 0 0
O N N 0 0 0 0 0 N N 0 0 0 0
H 0 0 0 0 0 0 H 0 0 0 0 0 0
0 0 0 N H 0 0 0 0 0 N H 0 0

0 0 0 0 H 0 0 0 0 0 0 H H
N 0 0 N 0 0 0 N 0 0 N 0 N
0 0 0 0 0 0 0 0 0 0 0 0 0
0
.
0 0 0 0 0 0 0 0 0 0 0 0
.
.

0 0 0 0 0 0 0 0
.

0 0 0 0 0

H N OO Vi
'
l - G K
O H N M V IO WD l\ OO O\
60 4 P R I N C I P L ES OF LEA TH ER MA N UF A C T UR E
‘
“

imply that t he acid actually attracted by the gelatine is greater

when salt is present but that the dissociation or hydrolysation
is less or on the Other hand th t the obviously doubtful a a
,

, ,
ss u mp ,

tion that the concen t ratio n in acid of the absorbed solution is

equal to that o f the extern a
.

l 1 s i nco rrect If as is probable the .

, ,

concentration of the absorb e d so l ut l o n 1 s really less the apparent ,

fixed acid will increase in some inverse ratio to the volume of

the solution absorbed .

On the other hand must be n oticed that the less 1 o n l s e d

,

FI G 1 24 a
(T b le — A b sc iss a Mg
e r a
m o l e c u l e s N Cl in I gr m so l u t io n
a a
-

a
. . . .

O r d in t e s = Mgr m o l H Cl in m d l t i = c o n c e n t r t io n o f

a
1 r r e
g y g n e o

aid fi
-

a
l
. . .

c x ed by 1 gr m d r y g e l t in e =wt o f so l u t io n b s o r b e d b y 1 gr m
a a
. . .

d r y g e l t in e Q x ed fis lt .

acid as determined by its non effect on the methyl orange is

a
-

, ,

proportionately n d even actually less in the salted than in the

, ,

merely acid solutions It is however by no means probable .

, ,

that methyl orange is wholly insensit ive to the aci di ty o i the _

acid gelat ine and unless this is the case the e ffect of the latt er
-

, ,

will be increased b y its greater concentration in the cont racted

j elly just as methyl orange is reddened by many organic acids
,

in concentrated solution which scarcely affect it when dilute .

An y direct action of the acid gelatine on methyl orange will -

diminish its apparent fixed acid as determined by this means .

An interesting point in Tables X I I and X I I I is that of the . .

amount of salt fi xed which in presence of hydrochloric acid ,

 P A P ER S ON G EL A TI N E E Q UI L I B R I U M 60 5

appears to he always negative the few apparent exceptions being

obviously due to experi mental errors and accompanied by a
,

b
norm a
,

l fig ures in one or other of the remaining determinations

while Table X I shows that in absence of acid a varying positive
.
,

amount is fixed The quantities were calculated by deter

mining the tot a
.

l chlorine in t he treated gelatine wi t h argentic

nitrate and potassium chromate n d subtracting from this
the hydrochloric acid found acidimetrically and the tot a l chlorine
,
a
calculated in the solution absorbed From the large tot a
,

l amount .

of chlorides present and the proportionately large e ffect of the

,

a — A b s c is s a; Mg r m o l H Cl
'

FI G 1 25 (T ble X III s e r ie s in 1 gr m
di a
-

a
. . . . .
,

s o l u t io n Or n t es = Mgr m o l H c l in
°
1 g r m d r y g e l t in e ; =wt of

a a
-

a a fi
1
. . . . .

s o l u t io n b so r b e d b y 1 gr m d r y g e l t in e ( b) O x edfi c id ; : xed

a
.

s lt.

absorbed solution great quantitative accuracy cannot be claimed

,

for t hese figures but they strongly support the View that the
,

chlorine absorbed as hydrochloric acid by the gelatine exerts a

corresponding expul sive effect on the chlorine ions ( both acid
and s a l t ) cont a i ned in the solution It is noted in connection
with the experiment a l work that in severa l cases where l a
.

rge
quantities of s a l t were used the sheets of gelatine instead of )

appearing homogeneous and transparent becam e white and

opaque and this must have been due either to the actu a
,

l crystal
l is at io n of s a l t in the gelatine or to the formation of a cellul ar or , ,

at least heterogeneous structure enclosing solution of a di fferent

refractive index to that of the sur rounding j ell y It is extremely
probable that thi s circumst a
.

nce may account for the irreg ularity

of the figures with rega r d to fixation of s a
lt .

From the curves given in fig 1 24 it will be seen that the swelling .

60 6 P R I N C I P L ES OF LE A TH E R
‘

M A N UFA C T UR E

di minishe s in a curve of hyperbolic character with increasing

somewhat above zero

a
concentration of s l t becoming asymptotic to a value apparently
,

Apparently a n y acid and its corresponding neutral s a

.

l t will
produce a dehydrating e ffect on swollen gelatine vary ng in
i

,
,

intensity with the electrolytic d issociat ion constant of the acid

a
-

and increasing with the concentration of the s l t The e ffect of .

sodium sul phate with sul phuric acid appears to be quite as great
as that of sodium chloride and hydrochloric acid in equivalent
a
concentrations while th t of the weak acids with their own
,

neutral salts is much less though di stinctly marked when com

pared to the swelling action of the ] acids alone a
,

s will be
'

obvious in comparing Tables X V and XVI with VI a

,

n d V I II
. . . .

With the weaker acids the ex cess of aci d absorbed in excess of

,

that due to absorbed solution apparent fixe d acid is much

l ess and very irregul ar as compared to that observed with the
a
stronger cids and this is particularly the case with the feebly
ionised acetic acid of which the ionisation is still further reduced
by the presence of its neutra
,

l salt
'

It is not necessary in order to produce contraction of swell

ing that the salt employed should have the sam e a nion as the
acid , and if the salt is one of a strong acid and in s ufficient con
cen tration good contra ction may be obt a
,
i ned even by a c idi fic a

tion with very weak acids Thus effective pickling may be

obtained with formic or acetic a cid in presence of common s a
.

lt
and at the writer s suggestion formic acid has been to some extent
’

used commerci a l ly for sheep skins as the antiseptic effect is

-
,

even greater than that of the customary sulphuric acid while

certain injurious e ffects of the latter on the fin a
,

l manufactured
product are avoided In the ordi nary com merci a l process as
has been stated sul phuri c acid and common s a
.
,

,
l t are employe d
but except for questions of cost hydrochloric acid and sodium ‘

sulphate wo ul d be equ a
, _

l ly e ffective as shown in Table X VII

Table XVIII shows results with acetic acid and common s a
.
,

. lt .

'

It will b e observed that both the dehydration and the acid

fixed are practic a l ly the same with acetic acid as they w oul d
have been if hydr ochloric acid had been used .

Table X IX gi ves a series in which potassium chloride is sub

“

stituted for sodium chloride with h ydrochloric acid The results

are again practic a
.

l ly identical with those of sodium chloride .

60 8 P RI N CI P L ES OF L EA TH ER MA N UFA C T UR E

H
0 0
> 0
0 E0 £ 0 N H 0 0
0
0
0 0 0 8 0 N H
.

0
0 0 O 0 0 O 0
0 0
0
3
0

0
0
.
0
0
H

0
0 0
3 0
.

3
.

0 0 0 0 0
0
0
0
E
H
0
0 H
0
0
0
0 0 0 0 0
0
w
. . . . . . .
.

3 0
0 0 0 0 0 0 0 0

0 8
0
H
.
H H H H H H H H

9
0

m
9 H
H
0
0 0 0 0 N
0 H 0 0 N 0
- H
.

0 0 0
0 E
.

N H 0 0

n
M .
H
. .
O
0 w 0 0 0

1 0 0 -
0 0 0 00
P A P ER S ON GEL A TI N E E Q UI L I B R I U M 60 9

0 0
0 H
.

H 0 0
O 0 N
0 0 0
H H 0
. . .

0 0 0

M ‘
d
‘
lfl KO N OO
61 0 P R I N C I P L ES OF LEA TH ER ~
MA N UF AC T UR E

m
.
1 0 E
3 H
Q
0 .
8 Q
N
0
0
0
0
0
0
H
0 0
0
0
N
0
0
0
0 0

a
0
0
0 0 E
H 8
.

H
.

H H
. .

H H
.

0
0 8 m 9
0
H

H 6 0 0 0
0
.
0 N 0 0
0
.

0
.

0 0 H
H H

N 0 0
0 0 0
H 0 0
0 N H
. .

0 0 0

0
0
61 L EA TH ER MA N UF A C T UR E
’

PR I N C IPLE S OF
‘

2
'

0 o m
Q 0 m o
0
.
o o
0 H é h

w
8 0
0
J i
0 m u
9 g g g

N m
R m w
o m o
m
.

0 h

¢ m
0 m
0 m m
0 o
0 é

0
0
0
0
0
0
0
N 0
w 0
w
0

H m v H 0
m o w 0
m m m 0
o 0 o 0
é
.

0 é 0

M V IO O
 PA P ER S ON G ELA TI N E E Q UI L IB R I UM 61 3

S u mm ay
r

a
Gelatine absorbs Water with evolution of heat and is capable
of exertin g large extern l pressures in the initial stages but as
the quantity of water beco mes greater the avidity of the gelatine
,

becomes less and there is no further perceptible evolution of heat

, ,

while the mechanical force exerted is exceedingly slight and may ,

be measured in a few dynes per square centimeter The process is .

completely reversible and water may easily be expelled from the

fully swollen j ell y by mechanical pressure a
,

n d compl etely r e

moved by evaporation in va
,

cu o and to a large extent by d eh y

dr a
,

t in g agents though as dryness is approached the last portions

,

of water are removed with great di fficulty The swelling does .

not proceed to infinity in cold water but reaches a defin ite ,

maximum which 1 3 an equilibrium between the affinity for water

,

and the elastic cohesive forces of the gelatine which are influenced ,

not o nl y by it s chemical character b ut by its original volume at _

setting In hot water complete solution takes place

. .

Gelat ine is insoluble in and water swollen gelatine is imper

,
-

meable to strong alcohol which deh ydrates and compresses it

‘

, ,
.

If however alcohol is incorporated in the liquid j elly which is

subsequently allowed to set a
, , ,

nd immersed in water the swelling

, ,

is increased beyond the ordinary maximum .

Gelatine swells in very dilute acids to a much larger extent

than in water In weak acids this swell ing increases with the
.

concentration of acid till finally solution takes place but with ,

strong acids the swelling reaches a maxi mum at very low dilutions ,

and subsequently diminishes in a curve of hyperbolic character

til l the j elly dissolves without further swelling which limits the
possible range of experiment If however a neutr a
,

l salt of the
.
, ,

acid be added the dehydration may be carried with strong acids

,

to a point at which the gelatine forms a solid and horny mass .

With weak acids and their salts the e ffect is less marked but quite ,

obvious If however a weak acid is used with large excess of

a sa
.
, ,

l t of a strong acid the gelatine behaves as if the strong acid

only was present while gelatine swollen with a strong acid and
treated with the s a
,

l t of a weak one naturally behaves as if the

weak acid had been used .
‘

In all cases the acid absorbed by the swelling gelat i ne 1 s m

a
excess of that due to the absorbed solution and this excess is ,

in any one series of experiments of an pproximately constant

amount over a wide range of concentration of the acid or acid
.

and salt solution ; while under no conditions does it pass a

maximum of about 1 2 5 mgr mols of acid per gram of dry .
-
.
6 r4 PR I N C IPLE S OF LEA TH E R M A NUFA C T URE

a
g e l t in e f In t he
case of strong acids which affect the colour of
methyl orange even at very great dilutions , it is sho wn that a
a
-

portion of the acid absorbed by gelatine which v ries with the

conditions of the experiment but a
,

l ways fal ls within the limit

'

above stated has become so considerably less ionised than the

,

free acid that it is i ncapable of a ffecting th e colour of methyl

orange though it may still be estimated by phenolphthalein
In the case of common salt it is sho wn that while in neutr a
.
,

l
solutions it increases the s well in g o f gelatine and an amount is
a
‘

a
,

bsorbed in excess of th t normally contained in the absorbed

s olution in presence of even small quantiti es of hydrochloric
acid great dehydration is produced a
,

nd the fixation o f salt is ,

negative .

Theoretic l a
As regards the explanati on of the foregoing experimental
resul ts anything which can yet be said must in view of the pre
,

liminary character of the i n vestigation and the somewhat rough

m ethods of experi ments be regarded as merely worki ng hypo
thesis As apreliminary to this it is necessa
,

. ry to have some
definite conception o f the actual structure of a gelatine j elly and
the View which is here a dopted is t ha
,

t of a networ k of gelatine .

molecules cohering to each other b ut leaving interstic es of ,

molecular dimensions containing water or aqueous solutions ,

which bein g within the range of molecular attractions are really

, ,

semi solid solutions in the gelatine and have wi t h it a common

-

internal pressure The gelatine molecule consisting as it does

of a
a
.
,
'

complicated chain of amido acids is pecul iarly fitted to pro

duce such astructure The r nge of molecular attraction does
-

a
-

not apparently exceed I O up ( millionths of millimeter ) and

ma y be much smaller ( 9p Freun dl ich Ka a
.
,

ill échemi e S 2 7 7 )
p
'
.
.
, ,
'

but as about 2 per cent of gelatine is required t o form a coherent.

j elly there would b e in each cubic space of

,
a weight
of gelatine over thirteen million times the estimated weight of a
hydrogen molecule and therefore ample molecules for a net of
,

molecul ar di mensions The facts mentioned as regards the e ffect

.

of concentration at the moment of setting on the subsequent

swelling give considerable support to the idea of a molecular
network formed at the time .

This View though apparently very similar to t h e currently

accepted one of van Be m m el e n and B ut schl i is re a
,

l ly very ,

di fferent since these investigators assume a cellular structure of

,

microscopic dimensions and hence far beyond the range of mole ,

.

o n lar forces That such cell ul ar j ellies or pseudo j ellies exist and
.
-
61 6 P R I N C IPLE S OF LEA TH ER MA N UFA C T URE “

fie d in the case of j ellies by the residual forces of solid cohesio n

which oppose change of volume It can be shown however that .
, ,

in or near the region of maximum swelling these forces are

1
extremely small P vo n Schroeder showed that a j elly swollen
. .

in water lost a large amount of weight and volume ( up to 7 3 per “

cent ) in an atmosphere of saturated water vapour but that this -

was co mpletely prevented if the j elly were saturated with a

.
,

N solution of an alkaline sulphate and co nsiderably

'

l esse n e d b y one of N
’

I t was subsequently sho wn by the

present writer that the energy involved in removing 1 grm
2 ‘

water against the osmotic pressure of a N sulphat e solution

( about 3 5 0 ergs) was quite comparable to that done against
'

surface tension in forming the surface of a sphere 1 grm weight .

r

and that no doubt the shrinkage might be accounted for in that

way It therefore follows that in most cases o f consi derable
. .

swelling the solid cohesion is almost negligible as compared to

osmotic forces On the o t he r ha . n d in the earlier stages of ab s o rp '
,

tion of water by dry organic colloids including gelatine the

for Ces involved are large a
, ,

s is evidenced by the marked evolution ,

of heat the contraction of common volume and the very con

'

s id e r a
, ,

b l e pressures obtained when the s wel lmg is opposed by

mechanical ob stacles
I f the swelling of gelatine in pure wa
.

ter b e ad mitted to be
osmotic still more evidently is this the case with regard to the
dehydrating action of a
,

l cohol on the swollen j elly since the latter , ,

though freely permeable to water is practically impermeable to

a
,

l cohol and the j ell y mass acts as a simple o s m o t ic c ell

,
-
Th e .

curve of swelling in mixtures of water and alcohol (Table II ) is .

of a simple type corresponding closely to a rectangular h yperbola

,
'

in the mid dl e portion but diverging at both extremes possibly ,

because of the solid rigi di ty of the j elly T here is no reason t o . .

doubt complete reversibility Al cohol shows considerable osm otic .

pressure in an osmometer with gelatine membrane and it is sho wn ,

that alcohol incorporated in j elly must produce a cell ular s t r u c

ture in which the j elly acts as a semi perm eable membrane I t
,
-
.

is possible that more complete investigation of the deh ydrating

e ffects of alcohol on j ellies might a fford some definite information
on their cohesion and osmotic pressures since the action is purely ,

physical .

Th e explanation of acid swelling and the peculiar maximum of

its curve and of dehydration of acid gelatine by neutral s a l ts is
much more complex and involves chemic a
, ,

l as well as purely
,

osmotic considerations In what follows the most detailed con .

,

Co l l eg i u m, 1 9 03,
p . 2 04 .
2
E vi l A ss oc R ep "
. . 1 9 0 8, p . 21 6 .
 PA PE R S ON GELA TI N E E Q UILI B RI U M 61 7

sideration will be given to the action of hydrochloric acid and

sodium chloride as these have been most fully investigated and
, ,

there is no reason to think that the results di ffer in principle

from those of other acids and their corresponding s a l ts
Gelatine j elly is known to be very permeable to both acids a
.

nd

salts and to their ions so that it is not easy to see how either
ca
,

n exert a direct osmotic pressure on the j elly mass It has -

.
,

however been shown that even very dilute hydrochloric acid is

,

absorbed with some avi di ty by the j elly which always contains

acid in considerable excess of an equ a
,

l volume of the surrounding

solution with which it is in equilibrium and this excess rising ,

rapi dl y at first , s o on becomes an almost constant quantity ( see

curve of fixed acid in fig strongly suggesting the idea
.

of a definite though hydrolysing chemical compound of the nature

of a salt in which the amphoteric gelatine acts as base This
,
.

idea is further supported by the fact that an approximately corre

s p o n din g quantity of acid becomes neutra l to methyl orang e
‘

though it can still be hydrolysed by Su fficient excess of water and ,

estimated by titration with caustic alkali with phenolphthalein

as indicator If such a gelatine chloride exists it is extremely
probable tha
.
,

t it will be much less permeable for hydrochlo ric

acid and other chlorides than the neutral gelatine or if we regard
the j elly as a solution that the solubility o f s a
, ,

l ts of a common
'

anion in the acid j elly wil l be much less than in the neutral
‘

while its affinity for water is likely to be greater owing per ,

haps to its greater ionisation The j elly of course must be in .

, ,

equilibrium with the surrounding solution in every respect and ,

firstly in r egard to hydrolysis in which it will obey the ordinary ,

law of mass— action A s regards its volume the case is quite

an a
.
,

l ogous to that of solutions of an acid and its salt separated

by a movable septum permeable to the acid and to water but n o t , ,

to the salt which in the present instance is an in di ffu sib l e c olloid

,
'

j elly The two solutions must be in complete equilibrium and

as the s a
.
,

l t cannot di ffuse water and acid m ust pass through the

,

septum till equilibrium is reached Firstly then the common .

, ,

anion must be at equal concentration in both solutions and ,

because of the sal t anions the free acid must necessarily be less
,

concentrated in the salt solution than in that of the pure acid

Secondly the anion of the acid in s a
.

, l t solution must be in e qu il i
b riu m with that of the salt itself and this can only occur by ,

abso rption or expulsion of water or acid till the ionic pressure of

the s a
‘

l t is equal to that of the acid contained in its solution

Thus the necessary data being given the volume of the s a
.

,
lt ,

solution or j ell y is definitely fixed and dependent on the con ,

 "

61 8 P RI N C I PLE S OF LEA TH E R M A N UF A C T UR E

centration of the acid ions and the ionisation and quantity of

the s a lt A gai n t he quantity of unh ydrolys ed and ionisabl e salt
.
,

for a fixed quantity of base de pends on the hydrion concentra

tion of the acid and t he hydrolysis constant of the salt and thus ,

di fferent acids with di fferent constants may produce very varied

e ffects of swelli ng
On e c onsequence of wh at ha
.

s j ust been said must be re marked .

It is evi den t tha t the fixed acid calculated on the assumption

a
,
.

that the bsorbed s olution is of equal acid concentration to the

surro undin g acid does n ot represent the whole of the u n hydro
,

lys ed gelatine salt but is less than it by the amount of acid ex

,

p e ll e d b y the salt from its solution Wh ether the whol e of this .

acid 1 s e xpelled by the ionised salt o r a part als o by the u n ionised

‘

, ,

which deman ds water f o r its solution is not easy to determine but ,

p robably unimp ortant for the g eneral theor y of the e quilibrium

It is of course impossible to treat t h e problem at present in a
.

ny

but it m a
a
rigid mathematical way while so man y of the fa ctors are u n
known a nd especi ll y that of the cohesive elastici t y of the j elly
, ,

y be interest ing to see h6 w far the experimental results

agree with theoretical assumptions .

We have assumed that the combinatio nof gelatine with hydro

chloric acid i s of the nature of a salt o f a weak base with a strong
acid of which the hydrolysis according to Wm Os t wa
'

, l d is r e p re ,
.
,

hB Kw
sented by the equation — k wh en h IS the hydrl o n con
K l
-

,
b
centration b that of ( colloid gel a
g

,
t in e ) ions and B of the hydro ,

lysed and u nionised b ase ( gelatine)

‘
Kw is the dissociation .

constant of water K that of gelatine as a base It may be taken

'

.
, g

without serious error that at the dilutions in question HCl is

fully ionised and that therefore its concentratio n x i n the solution
,

is proportional to h the concentration of the hydrio n s b is th e

,
.

concentration of the kation of the i onised but unhydrolysed salt

a
,

nd as the quantity of gelatine i s c onstant in the e x periment 3 ,

is obviousl y equal to 1 b The equation therefore takes the form .

b
, _ a n reso Vi ng IS as regar S We ave
x +k
the measure of t he proportion of unhydrolysed salt Th e sa me .
1

expression may also be obtained from the ordinary diluti o n

2
d
equation
(1 a
y ;
k ,
which ,
substituting the hydrolyt ic fo r

the dissociatio n constant also applies to moderat e hydrolysis ,

.

'

Th e hy d r o l y s e d p o r t io n is o b v io u sl y
1
62 0 PRI N C IPL E S OF LEA TH ER M A N UFA C T U R E

combine with 1 2 8 mgr mols of acid or in other words that the

- -

equiva
.
, , ,

l ent ( though not necessarily the true molecul ar ) weight

of the gelatine considered as monovalent is about 7 80 It Will
, ,
.
’

therefore be necessary to multiply the values of x by 1 2 8 to

a
-
'

obtain the ctual acid combin ed with the gelatine base .

We may now consider the further question of how the volume

of swelling is connected with the absorption of acid The ex
p e r im e n t a a
.
.

l curve is a very peculi r one with a marked maxi mum

‘

indicating that at first the swelling increases rapi dl y with in

creased concentration bu t afterwards diminishes inversely in a '

a
,
_

slo wer ratio A ccording to the theory which h s been Suggested

.
,

the swelling is due to the superior solubility or attraction for

water of the ionising gelatine chloride as compared to the n o n
ionising neutral gelatine and it should therefore increase directly ,

with the increase of the chloride On the other hand it is r e

’

pressed by the anion of the acid solution which not merely ,

causes the concentration o f the j elly with expulsion of water till

its tot a l 1 0 n 1 c pressure is equ al t o that of the acid but also ,

co mpels the expulsion o f fr e e acid from the j elly against the

'

same pressure of 95 so that the tot a l anion pressure of the j elly

,
-

mass may remain equal to x The force required to compress .

the j elly therefore vari es no t merely as 95 but as 962 and for a ,

g 1 ven i ncrement of x the swelling should dimi nish as W e

should expect therefore that swelling would be represented by

x
such an exp ression as (3 B where x and k
x

have the same values as before and (3 is a n empiric l constant

connecting the volume of the j elly with its pressure Such an

+k
,
x +k
-

a
.

expression will obviously give a marked maxi mum for some small
value of x and by di fferentiation it is sho w
,
n that this maximum
occurs when x = k We have thus a means of arriving at a
value for 13 since the experiment a
_ .

,
l maximum is clearly marked
at about x o o o s N and the swelling curve on fig 1 2 3 is there
: ~
, .

fore calculated as 7 8 g It is possible that the true value

a
.

x +k
of k is somewhat l ess than 0 0 0 5 N and th t the higher maxi ,

mum which this woul d cause is prevented by the c o he sio n o f the '

j elly ; and since the curve rises much more abruptly than it .

falls the e ffect of this rounding o ff of its summit would be to shift

,

the apparent maximum t o a slightly higher concentration but

in any case if the hypothesis be correct it cannot be much lo wer
, ,

that o o o s and at least the order of the quantity remains

-

unchanged .
 PA P E R S ON GELA TI N E E Q UI L IB R I UM 62 1

l
i a
w
Since k — and Kw is kno wn we can calcul at e an ro x i
z
, pp
l 9

mate val ue for K the ionisation constant of neutral gelatine ,

o
or of the order of 1 x It would be interest
o5
ing to confirm this by more di rect measurement
Of the direct experiment a
l resul ts only the va
.

l ue of the total
absorbed acid remains to be c a
,

l culated This is evi dently ( from

'

the mode of calculation of the fixed acid the sum of the

latter and of the volume of absorbed liquid in the j elly multi
plied by the concentration o f the extern a l solutio n A s the .

former approximates closely to o 8 mols from the maximum of ~

.

swelling onwards and the latter to , the curve has been

x

plotted on the sum of these and su fficiently well exp resses the
experiment a l va
,

lues but o ffers no explanation of the amount

and constancy of the fixed acid— a
,

question which is dis cussed ‘

in the next paragraph It is however interesting to note that .

, ,

t he curve of absorbed acid is al so well represented by =

y 87 96
0 41 -

t he logarithmic plotting of the smoothed curve being only slightly

convex to the origin and showing that curves quite of the a
, dso r p
tion typ e may arise as the sum of purely chemical actions .

It has been assumed that the resistance of the j ell y to com

pression by the acid of the o uter solution is the product of the
direct ionic pressure of the gelatine salt and of that of t he anion ,

of the acid which is expelled along with the water to maintain

'

equilibri um but which must carry with it its correspon ding

,

h ydrion The swelling pressure within the j ell y is thus the sum
.

of three partial pressures of which only one is that of t he anion

,

itself and the acid expelled is therefore only one—third of the

,

total ionised gelatine salt Since between and x = o 3

.
~

the quantity of gelatine chloride and its ionisation remain sensibly

total and constant and what change takes place in the one is
,

partially compensated by the corresponding change in the other

the apparent fixed and the expelled acid will also rem a
,

in
constant the one being about 0 8 and the other about o 4 mols
,
-
.

We have as yet no definite information as to the ionisation of

the gelatine salt t h e repression of which is no doubt negligible
a
,

within the limits n med but must become considerable in the ,

presence of much sodium chloride or oth er salt with a common

anion In this case the acid fixed as u n ionised gelatine salt will
.
-

‘
increase and that expelled will di minish so that the curve of ,

fixed acid must more and more closely approach that of the
62 2 PR I N C IPLE S OF LEA TH ER MA N UFA C T UR E
’

uh -
ionised gelatine salt as under these circumstances it is e xp e ri
,

mentall y shown t o do
A point much more di fficul t of explanation is the a l most vertic a
.

l
rise of the fixed aci d curve near the origin a n d its slight maxi ,

m u m correspondin g to that of the swelling curve It is ob vious

that the re a
_
.

ll y combined ac id cannot exceed that of a correct

'

hydrolysis curve and no constants or mo di fications can be

a
,

adopted for the l tter to make its rise more rapid which do not
at the same time throw the swelling curve derived from it entirely
out of harmony with experi m ent It is perhaps a som ewhat “

fo r Ce d though not I think a na

.

l together i mprobable explanation

that the uncombined gelatine at first ads orbs acid without actu a
, , , , ,

l
co mbination and that this adsorp tion is favoured by the large
'

volume of the j elly at the point of maximum swelling where the

small maximum also occurs on the fixed acid curve. This a
,

ds o r p
tion would of course tend t o increase the apparent fixa tion o f
acid and render it more uniform and wo ul d disappear with the ,

disappearance of free base since it is improbable that the chloride ,

woul d adsorb hydrochloric acid Some alternative explanations .

may be suggested but it is better to wait the results of further

,

experiment 1
.

It must I think be admitted that the complicated system of

, ,

curves which has been deduced from the theory of actual chemical
combination shows an agreement with experimental results
which is more than accidental a nd which in some sense really
represents facts whether these be strictly chemic a
,

l or not It
is not to be denied that a
.
,
'

n equally plausible h yp othesis might

conceivably b e based on physica l adsorption but to be satisfactory

it must show a correlation of experiment a
,

l facts at least as com

p l e t e as that which has been o ffered It is to be admitted that .

much remains to be done in explaining the still outstandi ng ,

deviations in adducing further proof and in replacing empirical

,
-

constants by those based on d e fin it e knowledge , but the present ‘

paper at least provides a wo r kin g hyp o t hesis The most marked

'

deviation of fact from theory consists in the more rapid rise of the
fixed acid to a small maximum above that allowed by the
curve of unhydrolysed salt and disregarding probable imper ,

fe c t io n s in t he dilution equation in such an extreme case it is ,

suggested that this may be explained by actual adsorption pre

liminary to chemical combination
It is obvious that t he theory a ffords a complete qu a
.

l itative
explanation of the dehydrating effect of common s a l t solutions
1
Th e exp l aa
nti on is c o mp l et ely g iv e n b y t h e t h e o r y a s s u b s e qu e n t l
y
d eve lo p e d . S e e Tm n s. . Chem S o c
. .
,
1 0 5, 1 9 1 4, p .
325 .
(H . R . P .
)
62 4
“

PR I N C IPLE S OF LEA TH ER MA N UFA C T U R E

a
other organic bases not only the anion but the hydrion enters
into the s a In all c a
,

lt ses the nion is the compressing and de

hydrating agent and in the absence of a neutra
a
.

l salt a maximum ,

with subsequent contr ction is produced by the acid itself This .

is however only obvious in the case of the stronger acids since

the weak acid a
, , ,

l though it may produce a gelatine salt is so little

io n is e d t ha
, ,

t its anion cannot reach a su fficient concentration to

overcome the pressure of the more i onised gelatine salt Thus .
,

while sulphuric acid produces a marked maximum that of formic ,

acid though still obviou s is much less dist inct and with acetic
, , ,

and lactic acids none is observable and the swel lin g b o n t in u e s ‘

t o increase with concentration beco mi ng in the end greater than

,

that produced by the stronger acids and going on without a ,

break to the final solution of the gelatine In these cases the .

apparent fixed acid is somewhat variable sometimes higher and ,

sometimes lower than that of strong acids according to whether

the ionic concentration is su fficient to prevent hydrolysis or to
attack addi tional amino groups .

It may be obj ected that sodium or potassium chlo rides will

pro duce vigoro us dehydration not only with hydrochloric acid
but with a
,

n y o t h er acid of su fficient hydrion concentration to

,

produce swelling but a li t tle reflection makes it obvious that any .

such combination simply leads to a quadruple equilibrium in which

each acid is balanced against its own neutra l sal t Thus in the .

case of acetic acid and sodium chl oride we have gel ions acet ions -

,
-

and an enormous excess of so di um and chlorine ions and if we ,

imagine combination we must by the law of mass action

,
'
-

have much gelatine chloride balanced against so di um chloride

Hence
'

and littl e gelatine acetate against sodium acetate .

the rule since the salt is always largely in excess that with
the s a
, ,

l t o f a strong acid the dehydrating effect is the same

whether the acidification has been by a weak or a strong
acid and vice vers a A cetic or formic acid will produce s
, .

e ffective a pic kling wi th common salt as sulphuric or hydro

. a
chloric acid .

As regards other acids and their Salts it has been shown that
in all cases depression of swelling is caused by a su fficient additio n
of the neutral s a l t but this is most marked with the s a
'

, l ts of the
stronger acids possibly because Wit h we ak acids the ionisation
'

of the salt added is insu fficient to repress that of the gelatine

compound itself .

I do not propose in this paper to discuss the compli cated e ffect

of the action of s a l ts on the swelling of neutral gelatine which ,

has been specially investigated by Pauli Ho fmeist er von , _ ,

 . P A P ER S ON G ELA TI N E E Q UI L I B R I U M 62 5

Schroeder and others but it may be suggested that it is quit e ,

1

conceivable that in many cases a portion of the salt undergoe s

dissociation or hydrolysis and that both aci d and base combine ,

with the gelatine and that the compound so formed swells or is

compressed by the rem a
,

i ning salt solution according to its con -

a
centration Faessler has shown that sodium acid sulphate is
2
.

dissociated by hide substance only the neutral s l t remaining -

in solution and it is clearly proved in the case of chromic ferric

, , ,

and aluminic salts t hat a si milar acti on takes place in which both
acid and base ( or a basic s a l t ) are absorbed This absorption of .

base may occur either by combination with opened u p COOH -

groups or as complex salts such as are often form e d by ammonia

,

with other bases ; and some of these may form complex ions
which are unrepress e d by those of the simple s a l t in solution .

The subj ect of alkaline swelli ng is also left untouched but it is ,

clear from some preliminary experiments that in certain respects

it di ffers radically from acid swelling Fo r instance swelling .
,

by sodium hydrate is not at all repressed y sodiu m chloride but

b 3

is so by higher concentrations of the hydrate showing that in

this cas e hydroxyl ions and not the kation Naare the swelling
,

and repressing agents It is hoped to pursue the question of

alka
.

l ine swelling .

It is o b vio u s that the facts discussed in the paper have an

important bearing on many physiological questions and in this ,

connection a crude attempt made in th e early stages of the

inquiry to imitat e muscular contraction may be worthy of men (

tion A slender spiral plat inum electrode was embedded in a

.

cylinder o f j elly which was immersed in a salt solution containing

a second electrode Wh en the gelatine electrode was the anode
of a su fli cie n t current to electrolyse the s a
.

a
l t the j elly contracted
admirably but its relaxation by a reverse current was somewh t
,

unsatisfactory owing to the evolution of hydrogen which broke ,

up the gelatine No doubt with a suitable depolari ser b etter

.

results might be attained and it is quite possible that the con ,

densation of the anion by a mere surface potential di fferen ce might

be su fficient to produce the e ffect .

P auli 4 has r e c e n t l y p ub l ish e d a paper on albumen in which he

'

1
P al i ( P ah
u se el e s ) Pfl ug A r c h:, 1 89 8 7 1 336 u 3 39 P al i u u Ron a
a
. .
, .
, ,
.
,

B e i tr C he m P hy s i o l 14 P t ho l 1 9 0 2 2 , 2 5 —2 6
2 H o fme ist e r , A r c h f u r
a aa
. . . . . . . .
, ,

exp e r i m P t ho l u P h r m co l , 1 8 8 8 2 4 , 4 2 4
. . . V o n Sch r o e d e r , Co l l eg i u m , .
, .

1 9 02
p 3 0 6:
a a a
.
,

2
Wi s sen sc h f tl z c he B e il g e des L e der m r kt , 1 9 0 1 , ii 1 0 6
’

ab a
. .

3
Th is h s ee n sh o w n b y l t e r wo rk t o b e not s t r ic t l y t ru e t ho u gh
ai aid
,

the r e p r e s s io n is ve rv m u ch l e ss t h n n t he c e qu il ib r iu m .
(H . R . P .
)
f t f ur Che m I n d d e r K o l l o i de S
'

4
Z e i t s c hr z . 14 . .
,
1 9 1 0, . 241 .
 LEA THE R MA N UFA C T U R E
’

62 6 P R I N C I P LE S OF
'

s upport s very similar v1 e ws to those just expressed though

l aying more weight on the hydr a
,

a
tio n of t he colloid ion than has
been done 1 n the present work In particul r he strongly d vo cates . a
the molecular as opposed t o the cellular or network structure
claimed by B ut schl i He also mentions the fact that acid j ellies
cannot b e dehydrated by pure alcohol which h a
.

s been confirmed ,

in the present investigation th ough it has also been found that ,

with acidified al cohol considerable contraction takes place .

PA RT I I .
-
TH E A CI D G L T N
E A I E E QU ILIB RI UM 1 -

By H and J A WI LSO N
'

. R . P R OCTE R . .

a
l

In an earlier p per by one of us ( Tr a n sa

cti on s 1 9 1 4 1 0 5 3 1 3

Jou rn a l of the A mer ican Le a ther Chemis ts A s s o cia

, , , ,

tion 1 9 1 4
’

, ,

pp 2 0 7 —2 5) it was shown that gelatine forms hydrolysable

.
,

salts with acids that swe lling is due to the ionisa t ion of these
a
,
.

n d the osmotic pressure s o produced and that an equilibrium

'

results in which the concentrations of anion h ydrion and

i oni sed gelatine salt can a
, , ,

l l b e expressed as functions of t h e
‘

concentration of acid in the external solution within the limit s ,

of e xperimental error In this e arlier paper t he concentration

-
. .

of the ionised gelatine chlo ride in the equilibrium gelatin e hydro -

chloric acid was shown to be approximately Clg 0 290 + 0 00 0 2 ,

where Clg was th e chlori ne ionised from the gelatine salt and x
a
,

the concentration in terms of norm lity of the extern al hydro

, ,

chloric acid ( Through an error Clg was given as

’

but a
.

l l actual calculations were made from the above formula ) -

It wa
.

s also assumed that the numerical values in the exp ressio n

a
were const nts as those adopted su fficiently closely repre sent ed
,

the experimental results then quot ed but closer theoretical in

v es t ig a t ion ha
,

s shown that this is not strictly the case but that

'

both Clg and x are functions of a quantity e which is the di fference , .

in osmotic pressure between two phases of which the ionic pro

ducts are equal but in one of which t he factors are unequal
,
'

and that it is this di fference which causes t he swelling of the j elly .

a
In the paper cited the hydrochloric acid and gelatine salt were '
,

for the sake of simplicity supposed to be wholly ionise d and s , ,

the ionisation in both cases i s very high and the solutions were
dilute such an assumption was quite j ustifiable as regards e x p e r i
,

mental results In the clo ser theoretical examination which we

.

now propose however we must define the concentrations as

, ,

1
Tr aati ns c on s o f t he Che mi c l S oc ie ty ,
'
a 1 9 1 6, pp .
3 0 7 ff .

62 6
 LEA TH ER MA N UFA C T UR E
-

62 8 P RI N C IPLE S OF

cannot simultaneously be fu l fill e d since in t he j elly [ Ht ] and ,

[ Cl ] are necessarily unequal the chlorion being greater than

’
,

the hydrion by the amount 2 and the sum of the sides of an u n ,

a
equal rectangle in necessaril y greater than that of the sides of
.

square of e qual area (see fig In other words 2y + z is

greater than 2 95 by an amount we sh a
.
,

l l call e and the corrected ,

,

equation becomes
2x + e = 2y + z
The concentration of diffusible ions of the j elly is therefore
greater by e th a
,

n that of t h e outer solution It is obvious since .

,

water and hydrogen chloride can pass freely into the j elly that
there must be some force equal to a
,

n d Opposing the osmotic

pressure produced by this excess e of concentratio n at e quili

b r iu m for otherwise the j elly would tend to swell to infin ity
, .

B efore attempting to speculate about the nature of this oppos

ing force we must consider its mathematica
,
,
l relations to t h e
other concentrations of the equilibrium as defined by equations
( 1 ) and
/
The general t heory of the equilibrium as developed
in earlier papers ( this book p 1 1 7 and ] A L C A 1 9 1 4 ,
.
, . . . .
, ,

pp 2 0 7 —2 5) is that when gelatine is placed in dilute acid it

.

ab sorbs it freely and forms a hydrol ysing salt the propor

_
_ ,

tion of which to t he whole gelat ine base present is determined

by the hydrolysis equation The gelatine salt like other salts .
, ,

is highly ionised into the anion and a colloi d kation which ,

either from polymerisation or other causes pecul iar to the

colloid state c a n n o t diffu s e a n d exerts no measurable osmotic
‘

pressure whilst its anion is retained in the j ell y by the

,

elec tro chemical attraction of the colloid ion but exerts osmotic
’

pressure which on the one hand causes the mass to swell with
, ,

absorption of the external solution and on the other expels a

portion of the aci d both ani0n a
, , ,

n d hyd rion
,
from this solution ,

absorbed the result in equilibrium being that the j elly is poorer

,

in hydrion and more concentrated in anion than the external acid

solution the di fference of concentration between anion and
,

hydrion in the j elly being of course equal to the ionised anion of

the gelatine salt and electri ca
, ,

l ly balanced by the positive gelatin e

,

ions Whilst the hydrio n concentration in the j elly is less con ‘

c e nt r a t e d than that of the outer solution by the amount of acid

expelled which may be called I) (t he isotonic volume o f hydr io n or
,

chlorion expelled at a concentration of x) v bears the simple

relation t o y that y + v= x and the concentratio n of ionised ,

gelatine chloride 2 2 1 ) e ,
: .

B y solving simultaneously equations ( 1 ) and ( 2 ) the fol lowing

interesting relations are derived
 PA P ER S ON GELA TI N E E Q U I L IB R I U M 62 9

_ 2
=
+y z

2ic + e ( z -

e )
2

x— y) = Z + 2 —
2
( 2\ /y +y z
2 295 + X/ x2 1
y :

4 +2
“

y
These relations can b e represented graphically for any value of
as is shown in fig 1 2 6
‘

x, . .

02 04 06 08 IO
'

. . . .

FI G . 1 26 .
— Cu rv es of Co n c en t r t io n a .

Any one variable can be derived in terms of any other two but ,

in no case from o nly the two equation s given can an equation be

, ,

derived containing only two variables A s was pointed out pre ; .

vio u sl y however
,
2 was found from ex eriment to be equal
, p
approximately to 000 2 which bears a resemblance to-

one of the derived equations namely z Putting , ,

:

e = o oos we get 02x + o 00 0 02 5 which is stri kingly

° - -

,
63 0 P R I N C IPLE S OF LEA TH ER M A N UFA C T UR E

like the one obtained empiric a l ly but gives low val ues for concem
t ra
,

t io n s less than x = o o 3 Theoretical co nsiderations rendered

~

it improbable that e considered in the genera

.

l way in which
we have done could be a re a
,

l constant but it is di ffi cul t to obtain

, ,

a smooth experimental curve from the formula e = ( 1

) —
W
y
cause Sma ll errors in y correspond with large errors in e and ,

it is not possible to determin e y in the most dilute solutions with

a
very great ccuracy by volumetric methods .

It occurred to us however that if we could incorporate the

, ,

volu me of the j elly Which can be determined with great accuracy

into an equation contai ning only two other variables it Wo uld a
, ,

t
once be possible to calculate any variable from V and a
,

t only .
‘

It was found that the theory could be su m med up in the fo rm of

such an e quatio n which could readily be subj ected to the rigid
,

test of e xperiment The notation used is that mentioned earlier

.

in this paper The degree of ionisation of any given electrolyt e

.
‘

MN is often expressed by the formula [ M+]

where K may be nearly constant a
,

s in the case of acetic acid or a , ,

variable as in the case of highl y ionisable electrolytes In the

,
.

following gelatine chloride is considered to be ionised into

gelatine ion and chloridio n a
,

n d t he gel atine io n to be ionised ,

still further into gelatine molecul e and hydrion : A similar case “

a
would be the ionisation of ammonium chloride into ammonium ,

and chlorion n d the further ionisation of the ammonion in t o

ammonia and hydrion We may therefore write
a
.

( ) gelatine ion] [ ] K [gel a

Cl = t in e chloride]
’

[ x

( b) [ gelatine mol ecule] [ H ]£ K [g e l a

t in e ion] + ’

or y (g — a —z = K z
)
'
.

By solving ( a
) and ( b) simultaneo usly to remove the term in a
( )
c Kgy z
y
2
2+ Kyz +y2 + KK z 2 ’
.

Taking Procter s figure of 83 9 for the molecul ar weight of a

’

unit of gelatine 1 grin of gelatine represents 0 0 0 1 1 0 gram

,
.

equivalent Therefore at any volume

.

1 9 1

Substituting ( d) in ( c) and si mplifying

63 2 P R I NC IP LE S OF LEA TH E R MA N UFA C TURE

TA BLE I .

B y Experiment . Ca
l culated .

V x

1 6 9 02 62
1 7 5 0 2 20
-

1
2 0 2 01 74
21
-
6 o 1 -

53
21
-
6 0 1 30
22 -

4 o 1 -
08
24 1 00 87
25 -

9 00 64
34 3 00 3 86
4 5 6 00 1 65

1 1 8

a
49 4 00

56 4 0 0 07 1

means of the bove formula It will be noted by reference to .

figs 1 2 7 and 1 2 8 that e apparently varies dire ctly as the volume

. .

Such a relation if it could be proved would simplify all other

, ,
-

relations to t h e extent that any variable could be expressed with ,

suitable constants in terms of any other one and the theory as

, , ,

such might well be said to be compl ete

,
.

It was conceived that by means of the hydrogen electrode we

could determine a l l the variables in a special experiment in which
the volume was kept more nearly constant On e gr m of gelatin e . .

was d issolved in such a quantity of water that at 3 3 the volume °

was 2 1 c c This hi gh temperature was used because it is n e c e s

sary to m a
. .

ke hydrio n determinations in the melted j ell y Th e

'

method of using the hydrogen electrode was similar to that used

and described by Sorensen A cid was added at interva . l s and
the hydrion concentration determined From the figures
obtained it was fo und possible to c a l culate a
.

l l the variables
desired Knowing the quantity of acid added it was possible
.
,

to calculate from the hydrion concentration found the amount

, ,

which had combined with the gelatine and consequently the ,

total concentration of gelatine chloride giving values for y and

a Whilst actu a
,

+z . lly th ere is no external solution there is a ,

theoretical one since the p ro d u c t s o f hydrion and chloridion

,

must be equal in both phases that is the product y (y + z ) of ,

the j elly is equal to the x 2 o f the theoretical external solution .

1
Th e s e c a t io n s a
l cul a e base d o n t h e fi g u e s f B ra
r
y ad H u n t (j o u r r o n n

ad ad F a
.

A mer . Che m S oc
. 1 9 1 1 , 33 , 781 ) n t ho s e of N o ye s nl k ( i bi d .
, 3 4,
 P A P ER S ON GELA TI NE E Q UI L I B R I UM 63 3

If as before we regard the gelatine chloride as ionised to bout

, ,

the same extent as hydrochloric acid we can take K as the

,
a
ionisation constant of hydrochloric acid at a concentration of
-

0 03 0 05

0 0I
.

a
'

+ which is known
z, . From the equation it
follows that

in which all terms on the right hand side are known and
-

,
c o n se
63 4 PR I N C IPLE S OF LEA TH ER MA N UFA C T UR E
'

a
quently 2 can be cal cul ted From y and 2 a l so all other vari
ables can be cal cul ated by formul a
.
, ,

e presented earlier in this paper .

The results obtained in this way are given in Table I I and are
shown graphically in fig 1 2 9 . .

The curve of special interest is that of the variable e which is ,

seen to increase to a maximum at a very low concentration and

then to fall in a manner similar to that of the volume curve

x
N

FI G . 1 29 .

Since
represents the measure of an o utw rd pressure
e a
we have when the j elly is free to swell an applica
,

tion of a special
case of H o o ke s La w a
, ,

t ten si o s ic vi s where stress = e >

< strai n ;
’

, ,

and since e is a uniform pressure it follows that it will produce

'

an increase in the size of the j elly but not in its shape and that
‘

the increase in volume will be directly proportion a

, ,

l to the pull .

If we take the volume of 1 grm o f dry gelatine as o 7 c c then

-

.
-
. .
, ,

so long as the elastic limit is not Where

the value of the constant is determined by the bulk modulus
of the gelatine or particul ar protein under consideration The .
‘

relation is therefore dependent on t he temperature and that this ,

is an appreciable factor is shown by the rough ex p e n m en t s

tabulated on t he foll owing page
It is probable t h a
.

'

t t he e ffect produced by this limited rise of

temperat ure is not due to material changes in ionisation or
chemical activity but almost solely to the diminution of the solid
,
63 6 PR I N C IPLE S OF LEA TH ER MA N UFA C T URE
0 0 0 0 0
0
0
0 0 5 0 0 00 .
.

0 0 0 0 0 0 0
3 w $
0
0 0 0
9 3 0
0 0
0 0 0 0 m 0
0 0 0 0 00 0 0 0 0
0 0 0 0 0 0 0 0 0 0

0 0 o 0 0 0
0 0
0 0 0
9 $
0 0
m 0 5
8
0 0 0
0 0 0 0 0 0 0 0 0
0 0 o 0 0 0 0 0
0 0 o 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0

$
0 0
$
0 0 0
0 0 0 0 0 0
0 m
3 0
0 0 0 0 0
0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0
0 0
.

0 0 0 0 0 0 0

0 0 0 0
0 30 0
0 0
0
0 0
0
0 0 m
0 0 0 0 0 0 0 5 0 0 0 m
0
0
5 0
0 0 0 0 0 0 0
0 0 0 2 0 0 0 m
0 0 0 0 0 00 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0

m 0

m
0 o
$
0 0
1
0
0
0
0 .
0 0
u 0
m 5 3 0
0
0
0
0

0
0
0
0
0
0
0 0
0
0
0 8 8 0 0 0 0
5
0 0 0 0 0
0 0 0 0 0 0 0 0 0
0 0
0
0
0
5
0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0

$
0 0 0 0 0 0
0 5 m 0 0
0 0 0 0 0 0 3 0 02
0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0

0 0 0 0 0 0 0 0
0 0 0 0 3 0 0 0 0
0 3 00
a m
0 0 0 0 0 0 0
0 0 0 0 0
0 3
0 0 0 0 0 0 0 0 0 0 0 0 0 m 0
0 6 0
.
0 0 0 0 0 0 0 0 0 0 m 0
0
0
3
0
0
0 0 0 0 0 0 0 0 0 0 0 0o 0
0 : 0 0 0 0 0 0 0 0 0 0 0 0 0 0

0 0 0
0
0 0 0 0 0 0 0
5 3
3
m
0
0 0 0 0 0 0 0
3
0
0 0
0H
0 0 0 0 0
2 0
0 0 0
0 3 9
0 0
m9
0
0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0

0 H 0 0 0
. .

H H 9 9 0
0 0 0 0 0
 PA P E R S ON G ELA TI N E E Q UI L I B R I U M 63 7

apparent decrease in z in the most concentrated solution given ,

in Table I I is due chiefly to the increased volume .

An interesting point is raised here regarding the action of salt

in repressing the swelling of j elly swollen with acid Whilst the
sa
.

lt undoubtedly represses the ionisation of the gelatine chloride

to some extent it woul d scarcely be su fficient to account for the
,

fact that salt reduces the volume of j elly almost to that of dry
gelatine The chief action is probably that the addition of salt
.

corresponds with an increase in the value of x and that this

incre a
,

s e in x must according to the equation just discussed pro

, ,

duce a decrease in the value of (3 with a correspondin g diminution ,

of the volume of the j elly .

Summ ay r

When gelatine is immersed in a dilute solution of an acid

combination take s place between the gelatine molecules and the
hydrogen ions resulting in the fo rm a
‘

t io n o f a highly ionisable
sa
,

l t of gelatine the anion of which in tending to di ffuse exerts

,

on the j elly mass an outward pull which being uniform in all

directions produces according to H o o ke s La
, ,

w an increase in
’

, , ,

the volume of the j elly proportional to the magnitude of the pull .

In the case of gelatine immersed in a very dilute solution of a

highly ionisable acid ( say I grm of gelatine in 1 0 0 c c of N/I o o o
hydrochloric acid ) almost a
. . .
,

l l the acid combines with the gelati ne

and we have the simplest type of equilibrium where practic a
,

l ly
a
, , ,

x o y o n d the con c entration o i th e anion of

'

z z
, ,

the j ell y is the measure of the outward pul l and consequently

of the increase in volume In more concentrated acid solution .

( say I grm of gelatine in 1 00 c c of N/I O hydrochloric acid )

only apart of the acid combines with the j elly and we have
.
, . .

'

y + z > z > 6 but here it is n either the total concentration of

,

anion of the j ell y nor that of the ionised gelatine salt which is
the measure of t he fo r c e producing swelling but it is the excess
‘

, .

of concentration of di ffusibl e ions of the j elly over that of the

external solution This quantity 6 is a direct measure of the
a
.

swelling so long s t he swelling does not exceed the elastic limit ,

and o ffers a complete explanation of the pec ul iar swelling curve

obtained by immersing gelatine in increasing concentrations of
hydrochloric acid ( see fig In the most dilute solutions 6
wi ll increase a l most directly with the increasing initi a
.

l concentra
tion of acid but will approach a maximum as the formation
,
'

of the gelatine monochloride nears completion and must

then decre a
,

se as x becomes larger accordi ng to the equation ,

63 8 PR I N C IPLE S OF LEA TH E R M A N UFA C T URE

e = — 2x where 2 has a limiting maximum Value .

The repression of swelling by the addition of salt is c aused by

the apparent increase in the value of x produced which results ,

in a di minution of t he value of e and consequently in a r e p re s

sion of the swelling this action being assisted to some extent by
,

the repression of the ionisation of the gelatine salt .

In the case of weak acids like acetic a greater total concentra

, ,

tion of the acid is required to produce nearly c omplete com

bination of t he gelatine with the acid because the degree of ,

a
combination is determined by the value of y which even in the , ,

more concentrated solutions will be small bec use of t he r ep r e s

,

sion of the ionisation of the acid by the highly ionisable gelatine

salt Fo r this reason the swelling of gelatine in acetic acid
increases wi th incre a
.

sing total con centration of acid and 1 5 not ,

r e pressed by the addi tion of an excess ; in fact the swelling ,

continues up to a strength of acid of N/I beyond which solution ,

of the gelatine takes place The somewhat stronger formic .

acid actuall y shows slight repression whilst ver y weak acids , ,

such as boric as would be expected produce little if any swelling

, , , ,
.

In pure water combination must take p lace although probably

, ,

only to a very slight extent between the gelatine molecul es and

,

the hydrion of the slightly dissociated water leaving in the j elly ,

a corresponding excess of hydroxyl ions which tend to diffuse

outward causing the j elly to swell Th e pr esence of sulphites
,
.

in the gelatine and carbonic acid in the water tend of course to , ,

produce a greater swelling than the minimum which would result

a
,

from pure gel tine and water di fficult if possible to obtain, , ,

.

Some work has been done on the equilibrium of gelatine and

‘

alkalies b ut solution of the gelatine took place at so low a c o n c en

t ra
,

tio n of the alkali ( at about 96 0 0 4 for sodium hydroxide at

2 0

that the work could not be carried out to the extent desired
Work on hide ha
.

s shown that the swelling is repressed either by

the addition of excess of alk a l i or by the addition of ammonium

chloride In the former case the swelling is repressed by the
.

increase in the value of x according to the law derived for acids

in the latter case by bringing the solution back a
,

l most to a con
dition of neutrality the gelatine compound being again de c o m
,

posed It is probabl e that the laws governing alkaline swelling

.
.

are the same as those governing acid swelling

It wi ll be seen that t he laws discussed are quite gener a
.

l and ,

that for any particular sample of gelatine at constant temperature

any variable can be expressed as a direct function of x and that
for all acids the value of K will be the same whilst the va
,

l ue of
’
,
.

K is merely d ependent on the degree of ionisation of the gelatine

 A PPEND I X C

COA L TA R D Y E S T UF F S S UI TA B L E F OR D YE I N G A N D S TA I N
-

I N G VE GE TA B L E A N D CH R OM E TA NNE D L EA TH E R

a
By Mr M C LA MB Director of the Light Leathe r D epart
ment Le a a
. .
,

t h e r s e ll e r s Comp ny s Technic l College Tower

’ ’

, ,

Bri dge R oad London S E r , , . .

-

A bb reviations of the names of dye manufacturers

Alliance Colour a n d Chemical Co R adnor Street Works .
,

Stretford Manchester , .

B . British Dyestu ffs Corporation Blackley Manchester , ,

.

C . The Clayton A niline Co Lt d and The Society of .

,
.
,

Chemical Industry in B asle Clayton Manchester , ,

John Campbell Co . 7 5 Hudson Street Ne w Y ork

“

, , ,

U SA . . .

Co Colne Vale Dye and Chemical Co , Lt d Mil n sb r idge

. The . .
, ,

Huddersfield .

D E I du Pont de Ne m e u r s
. . Company In c Wilmington
. .
, ,

D elaware U S A , . . .

G J R Geigy S A B asle Switzerland

. . . . .
, ,
.

L B H olliday Co Lt d Huddersfield
. . .
, ,
.

L London Dye Manufacturing Co Lt d City Mills High

. .
, , ,

Street Stratford London E , , ,

.

J B W R Sharp
. L t d Lumb W orks
.
Ed e n fie l d . .
,
.
, , ,

Lancs
Sa Sandoz Chemical Works Basle Switzerland
.
, ,
.

Y orkshire Dyeware and Chemical Co Lt d Kirkstall .

,
. ,

R oad Leeds ,
.

D YE I N G

Single A cid Colours suitable for Dyeing Vegetable -

tanned
Leathers

B r own s

A cid Brown 7 9 1 86 ( B ) . Manilla Brown ( B) .

7 94 8 7 ( )
B . Nu t Brown D ( B ) . .

B .
( o) . Y ( B) n
 C O A L TA R D YES T UFF S -

64 1

Brown s ( continued )
A cid B rown G ( C) . . R esorcine Brown A . Conc .

L 3 48 ( C)
. .
(B ) .

1 5 80 ( C) . R esorcine B ro wn ( C) .

G .
( G) .

L 60 0 ( S)
. . A .
(B) .

Leather B rown G (A) ( H)

aBrown R R
,
. . .

SX ( A ) T n ( B)
Leather Ta Light Ta( L)
. . . .

n B rown
( )
A n

D ark Ta( L)
. .

Orion Bro wn G ( S) . . n .

Yel l o ws

A cid Y ellow 7 9 2 1 0 ( B ) Leather Y ellow SX ( A)

a Me t a
. . .

Air e d l e Yell o w ( Y ) n il Y ellow S ( Ca )

‘

. . .

A z o Y ellow I ( C)
. . Naphthol Y ellow S ( C) . .

Ca S ( Ca )
( )
a
a

ai
. . .

Az o fl v ne C ( C)
. . Tartr zine ( C)
7 0 3 2 ( C) .

Cit ro n in e Y . Conc ( B) . . S ( H)
. .

( B) . Pure ( H) .

000 : ( C) .

Fast Leather Y ellow C ( C)

at a a
. .

4G ( C) . . T r rph e n in e
(S ) .

R ( C) . .
Quinoline Y ellow ( C) .

Kiton Y ellow R ( C) . . Kiton Fast Y ellow G ( C) . .

S ( C) . . Z G ( C) . .

SR ( C) . .
3 G ( C) . .

G ( C) . . R ( C) . .

Z G ( C) . .

Or ag
n es

Ac e ko Orange I I Ca
( ) Orange II ( C)
a
. . . .

A cid Orange G ( B) . . II .
( )
S .

Crocein Orange SX (A ) . . II .
(A ) .

Kiton Fast Orange G ( C) . . II .

Z R ( C) . . MNO ( C) . .

Orange I I ( H) . . R ( C)
. .

II .
( B) .

Sc al f
r e s

A c e ko Scarlet R ( Ca ) . . Leather Scarlet ( A ) .

Z R ( Ca ) . . Ponceau R ( H) . .

3 R ( Ca ) . . Z R Conc ( H) . . .

41
64 2 P RI N CI P LES OF LEA TH ER MA N UFA C T URE
'

S our l ets (continued )

Ac e ko Scarlet 4R Ca
( ) . . P onceau SS ( L) . .

(Ca)
Z G . . Scarlet R ( B )
. .

Coomassie Milling Scarlet G

'

. z R( B)
. .

3 R ( B)
Coomassie Sc a
. .

rlet QOI Z K ( B) . .
50 ( B ) .

Croceine Scarlet 9 I S7 K ( B)
'

. . Z R .

( Ca ) . Mil hn g Scarlet 5E
P onceau 4R ( H) . .

a
F st R e d (Ca )
A ce ko . Fas t Leather R e d PSNR .

A cid Milling R e d G Conc . . C ( C) . .

( G) Red A .
(A ) .

A cid Milling Red R . COn c . A .

( )
G . S Ex (A )
. . .

A cid Magenta NS ( Co ) . . A Ex ( S) . . .

A cid R e d 9 0 3 EA S ( B) . .

A ci d R hodamine R .
( C) . Kiton R e d S ( C) . .

Z R .
( C) . G ( C) . .

3R 6 B ( C)
( Sa
. .

Brilliant Sul p h o n R e d B .
) . R occell ine ( C) .

Cardinal R e d J ( B) . .
( Ca ) .

3B .
( )
B . Toney R e d B D ( B) . . .

Claret Red ( Ca ) .

B orde a ux

A z o R ubine ( S a
) . C am i i
r Conc ( Sa
o s ne ) . .

( Ca) . Erio Fast Fuchsine B L Conc . .

B enzyl Bordeaux B . C
( ) .

Bordeaux B (A ) .
.
. Helianthine G ( G) . .

Brilliant Bordeaux B ( H) Jasmine ( G)

a
. . .

C r m ois in e ( Ca ) . Pure B ordeaux B . ,

( )
B .

A c e ko Blue CY ( Ca ) . . Kiton Fast Blue V ( C) . .

B enzyl Blue S ( C) . . Leather Blue R R .

(A) .

B ( C) . . SX .
(A) .

Fast A cid Blue R H ( B ) . . BB .

( )
A .

Fast Leather Blue L ( C) . . Marine Blue ( H) .

A I ( C) . . Orion Blue
AR I .
( C) . Soluble Blue NS .

I nduline ( C) . A .
(A ) .
6 44 PR I N C IPLE S OF LEA THER ‘

MA N UFA C TU R E

Single B asic Dye s s u ft b l e forn -

a ei n g V egetable -
tann ed
Leath ers
B ro wn s
B asic Brown BX N ( D)
. . Canelle 33 7 3 ( C) .

GX ( D) 57 3 3 ( C)
55 7 1 ( C) . 8 33 7 ( C)
Bismarc k Bro wn R . 1 005 .
( B) . 63 N: ( C) .

G ( C) . . OF ( C)
. .

R ( C) . C
( ) ES . .

-
M ( C) . . Ch o colat e Brown 3 9 3 6 (C) .

8 63 4 ( S) . MNB 86 ( C) . .

(A) . H avan n a 3 52 ( C)
R . Conc ( H) .

R . H
( ) .

R . Conc ( Co ) . .

Y .

R ( Ca )
a
. .

Brown A T .
( G)
. . Ve s u vm e GS .
(S )
Canelle 1 3 52 ( C,
Yel l ows
A cridine Yellow R H
( ). . B rilliant P hosphine ( C) Z G . .

Z R ( H) 5 G ( C)
( Sa
. . . .

A ur o rriin e 0 .
) . R ( C) . .

0 . H
( ) . P atent Phosphine G ( C) . .

O.COn c .
( H) .
Z G ( C) . .

II . M ( C) . .

O ( B) R ( C)
“

. . . .

aa
II ( C) . .

O ( C) S bPhosphine G
a
. . .

0 0 pure . C
( ) . Z G .
(S ) .

O ( G) Sella Flavin e G ( G)
‘

. . . .

O ( D)
. R .

Conc ( D ) Sel la B rilliant Y ellow P

a
. . .

(C ) Conc ( G)
a flai ( Sa
. .

Brilliant Phosphine G . T nno v ne T .

) .

Or ag
n es

A cridine Orange L .
( B) . Chrysoidine R ( D)
. .

Chrysoidine YR P ( B) 1 60 6 ( S)

GS ( Sa
. . .

) . . G ( D)
. .

R ( G) . . Ca
( ) .

R (A ) . . Pure Chrysoidine YD .
( Co ) .
 C OA L -
TA R D Y E S T UFFS 64 5

Magenta 87 9 52 ( B ) . R hodamine B Ex . .
( D) .

( C) . Safranine G OOO .
( C) .

R ussian R e d B
( C) . . MN ( C) . .

G ( C) . . BS H
( ) . .

Rhodamine B ( C) : . RFF ( H) . .

G ( C) . .
( Ca)
Y
. . .

6G ( C) . . Tannin Pink C ( B) . .

B ( D) . .

B l n es

B asic Marine Blue ( Ca) Methylene Blue XD ( D)

B eng a
. . .

l Blue R ( G) ( D) B
Fast Blue 3 R ( Sa
. . . .

a
1 5 65 ( S)
) . . .

Methylene Blue 2 B ( B) .
( )
C .

F (B - Turquoise Blue G ( B) . .

B EH H) . . Victo ria Blue BX ( D) . .

BB Ex ( H . . Co nc ( D) . .

R Ex ( H) B B ase ( D)
( Sa
. . . . .

2B .
) . B ( Ca ) . .

D .
( G) .

Green s

B asic Green Conc ( H)

B . . . Methylene Green G ( H) . .

G Conc ( H) P ( C)
G Ex ( Sa
. . . .

Fast Green 0 ( C) . .
) . . .

YYO ( C) ( )
G
Malachite Green Cryst a Victoria Green Smal l Cryst a
. .

ls A . ls

Mal achit e Green Crystals ( C ) a . Victoria Green B . Powder

Methylene Green B ( H) . .

Viol ets

Cryst a
l Violet Powder ( D) . Methyl Violet 6B . Conc ( H) . .

B ase Z B . Conc ( H) . .

Methyl Violet NE .
( D) . 2B ( B) . .

C I OLB ( B) . .

Z B . Ca
( ) . Violet R N ( C). .

c R ( C)
12 ( C)
2B . Conc ( S) . . 3
B3 (C
.

BE . G
( ) .
5 BO ( C) . .
6 46 PR I N C IPLE S OF LEA TH ER MA N UFA C T UR E

Bl ak
c s .

French Black 67 445 ( H) . Leather Black SM C

( ) . .

Jute Black G Conc ( H) . . . CB D ( C) . .

Leather Black A ( Sa ) . . Nigeria Black B X ( D ) . .

CII ( C) . . X .
( D

STA I NI NG

Single A cid Colours suit able for St a

1 n1 n g Vegetable -
tanned
Leathers

B r own s
A cid Brown 7 9 1 86 ( B ) . Leather T aBrown
n (A ) .

B ( C) . . Orion B rown G ( S) . .

G ( C) . . R esorcine Brown A . Conc .

L 3 48 .

1 5 80 ( C) . R esorcine B rown ( C) .

RN C
( ) G G
( )
a
-

. . . .

( S)
L 60 0 T n B rown RR ( B)
a
. . . .

Leather Brown G (A ) Light T n ( L)

a
. . .

SX ( A ) . . Dark T n ( L) .

Y ell ows

A cid Y ellow 7 9 2 1 0 ( B) . Cit ro n in e 0 00 .

( C) .

A iredale Y ellow ( Y ) Leather Y ellow SX ( A)

a
. . .

A z o Y ellow I . C
( ) . Me t n il Y ellow S ( Ca) . .

( Ca) Naphthol Y ellow S ( C)

ai
. . .

Az o fl v ne C ( C) S ( Ca)
at a ( Sa
. . . .

7 0 3 2 ( C) . T ph
r r e n in e ) .

Or ag
n es

Ac e ko Orange II Ca
( ) Orange I I ( )
A
a
. . . .

A cid Orange G ( B) . . II .
(S) .

Crocein Orange SX ( A) . . I .
(S
Orange I I ( H)
. . MNO ( C) . .

II ( C)
. . R ( C)
. .

Sc al t
r e s

A c e ko Scarlet R Ca
( ) . . Coomassie Scarlet 9 0 1 2 K .

Z R ( Ca ) . . Leather Scarlet ( A) .

3 R ( Ca ) . . Scarlet 5 0 ( B) .

4R ( Ca ) . . Z R .
( S) .

2 G ( Ca ) . . Croceine Scarlet ( Ca) .

6 48 P R I N C I P L ES OF LEA TH ER MA N UFA C T U R E

Vi ol ets

Ac e ko Violet 4B ( Ca ) . . B enzyl Violet 5BN ( C) . .

I OB ( Ca) . . 6B ( C) . .

A cid Violet 6B ( G)
a
. .

4BNS ( S .
) . Coomassie Violet R ( B ) . .

3 BN Direct Violet L 7 2 3 ( S)
a
. . .

F st Leather Violet 4R ( C)
a
. .

Fast Sulp ho n Violet 5 B S ( S ) . .

( C) 73 Leath er Violet ( L) .

B enzyl Violet 5R ( C) . . Victoria Violet ( C) .

43 ( C)

B lu e -
Bl a
cks ad Bla
n k c s

A cid Black 4ENN ( C) . . Naphthol Black ESN ( S) . .

HA ( C) . . Nigrosine G Crystals ( B)
. .

PR ]
.
( C) . B Conc ( S)
. . .

PB ( C) ES Crystals
‘

. . . .

( Ca ) Crystals W (Co )
a
. . .

Fast Sul p ho n Blac k F ( S ) S (A )

a
. . . .

Naphth l ene Black 1 2 B ( B ) . . B .

( )
A .

( B) B . . A .
( C) .

BD ( B) . . B .

Naphthol Blu eBlack ( C) . K ( C) . .

Naphthol Blue Black B . S 1 47 1

.

Conc ( G) SS ( B)
'

. . . .

Single B am Dyes suitable fo Staining Vegetable tanned

s r -

Leathers

B rown s

Basic Brown BX N ( D) . . Canell e 33 7 3 ( C) .

GX ( D) . .
57 3 3 ( C)
1 5 57 ( C) . 833 7 ( C)
Bismarck Bro wn R 1 005 . . 63 N ( C) .

G ( C) . . F (C .

R ( C) . . ES ( C) . .

Chocolate B rown 3 9 3 6 ( C) .

863 4 ( S) .

(A ) . Havanna 3 5 1C
( ) .

R . Conc ( H) . . Leather Brown A C

( ) . .

( H)
R . . G ( C) . .

G ( H) . . 1 3 5 ( C) .

R . Con c ( Co ) . .
33 7 8
 C OA L -

TA R D Y ES T UFF S 64 9

B r o wn s— e
( c o n t in u ed )
B ismarck B rown Y .
( Ca ) . Leather B rown 4 1 83 ( C) .

R ( Ca ) 8669 ( C)
a
. . .

B ro wn A T
.
( G)
. . V esuvi ne G S ( S ) . .

Canelle 1 3 52 ( C) .

Yel l o ws

A cri di ne Y ellow R ( H) B rill iant Phosphine Z G ( C)

m
. . . .

Z R ( H) G )
O ( Sa
. .

Auro min e .
) . R (c
0 ( H) :
. Patent Phosphine ( C)
O Conc ( H)
. . . GG
G C
II ( H)
. . M C)
O ( B)
. . R ( .

I I ( C) GG MK ( C)
Saba Phosphine G ( Sa
. . . .

O ( C) )
Z G ( Sa
. . . .

0 0 pure ( C)
. .
) . .

O ( G)
. . Sella Flavin e G (G ) . .

O ( D)
. . R ( G) .

Brilliant Y ellow P .

( Ca) Conc ( G)
Ta n n o fla
vin e T ( Sa
. . .

B rill iant Phosphine G ( C) . .

) . .

Or ag n es

A cridine Orange L .
( )
B . Chrysoidine R ( D). .

Chrysoidine YR P ( B) 1 60 6 ( S)

GS ( Sa
. . .

) . . G ( D)
. .

R ( G) . . Ca
( ) .

R (A ) . . Pure Chr ysoidine YD . Co

( ) .

Magenta 87 9 52 ( B) . Rhodamine B Ex ( D) . . .

Safranine G OOO ( C) . .

R ussian R e d B C
( ) . . N (C -

G ( C) . . S (H -

Rh odami ne B ( C) . . RFF ( H) . .

G ( C) . .
( Ca)
Y . .

6G ( C) . . Tannin P ink C ( B ) . .

B ( D) . .

B l u es

B asic Marine Blue ( Ca ) . Methylene Blue X D ( D)

. .

B asic B lue ( C) . B .
( D) .

B engal Blue R ( G ) . .
6 50 P R I N C I P L ES O F LEA TH E R M A N UFA CT UR E
B l u es (continued)
Fast Blue 3 R ( Sa
.
) . Methyl ene Bl ue 1 565 ( S) .

Methylene Blue 2 B ( B . Ca
( ) .

F -
( B
B EH . H) . Turquoise Blue G ( B) . .

BB Ex ( H) . . . Victoria Blue BX D
( ) . .

R Ex ( H) Conc ( D)
B <Sa
. . . .

> B B ase ( D)
. .

D ( G) . B ( Ca ). .

a
Green s
B sic Green Conc
B . .
( H) . Methylene Green G ( H) . .

G Conc H
( ) P ( C)
G Ex ( Sa
. . . . .

Fast Green 0 . C
( ) .
) . . .

Y YO .
( C) .
( G) .

Malachite Green Crystals A . Victoria Green Small Crystal s

Mal achite Green Cryst a

l s ( Ca) . Victoria Green B . P owder ( D) .

Methylene Green B ( H) . .

Viol ets
Cryst a
l s V iolet Powder ( D) . Methyl Violet 6B . Conc ( H) . .

B ase ( D) . 2B. Conc ( H) . .

Methyl Violet NE . D
( ) . Z B .

6B .
( Ca) . I OLE .
( )
B .

Z B . Ca
( ) . Violet R N ( C) . .

4B .
( Ca ) R ( C). .

3 R ( C) . .

2B Conc ( S) B ( C)
'

. . . . .

BE .
( G) .
5BO .
( C) .

Bl ak c s

French Black 67 445 ( B ) Leather Black SM C

.

( ) . .

Jute Black G Conc ( H) CBD ( C)

Leather Black A ( Sa
. . . . .

) . . Nigeria Black B X ( D) . .

CI I ( C) . . GX .
( D) .

2 2 ( C)
1
7 .

Acid Mixtures suitable for Dyein g a

n d St aining B ro wn s
‘

upon Vegetable tanned Leathers -

R esorcine Brown A Conc ( B) a

Dark T n ( L)
a
. . .

Acid Y ellow 7 9 2 1 0 ( B ) A z o fi vin e C ( C)

a
. . .

N p ht ho l Green 9 2 1 1 K .
( )
B . A cid Green G . Ex . C
( ) .
6 52 P R I N C I P L E S OF LEA TH ER MA N UFA C T UR E
“

Dye s s u it a
bl e f o r d ye in g Ch r o m e -
ta
n ne d Le t h e r sa
A cid C ol our s dyed in a weak su lp hu rl c o
,
r formic acid solution

B ro wn s

A cid Brown R N . G
( ) . Nu t Brown D ( B) . .

7 91 8 6 ( B) . Y ( B) . .

7 9 48 7 ( B) . R esorcine Brown N ( G) . .

C
( )
B a . . A Conc . . .

G ( C) . .

L 3 48 ( C) . . R eso rcine B rown ( C) .

1 5 80 ( C) . G .

Manilla Brown ( B) . A .

Yell ows

A cid Y ell ow 7 9 2 1 0 ( B) . a
A z o fl vin e 7 0 3 2 ( C) .

A cid Orange G ( B ) Leather Y ellow SX

a
. . .

A ired l e Tartrazine ( C)
fla
.

Az o i
v ne C ( C)
. . S .
( H) .

R eds Ma
r oo n s

B enzyl Bordeaux B . C
( ) . Kiton R e d ( C) .

Car di nal Red J , ( B) . 6B .

( C) .

,
3 B ( B) . . Pure Bordeaux B . ( C) .

Fast Leather R e d C ( C) . . R occelline C

( ) .

Kiton R e d 3 ( C). .

Bl ak c s, mordant with 3 pe r cent hematine

.

A cid Black 4ENN ( G) . . Nigrosine G Crysta

. l s ( B) .

HA ( C) B Conc ( S)
ES Cryst a
. . . . .

PR l s ( S)
Cryst a
. . .

PB ( C) l s W ( Co )
’

. . . .

( Ca) . S (A )
. .

Coomassie Black DW ( B ) B (A )
Fast Sul p ho n Black F ( Sa
. . . .

) . A . C
( ) .

Naphthalene Black 1 2 B ( B ) . . B .
( C) .

(B) B . .

BD ( B .

Naphthol Black ESN ( S) . .

 C OA L -
TA R D Y E S T UFF S 6 53

B asic B rown BX N ( D ) . .

GX ( D ) . .

I ssr ( C)
Bismarck B rown R . r oos ( B) . .

G ( C) . .

a
’

E
U
F

U
F

P
W
K Vesuvine G S ( Sa
)
( Sa
. .

W R .
).

Yell o ws
Brilli ant Phosphine
G ( C) . . P atent PhosphineM ( C) . .

Z G ( C) . . R ( C) . .

5 G ( C) GG MK
Saba Phosphine G ( Sa
. . .

R ( C) )
2 G ( Sa
. . . .

Patent Phosphine G ( C) )
a fiai ( Sa
. . . .

2 G ( C) . . T nno v ne T
.
) .

Bl ak c s, mordant with 3 per cent hematine

.

French Black 67 445 ( B) Leather Black SM ( C)

Leather Black A ( Sa
. . .

) . . CEB ( C) . .

CI I ( C) . .

Direct Dy es ,
dyed in a we a
k cetic acid bath a
B r own s
Chrome Leather Brown G 9 8 Chlorazol Brown H X ( B)
Dia
. . .

n o l D ark Bro wn B M
( B) . .

Chrome Leather Brown R 9 9 B rown GM ( B)

Diphenyl Brown G R s up ra
.
-

. .

Chlorazol Brown G ( B) . .

Chl orazol Brown GN . Ex . Omega Chrome Brown G .

Chl orazol Brown RN Ex Omega Chrome Brown P

a
. . .

(S ) .
6 54 P RI N C I P L ES OF L EA TH ER M A N UF A C TU R E I

Yell o ws ad O ag
n r n es

A fghan Y ellow GX ( B) Chrysophenine G ( B )

( Sa
. . . .

Alizarine Y ell ow G ) Diphenyl Chlorine Y ellow

a
. .

Orange R ( )
S FF ( G )
Dia n o l Ea
. . . .

Chlorazo l Fast Y ellow B . s t Orange G

( )
B . .

Po l yp h e nyl Y ellow R ( G )
.
. .

: Po l yp h e n yl Orange R Ex . .

FG ( B )
Orange R Ex ( B) . .
.
Sun Y ellow 3 G ( G ) . .

R eds ad Ma
n r o on s

B enzo Purpurine 4B ( B) Dia l Fa

st Pink B K no
( B)

a
. . . .

Chicago R e d ( G) . Fast Re d K ( B) . .

Chlor zol Pink Y ( B) Diphen yl Fast R e d B ( G ) :

Dian o l Fa
. . .

st R e d F ( B) . . Jasmine ( G) .

Gr een s ad B l
n u es

Brilliant D elphine Blue B . Chlo razol D rk Green PL ( B)a . .

Diphenyl D eep Blue R ( G)

Green KGW supra
. .

Chlorazol Sky Blue GW ( B ) . . .

,

FF_ ( B) . .

Blue 3 B ( B) . . Diphenyl Blu e KF . G

( ) .

Gre en B ( B ) Fast Blue 3 R

'

a a a
. . .

D ark Green PL ( B) . . G l l o c y mn e ( S ) .

Viol ets

Chlorazol Violet WBX ( B) . . Di a l Violet R

no .
( B) .

Bl ak c s

Dial Black B H
no .
( B) . Chrome Leather Bl a
ck E
'

Chlorazol Black E Ex .
( B)
. .

DV .
( )
B .

Chrome Leather D eep

'

Black Chrome Leather Black E .

G Conc ( C)
. .
‘

. Ex Conc ( C)
. . .

Chrome Leather D eep Black

C Conc ( C)
. . .
 APPEND I X D

TH E D E TE R M I N A T I ON A N D CON TR OL OF A CI D I T Y
IN “
TA N L I Q UOR S

W . R . A TKI N and F . C . TH OMPSON

TH E importance of the acidity of tan liquors 1 8 sho wn by the '

ample literature on the subj ect describing for the most part
work which has not achieved its a
,

im namely the actual measure , ,

ment of the swelling power of tan liquors At the outset we may

"

state our opinion that acidity even when the presence of salts
of weak acids is taken in t o a
,
.

cc o u n t is not the o nl y factor govern ,

_
’

ing swelling Two factors the influence of which is obscure

are ( a a
.
, ,

) the s tringency and actual tanning effect of the tannins

present and ( b) the e ff ects of neutra
,
l sa
l ts of strong acids such
as sodium chloride sodium sulphat e etc A well—conceived and , ,
.

di rect method of arriving at the effe c t of astringency etc is that

of Cl a
.
, ,

a
flin who carries out swelli ng experiments with hide powder
,
-

n d the liquor under investigation , where the amount of liquid

absorbed by the hide— powder measur e s the swelli ng power The

influence of neutra
.

l salts has been well brought out i n numerous

papers by J A Wilson and his collaborators A W Thomas and
M E B aldwin and by J W Mc B a
. . . .
,

. . in Th e e ffect of addin g sodium

,
. . .

chl oride to dilute hydr ochloric acid is to raise the hydrion con
centration as measured by the hydrogen electrode whereas
sodium s ul p ha te a
,

dde d to weak acids has an opp osite e ffect

'

Mc Ba i n found that the parti a

.

l vapour pressure of acetic acid

in dilute solution was greatly augmented in the presence of

added ions whereas Mc B a

a
so di um chloride These interesting effects are beli eved by Wilson
to be intim tely connected with the degree of hydra
in speaks of
.

tion of the
enhanced chemical
potenti a
,

l Whatever the cause the e ffect is of great importance

.

particularly in chrome tanning .

In this paper however we are conce rned only with a direct , ,

determination of aci di ty All previous attempts have depended .

upon titration of the tan liquors with alkali H R Procter

a a
. . .

nd R A Seym our Jones published in 1 9 1 0

. . comprehens ive -

review of the earlier work on this subj ect and in addi t ion described ,

65 6
 A C I DI T Y I N TA N L I Q U OR S 6 57

several variations involving the use of indicators The two main .

di ffi culties however were

, ,

a
( ) T h e colour of the tan liquors masked the colour of the

indicator
Except in a neutra l atmosphere there was always a con
s id e r ab l e oxidation and darkening on the addition of
alka li .

A ttempts have been made to overcome the first difficulty by

de t a n n isa t io n previous to titration but this procedure causes
serious errors as in almost a ,
l l cases there is marked c o precipita
tion of acid This obj ection applies to the present o fficial method
,

a -

in which det a n n is a
.

of the t io n is effected by means of

an alcoholic solution of gelatine St ia s n y however det a
. n nis e s , ,

with a mixture of hydrochloric acid and formal dehyde and in ,

this case there appears to b e no loss of acid but the method can ,

only be applied to catechol tans

The question now to be discus se d is what a
.

cidity should be
measured It is necessary to define at the outset what is meant
by acidity and to show that measurement of tot a
.

,
l content
in acid even if this could be accurately performed would not give
, ,

the information which is desired by the sole leather tanner A .

concrete example may make this point clear Consider the two
following cases : ( a
.

) 2 5 c c of N /1 0 acetic acid and ( b) 2 5 c c

. .
,
. .

of N /1 0 acetic acid containing 0 20 5 grm of sodium acetate

and consequently a
.
,

l so N /1 0 in this substance If these two .

solutions were titrated with alkali using phenolphthalein as ,

~

indicator the sam e result woul d be obtained in each case but if

, ,

an attempt were made to titrate u sm g methyl orange it would

be found that mixture ( 6) was already a
, ,

l kaline In harmony .

with this the swel ling power on water swollen gelatin of solution
a
-

( )
6 would be nil whereas ( ) ,
would p roduce a pronounced increase
of swelling The explanation is foun d in a consideration of the
.

ionisation phenomena in the two cases .

As is well known the property of acidity is due to the presence

,

in solution of hydrogen ions A n acid in solution dissoci ates .

-

into ions according to the following scheme

HAc —> H + A o ’
.

In the case of weak acids the extent of this dissociation i e , . .

the concentration of ions produced is in accordance with the well ,

known law of mass action '

-
.

This states that under given circumstances of original c o n c en

t ra
t io n and temperature the concentrations of the products of
reactions at equilibrium are when multiplied together in strict , ,

42
6 58 -

PR I N C I P L ES OF L EA TH ER M A N UFA C T U R E

proportion to the concentrations of re cting substances a l so a ,

mul tipli ed together In other words if A and B react together

.
,

to form X and Y then at equili brium [A]x [ B]= K[ X ]x [Y]:

The square brackets indicate c on cen tr a
,

tion s and K is a nu mber ,

termed the equilibrium constant of the reaction .

Consi der from this point of View the electrolyt ic di ssociation

or ionisation of aweak acid i e one which is only ionised to a
'

. .
,

slight extent Here we o nl y have on e reacting substance namely

.
“

, ,

the acid which is part ial ly split up into the t wo reaction products ,

the kation ( H and the anion (Ac ) '

K[ HAc]= [ H
Here K is the disso ciation or ionisation constant and in the
case of weak acids is always very sm a
,

ll e g 00 0 00 1 8 for acetic ,
. .
"

acid The square brackets indicate concentration in terms o f

norma
.

a
l ity t e for N /1 0 acetic acid of which over 9 8 per cent
, . .
,
. .

remains un di ssociated [ HAc ]= o 1 approximately being actu ll y ~

a
, , ,

: little less
a
.

Whatever other ions m y be present in solution at the same

time a s those of acetic acid the above equation holds good ,
.

Consequently if the concentration of the anion [A c ]be increas ed '

by some me a
,

a
ns without increasing the concentration of undis
s o ci t e d acid then in order to maintain the equality the
concentration of the kation [ H ]must dimini sh In other words ~
.

'
,

the aci di ty is diminished In the case of decinormal acetic acid .

we have
[ CH3 COO
'

since hydrogen and acetate ions are necessarily equal in number

l and almost a
Since the acid is decinorm a
.

l l undissoci ated we have ,

approximately
o I -
K= [ H

o o o r 34 = 1
-

The e ffect of adding sodium acetate is to increase largely the

nu mber of acetate ions U su a l ly the salt of even a weak acid
is largely dissociated; and in extending the c a
.

l culation to the case

of mixt ure we shall assume as a n approximation that sodium

acetate is completely ionised in decinorm a l solution Thus .

[ A
’

] ow = o 1 whilst [ HA c ] is unaffected The sod ium ions

‘

o n -

, .

produced do not a ffect the case We still have .

K[ CH3 COOH] [ H ] 0

~
o 1 -

>
< o 1

[H ] o
x10 7 5
.
6 60 P RI N C I P L E S OF L EA TH ER MA NUFA C T UR E

the mass of
‘

the free ions we might regard it as also constant so ,

H H =
] Kw
'
’

[ ] [
X O .

H ere Kw is the dissociation constant for pure water and has ,

the very low value at 2 1 C of I o 1 4

and thus the val ue for [ H ] °
.
“

or is I o 7 grm ions per litre "

. .

If an acid be added t o distilled water the acid is dissociate d

either partially or wholly into hydrio n s and the anions of the
acid employed Thus [ H ] in such a mixture is greater than
.

”
and the solution is acid Suppose acid had been added .
“

—1 1
so that [ H ] was then?[ OH ]would be 1 0 for ’
,

H
[ ] [
x OH =
] IO
’ ‘
1 4
_

From the above it will be understood that a sol ution is neutral ,

acid or alkaline according to whether [ H] has a value

,

—7
equal to greater than or less than 1 0 respectively Obviously
, ,
.
,

—7
if [ H] does not equal 1 0 then it cannot be equal to
Soren sen in order to facilitate the plotting of curves h a
,

, s ,

introduced the symbol PH to d enote what he calls the hydrogen -

ion exponent where PH is the logarith m to the base 1 0 of [ H ]

“

but with the n egative sign o mitted or PH —log 1 0 [ H ] Fo r , .

example N /I o acetic acid has [ H ] = —3

,

=1 0 so PE = Z 8 67 -
.

It should be noticed that PH decreases with increasing acidity

and that if [ H] be increased tenfold the va
,

l ue of PM is decreased
by 1 0
From the case of acetic acid and so di um acetate m e ntioned

above it will be seen that PH cannot be d e t er m me d by ordinary

titration
The most a
.

ccurate method of determi ni ng the [ H ] or PH is by

'

means of the hydrogen electrode and this method has been applied
by Wood Sa nd and La
,

,
w in the case of tan liquors
,
The method '
.

is an electrical one requiring a consi derable amount of apparatus , ,

and does not seem to have b ecome universall y p opular with

tannery chemists .

Other methods depend upon the measurement of the velocity

of che mical reactions such as the hydrolysis of cane sugar or ,

methyl acetate where acids are used as catalysts but these involve
, ,

too much time The simplest method is by th e use of indi cators

.
,

and may be called the colorimetric method It has the great

advantage th a
.

t it is rapid and does not require any elaborate ,

apparatus .

As is well known indicators are substances that vary l n colour ,

with varying acidity or alkalinity of t he solution to which they

are added This change of colour takes place over a definite
.
 A CI DI T Y I N TA N L I Q U OR S 66 1

range of PH and at various points within this range the indicator

sh ows intermediate tints The solution is neutra
,

l to the .

indicator at the mid point of the range This neutrality does not
a
.

mean that [ H s in pure water Fo r example

neutrality to phenolphth a
.
,

l ein occurs about PH = 9 whilst in

“

,
”
the case of methyl orange neutrality is in the region PH = 4
the [ H ] in the latter ca
,

se being ti mes greater than in the

case of phenolphthal ein Litmus however has its neutra .l , ,

point at about 6 6 and brom thymol blue at about 6 8 Table I

- -
. .

shows a list of convenient in di cators many of which are of the ,

new sulphone phthalein type described by Mansfield Clark Lubs

and A cree On e of them thymol blue it will be noticed has a
, ,

.
, , ,

double change one in fairly strong acid solution and the other
like that of phenolphth a
, ,

l ein .

The colo ri metric method has been described by various workers ,

inclu di ng Veley and Sorensen but the results obtained wer e

only rough in the case of coloured fluids SOre n s en a
,

l so p o in t e d
‘

out that the presence of proteins vitiated the r esults with certain
indi cators This was especiall y t he case with colloid indicators
.

such as Congo red Walpole surmounted the di fficulties d u e to

.

the colour of the fluids by matching the solution under investiga

t ion ( which contained the in di cator ) aga i nst a colourless solution
of standard PH con t a i ning the same a mount of in di cator observed
through a layer of the coloured fluid His method was modified
by Hurwitz Meyer and Osterberg w
.

,
ho used test tubes held m a
, ,
-

box and finall y by Cole and Onslow who have further improved
, ,

”
this latter device which is termed a comparator by the
addi tion of a ground gl a ss plate as shown in t he dia gr a
, ,
'

m (p
a
-
, .

Fo r determining the acidity of tan liquors a comp rator which

takes two pairs of tubes is as large as is necess a ry The method .

of procedure is as follows
Test tube A I contains I O c c of fil tered tan liquor A 2 contains
-
. .
,

1 0 c c of a solution of standard PH together wi t h five or ten dr ops

'

a
. .

of a suitable in di cator t e an indicator which is ch nging its ,

. .

shade di stinctly in that region of aci dit y Te st tube B 1 contains .

-

di stilled water and B 2 1 0 c c of fil tered tan liquor and the sa me

, . .

number of drops of indicator solution as in A 2 If on looking ;

through the two p a irs of tubes the colours match then the PH
.
,

of the tan liquor is that of the standard used in A 2 If not .

,

other standards of deeper or lighter shade as may be requir ed are ,

substituted for that in A 2 The matching is usuall y performed .

in a minute or so provided that the necessary ranges of standards

are to hand The test tubes must be of colourless glass a
,

n d o f the
'

same diameter A selection can ea

-
.
,

. sily be made by pipetting

6 62 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

0
0 0
0 0 0 0
0 0 0 0
0 0
0 0 0
0 0 0 0 0
0 0 0 0
0
0
0 0 0 0
0 0
0 0 0 0
0

0
0 0 0
0
0 0 0 0 0
0
0 0 0 0 0
3 0 3 0 0 0
.

3
-
0 0 0
0 0 0 0 0 0 0
0 0 0 0
2
0
3 2 -
0
-
0
0
0

0
0 0 3 3 0

0 0 0 0 0 0 0 0 0
6
- -
2 0
0 0
0
0 0 0
0
0 0 0
4 0 0 0
0
0 0 0 0

0
0
0
a
m
0
0

1
.

0 - 1 1
M0
0 0 0 0 0
0 0 0 0

0
0
0 0
.

0 0
0 0
0
0 0
0
0 3 90 0 0
0
0
0

0
0 0 0
5 0
0
0
0
0
0
0 0
0 0 0
0 0 0
0 0
2
0
3 0 0 0
0
0
0
0 8
0
0
0
0
0
0 0
0 0
0
0 0
0
0
0 0
9
0 0
0 0 0 0 0 0 0
0 0 0 0
0 0 0 0 0
3 0 0 0 0 0
3
0
0 0
0 0 0 0 0
0 0
0 0 0
3
0
0
0
0 0 0 0
0
0
0
0
0 0 0 0 0
0 0

5 6
0
0 0
2
0
0

5
.

0 0 0
0 00 8 0 8
0
0 0 8 0
0
0 0
5
0-
0 0 0 0 0
0 0 0
0 0 0
5
0
0 0 0 0
0 0 0
0 0 0 0 0 0 0

3
0
0
0
2 5
. 0 0 00 00 0
-
0 0

0 0
0 0
0
0 0 0
0 0

8
0
0 0
0 0
0 2
2
0
0 0 0 0 0
0 0 0 0
0 0 0 0 0
- -
0 0 0
0
8
0
0 0
8 0 0
0
0
0
0
0
0 0 0
0 0
0 0 0 0 0
m m
0
0 0
0
0 0
6 64 P RI N C I P L E S OF L EA TH ER MA N UFA C T UR E

necessar y to go nearer to neutrality than PH = 4 7 The other -

.
_

limit may be taken as PH 2 8 for most purposes Only synthetic : ~

.

or treated tannins are likely to lie outside this range The .

standards used were mixtures of ( I ) acetic acid and sodium

acetate ( 2) acid potassium phth a l ate and hydrochl oric acid
'

.
,

The best indicator appears to b e tetra brom phenol sulphone

phth a
- - -

l ein or brom phenol blue The colour of this indicator

-
.

changes continuo usly from PH = 2 8 to PH = 4 6 though not very - -

much near the limit s B rom phenol blue however is dichroic.

-

, , ,

and is best observed throu gh a yellow colour screen which cuts

‘

o ff blue rays A convenient mode of making such a screen is to

.

paint transparent parchment with a mixture of 0 6 p er ce nt “

solution of phenol red and M 5 solution of potassium dihydrogen

phosphate ( 2 7 2 3 gr a
'

m s /l it er)
~
The preparation of the standards
.

is a very simple matter following the tables given The solutions

,
.

required are N 5 acetic acid N /5 sodium acetate prepared by ,

neutralising z o o c c N /I caustic soda with N /I acetic acid and

di luting to I liter M/5 ha potassium phth a
. .

c id l ate ( 40 8 2 8 -

a
,

g r m s
/l it e r
) N/5 caustic soda and N /5 hydro chloric acid :
, ,

STA ND ARD P H SOLU TIONS .

SERI E S I .

so cc . . M 5 aci d potassium phthalate x cc . . N /5 H C] , mixed

and di luted to z o o .
c c
. .

SE RI E S 1 1 .

50 cc
. . M 5 acid potassium phth a l ate x c c . . N /5N OH a ,
mixed
and di lu t ed to 200 c c . .
 A CI DI T Y I N TA N L I Q U OR S

SE R I ES I II .

x cc N /5 sodium at a
t +
ce e I oo —x ~
cc
. . N /5 a
cetic acid .

95 .

Fo r instance a solution of PH = 3 8 may be prepared in either of -

the two following ways : ( a

,

) 5 0 c c M /5 phthalate + 2 63 c c . .
-
. .

N 5 hydrochloric acid diluted to 2 0 0 c c or ( b) 1 2 c c N /5 . .

,
. .

so di um acetate + 8 8 c c N 5 acetic acid I O c c of either of t hese

. . . .

solutions together with five drops of brom phenol blue solution

,
-

is pipetted into a test tube corked well and labelled P H = 3 8

-

, ,
-
.

It will be found convenient when working in the range from .

PH 2 8 to PH = 3 7 to use ten drops of indicator solution in order

: - ~

to intensify the colour di fferences The whole rang e required .

Sh o u l d b e made up and kept in a test tube stand preferably in

‘

the dark The authors have found that the colours do not change
.

appreciably in the course of a month These sets of standards .

.

have been worked out by Clark and Lubs and have been ,

standardised against the hydro gen electrode .

A number of tannin solutions have been exam ined both in the ,

above way and by Procter s lime water method with the foll owing
’
-

res ults which have been arranged in order of increasing acidity

,

Procter lime
water metho d Colori metri c Method .

Ta n Liquor c c satd lime [H ] °

as norm a
. . . .

water per I O c c l ity . .

.

tan liquor .

56
6 2

1 6 2
I 7S

3 46

Itwill be noticed that the lime water figures are in the same order -

as the acidities though no exact correspondence is revealed

,
.

There is no necessary connection between PH and the lime water -

figure .
666 P R I N C I P L ES OF L EA TH E R MA N UFA C T URE

If it be required to raise the acidi t y of a tan l iquor this can

easily be done by titrating the liquor with a st a
,

ndard solution
of the acid to be used until its aci di ty reaches the required PH
as shown in the comparator a c a l culation will then show how
much commercial acid should be added to the liquor in the pit .

What however is a desirable PH must be fixed by the tanner

, ,

according to the class of leather he is dealing with The best .

way is to note carefully the acidities of liquors which he finds

satisfactory and to reproduce these as requi red It will be
obvious that acid is titrated by acid no a l ka
.
,

l i is used and the ,

di fficulties due to oxi dation and darkening entirely disappear .

A n interesting application of this acidi t y method is in the case

of freshly made a nalytical solutions of tannin A surprising
variation in acidity wa
.
,

s found the range being a l mo s t as great ,

as in used l iquors .

Materi a
Tanning l R A NG E OF PH .

Solid mimosa extract ( 4 samples )

Sumach ( 4 samples)
Liqui d myrobalan extract ( 3 samples)
So li d quebracho extract ( 2 samples )
Liquid quebracho extract ( 3 samples )
Soli d chestnut extract ( I s ample )
Liqui d chestnut extract ( 2 sam ples ) —
3 7 3 75
- 0

Wood Sand and La , w have previously determ

,
ined the acidity
of tan liquors di rectly by the hydrogen electro d e which is the
'

standard met hod and much more accurate than t he method

,

described in this paper However it has not become popular

with tannery chemists and our purpose is to give a
.
,

m e t ho d which
'

whilst sufficiently accurate is yet simple in exe cution and easy

to understand The electrometric method is no doub t easily
.

and quickly car ried out when the complicated apparatus is once
set up but to understand and appreciate the met hod of working
“

requires a considerable acquaintance with di fficult thermo

dynamic theory Once the standard bu ffer mixtures desc r ib ed
.

above ( witho u t in di cator) have been prepared it will be found ,

convenient to keep them in well stoppered and carefully labelled

bottles Thus new colour standards may be quickly prepared by
.

adding the indicator to I O c c wh en n e e de d . .

‘

.
 P RI N C I P L ES OF L EA TH ER MA N UF A CT UR E
I

668

titratio n not only the caustic alkalinity but all the ammonia
hydrosulphide and also the sodium and calcium s a
,

, l ts of the
decomposition products of the di ssolved proteins and as B ennett , ,

points out this titration with methyl orange estimates the t otal
a Ho w
,

l kalinity ever by the aid of the i onic theory and the

.
, ,

employment of the comparator recen tly described it has been ,

foun d p ossible to determine quic kly and with reasonable accuracy “

the c austic a
, ,

l kalinity of lime liquors Consider the case of .

ammonium hydroxide which is a weak base and therefore is only , ,

Slightly dissociated into iO n s in aqueous soluti on ,

NH 4 OH —NH0
4
'
OH
’
.

By the law of mass action we have

[ NH 4 l [ OH ]
'
’

[ NH OH] 4

where K is a constant known as the dissociation constant and ,

at 2 5 C has a val ue of 2 3 X I O [ NH 1 denot es the concentra

° 5 “
° -
. .
4

tion of ammonium ions [ OH ] the concentration of hydroxyl ,

’

ions and [ NH OH] is the concentration of the undissociated

, 4

ammo ni um hydroxide As [ NH or [ OH ] is relativel y very .

4
’

small compared with [NH OH] we may regard the latter as 4 ,

constant so that the above equation may be simplified to

,

[ OH =
] constant
’

If now a considerable quantity of NH ion be added to a solution

, , 4

of ammonia as an ammoniu m salt e g ammonium chloride which ,

. .
,

is almost completely ionised in dilute solutio n we have [ NH , 4

considerably increased but as the product [ NH ]X [ OH Tmust , 4

~
’

remain constant it follows that [ OH ]must be correspondin gly

,
’

decreased .

This reas oning is exactly analogous to th t of the case o f

acetic acid and sodium cetate discussed on p 65 8 except that a a
.
_

, ,

in this latter case the [ H is considerably decreased by

the addi tion of sodium acetate to the weak acetic acid
Michaelis has ca l cul ated the [ OH ] of various mixtures of a
.

m
'

m o n iu m hydroxide and a mmonium chloride which are given in ,

the following table A t 1 8 C however .

°
.

[H x [ OH ]
’
3 064 x 1 0 —1 4
,

so that knowing [ OH ] it is possible to calcul ate [ H ] Fo r '

o
.

curve pl o tting the symbol PH which is — log 1 0 [ H is used

therefore both [ H ] and PH va
,

l ues are appended to Mi chaelis

'

figures .
CA US TI C A LKA L I N I T Y OF L I ME L I Q U OR S 6 69

TA BLE

Calculated figures by Michaelis sho wing [ OH ] of various

a
’

mixtures of mmonium hydroxide and ammonium chloride ,

and als o the corresponding [ H ] and P values H .

Pe c en t R c ent
R atio
i/ E
I/
. .

NH4 0 H NH 4C1
IO T1 0
[ OH [H PH .

NH4 OH NH4 C1
° '

. .

96 7 6 4x 4
x IO 1 1
‘

3 1 0 I I I o
-
- - -

—1
94 I
-
x IO “ ‘
4
2x Io 1
1 07
—1
88 9 6X 1
“
1
I I I I Io 4 x Io Io 4
- ' ’ -

—5
8o o 20 0 8X IO 8x IO 1 1
I o ~I
“
- -

4x
5
33 3 IO 6 x 1 0
8
-

1 Io 9
-
-

50 0
-

50 0
-
2 x IO
“
5
x IO “
1 O
9 0
1

33 3 66 7 I X 6 4X Io
1 0
9 N
-
-

—6 —9
.

zo o
-
80 0 -

5x IO 1 3 x Io 8 0
6 —9
88 9 2 5X IO 2 6>< 8 0
“

I I I Io
- - ' -

—6 —9 '

5 9
-

94 1
-

I ~2 x 1 0 5
-
2 x Io 8U J

96 7 6X IO 7 x IO 8
8 O
‘
“

33 I
“
0

_ must be pointed out that dilution has little influence on the

It
( OH ) of mixtures of ammonium hydroxide and ammoniu m
’ “

chloride as it , 15 really th that is the deciding

factor as will be seen by r e writing equation ( I ) in the form

,
-

K x [NH 4 0 H]
[ NH 4 l ’

Thus from the table and curve it follows that a m ix t u r e o f equal

parts of ammonium hydroxide and ammonium chloride has
[ OH =
] 2
’
Io

correspon di ng to a PH value of 9 5 °
.

No w consider what happens when a solution of ammonia is

,

titrated with standard acid using phenolphthalein as indicator ,

.

Phenolphthalein has a range of colour change from PH= 8 3

( colourless ) to = deep red Thus at P = 8 ammonia
P H I O 0 ( ) H 3 .

is 9 4 per cent neutralised whereas at PH = 1 0 O it is only 2 4 per

.
,
°

cent neutralised
. .

No t only have we to consider the ammonia however but

St ia
, ,

s n y s res u lts seem to suggest that the presence of calcium

’

salts might have a profou nd influence on the owing to the

formation of complex calcium ammonia ions but experi ments
carried out on the follo wing lines proved conclusively that c a
,

l
67 0 P RI N C I P L ES OF L EATH ER MA N UFA C TUR E

c iu msal ts do not a l ter the [ OH ]of mixtures of ammonia and

’

ammonium chloride to any appreciable extent .

Various mixtures of N /I O ammonia and N /1 0 ammonium

chloride were made up and the PH determined exactly as in the
manner recently described for the determination of acidity in
tan liqu ors ( l oo cit ) except that
.
,
course a di fferent in di cator
, ,

“
Z O NHu O H .

60 ”
0

FIG . 1 30 .

( phenolphthalein ) and di fferent standards were used . These

standards were made up according to the instructions given by
Cole The actual va l ues of PH obtained were found to agree
very well with the c a
. .

l culated figures of Michaelis ‘

.

The PH values of various mix t u r e s o f ammonia and ammonium

chlorid e to which varying quantities of N/5 c a l cium chloride
or N/I O sodium chloride had been added were det e rmined as
Shown in the table o n next pa e
g
From these resul ts it will be obviou s that calcium s a
a
.

lts do not
cause any appreci ble di fferences in the P and therefore i n
67 2 P R I N C I P L ES OF L EA TH ER MA N UFA C T UR E

No w in practice lime li quors are seldom used W

, ith a higher
concentration of sul phide than corresponds to N /2 0 in sodiu m
sul phydrate .

If we substitute in the above equation we then have ,

2 05-
x IO “
3
8
57 X IO
“

1 = —3
[ OH ] 2 O5 -
Io x 06 5
= I 0 25
-
IO
‘
4
normal ,

which at 2 5 C corresponds to [ H ] of I
°
. 1 0 or a PH 4 0
,

value of 9 9 3 i e practically P I o 0
, . .
fi
z .

From t h e above it i s clear that if a lime liquor be titrated to a

point corresponding to PH = I O O the sodium and calci um hy
dr o x id e s will be practically com pletely neutralised the ammonia
will be neutra
,

l ised t o t he extent of 2 4 per cent ( see curve ) but .

,

the sulphydrat e will not have been affected Thus the titration
will be a measure of a It is worthy of note that in a
.

+ 6 + O z 4d ~
ll -

titrat ions to PH = I O O no smell of escaping H z S was detected

°

but if the titrations were carried beyond this point the s mell of
H 28 became quite di stinct .

Hence by estimating the ammoni a preferably by distillation

i n va
,

cu o as described by Thompson and Suzuki the value of

a
, ,

+ b ( the caustic alkalinity) may be obtained from two deter

min a t io n s instead of four as described in our earlier paper
a
.
,

The choice of indicator in order to titrate to a PH v lue of 1 0 0

is important Phenolphthalein ha . s a range of colour change

from 8 3 to 1 0 0 and at the latter value it is coloured deep red

-

As a genera
.
,

l rule an indicator is not suitable near the limits of

the colour change so that the most suitable in di cator for our
,

purpose appears to be thymolphthalein which changes from ,

'

colo urless to blue over the range of PH 9 3 to 1 0 5 Thus at

a
.
_

PH = I o o we are near the mid dl e point of the colour ch nge

-

The titration to a va
.

l ue of PH = I O O was carried out in the °

comparator previously described ( ZOO cit) usi ng boiling tubes .

,

( 6 inches by I inch ) of the same internal di ameter as Sho wn

in the diagram ( p .

N /I O HCl was run slowly into tube B z stirring continu ously

'

, , .

and when the match was nearly complete di stilled water added
until the tot a l volume in B 2 was nearly 5 0 c c ( It is convenient . .

to scratch a mark on the boiling tubes corresponding to a capacity

of 50 c c ) The titration was continued until the colour seen
. .

through the tubes A I and A 2 matched that s een through 131 and B 2 .

It was noted that the blue colour of the thymolphthalein .

 C A US TI C A L KA L I N I T Y OE
“ ;
L IME L I Q UOR S 67 3

a a after so me t i me so it is better to make up tube

in dic t o r f de d , A2
each time that a titration is being carried out .

LI G H T
A B
25 c c lime liquo r
. .
50 c c distilled water
. . .

+ 2 5 c c distilled water . . .

B2
50 c c solution of standard 25 c c lime liquor
+ 1 0 drops t hym o l p ht ha
. . . .

al kalinity PH = I O O
1 0 drops of t hym o l p ht h a
°
.

lein solution .

lein solution .

Asthe standard solution of PH = I O O a mixture of 7 6 per cent °

N /I o NH OH and 2 4 per cent N /Ip NH Cl wa

, .

4 s used A liter .
4 .

of solution of this composition may be made up and kept in a

stoppered bottle the thymolphthalein being added to 5 0 c c , . .

as required
'

D etermi nations of the caustic alkal inities of four lime liquors

were made and these res ul ts compared with res ul ts obtained by
,

the method previously described All titrations are given in .

terms of c c N /I o acid or alkali per 2 5 c c of filtered lime liquor

. . . . .

No of Lime Liquor
. 2 3 4
Titration to PH = I O O I6 8 1 7 05

(a
° -

Method +b+ o 2 4d
-
.
)
described A mmonia ( d)
in o 2 4d
-
.

this
paper .
.
a
+b 1 3 55 1 5 65
-
1 53 5
( caustic alkalinity)
I st H CH O
titration I 3 3 I 9 9 1 8 9
a
- -
.

— amino acids )
( + + 6 0

2 n d H CH 0 titration 1 2 6 5 0 7 35
- -
.

( d + amino acids )
A mm o nia ( d)
Sulphide ( O)

Io I 1 32 1 57 1 5 55
a
- 0 -
.

( caustic l ka inity)
l

It will thus be seen that the agreement between the two meth ods
is quit e satisfactory .
 IN D EX
‘

A b d e rh l d e n , a 1 36 ; ( ad n F is c h e r ) , a a
A l u m in in w t er , 7 9
a
.

s lt s 2 4 1
37
a
1 .
, .

A b ie s 2 8 2 su l p h t e 2 0 9

a a
,
.
, .

z
A b so l u t e e r o o f t e m p e r t u r e , 8 5 . A l u m in iu m s u l p h t e , 2 4 1
”
.

A b so r p t io n i so t h e r m 9 4 ,
. A l u m in o f e rr ic , 5 6 4 .

Ab t 3 6 3 8 A lum s 2 4 1
aa aa
.
, ,
.
,

Ac ci Al u m t n n ge 2 40
32 9
aa
,
,
, .

A c id c o l o u r s 4 8 8 , .
A m e r ic n g l l o n 5 8 1 , .

d e l i m in g 3 5 5 A m in e s , 2 2 1
a a
. .
,

g e l t in e qu il ib r iu m 6 2 6 A m in o c id s 1 2 7
a a a
-
-
.
, , .

v l u e o f o il s 4 3 3 c t io n o f f o r m l d e h d e , 1

a y 44
.
, .

Ac id it y in t n l iqu o r s 6 5 6 p r o t e in s 1 3 5
a
.
, , .

o f li qu o r s 3 7 0 Ammo ni 1 6

a
,
.
, .

o f t n l i qu o r s 6 5 6 in u n w o o l in g , 3 3 , 1 6 6
a a a
.
, .

o f t n n in g m t er i l s 6 6 6 A m m o n iu m c hl o r id e 2 0 9
a a
.
, , .

A c id s c t io n O f 1 9 su l p h t e 2 0 9

aa a a a
. .
, , ,

l k l ie s nd s lt s c t io n on f o r p ic kl in g 5 7 6
a a
, , , .

g e l t in I I 5 A m oe b 1 0

a a
. .
, ,

m in o 1 27 A m p h o t e r i c c id s , I Z S
a
. .

o r g n ic 1 27 p r o t e ins 1 1 0
aa aa
,
.
, .

s t r e n gt h o f 9 9 An c r di ce e 30 6
a aa a a
.
, , .

A cr e e 6 6 1 A n e r o b ic n d e r o b ic b c t e ri 567
a a a
.
, , .

A c r o l e in 4 4 9 A n l y s i s o f Oil s n d f t s 4 3 1
a a a
.
, ,

A c t io n o f c id s o n g e l t in 1 1 5 A n dr e sch 30 9
a aa
. .
, ,

A d ip o s e l y e r 6 1 , . A n g ic b r k 3 3 4 , .

A d s o r p t io n 9 3 , . A n il in e d y e s , 4 8 7 .

A e sc h e r n 1 8 1 An o d e 9 7
a
.
,
.
,

Z Et h l iu m s e p t ic u m 1 0 A n o g e is su s 3 2 2
a a a
. .
, ,

A f r ic n o k 2 9 3 A n t hr x 2 6
a
.
, ,

A g e in g 2 4 7 2 5 2 b c t er iu m , 1 7
a a a a
. .
, ,

A il n t u s gl n d u l o s 31 1 , . A n t i c l c iu m 2 9 , .

fi
A ir l t e r s A n t i s e p t ic s 2 1
aa
.
, ,

l if t f o r l i qu o r s 5 5 4 A p o c yn c e e 3 1 8
zz a
-
.
, , .

Alb i i 335 Arb u t u s 3 1 9

a
. .
, ,

A l b u m in s 1 3 1 1 5 4 A r chb u t t n d De eley 6 8
a
.
, , , .

Al b u m o se s 1 32 A r c t o st p h yl o s 3 1 9
a a a
.
, , .

A l c o h o l n d g e l t in , 5 8 5 5 8 7 Ar e c 2 84

a
. .
, ,

A l c o h o l ic f e r m e n t t io n 1 6 , . A r i sz 1 1 3
, .

A l c o h o l o s m o t i c p r e ss u r e 1 1 5 A r r e c t o r p il i, 5 5
a
. .
, ,

p r e c ip it t io n b y 1 1 5 ,
. A r se n ic 2 7 , .

A l d eh yd e s 4 6 1 , . c u r e s, 42 .

Al d e r 2 8 6 , . red, 85 1 , 1 89 .

A l e p p o p in e 2 8 3 Su l p hi d e , 2 7
’

a a
. .
,

Alg e 2 7 A r s e n io u s c id , 2 7
a a
. .
,

A l g r o b il l 32 8 A s p id o s p e r m u m 3 0 7 , 3 1 8
a a a
.
, , .

A l k l in e c r b o n t e s in l im in g 1 8 4 ,
. A t kin 6 5 6
, .

h y d r o l y s is o f p r o t e in s 1 3 5 66 7
a
. .
,

A l k l in it y o f l im e s 6 6 7 , . W B 667
. .
, .

A ll en 446 A t o m s 84
a
. .
, ,

A ll e y w y s 5 5 0 A t t fi el d 4 1
a
. .
, ,

A l n u s 2 86 , . A u t o m t ic d r ie r , 5 3 4 .
67 6
“

P R I N C I P LE S OF L EA TH E R M A N UFA C T URE
Bru n n er 4 I Ce l l t h e l iv in g 1 0
a a
.
, , , , .

Br u sc 31 9 , . Ce ll s m u l t ip l ic t i o n
, o f, 1 1 .

B T U 51 4 Ce l l u l o s e 1 2
a at a
. . . .
, , .

B u ff l o m e t h o d of l im in g , tce e, 4 86 .

Ce l s iu s t h e r m o m e t e r , 5 8 1
B u ff e r s 37 0 Ce m e n t su b s t n c e 6 0 a
a a a a
-
.
, , .

B u ff l e t h e r , 4 5 7 Ce n t ig r d e F h r e n h e it t b l e 581
aa
-
. .

B u il d in g s , rr n g e m e n t o f, t h erm o m et er 5 8 1
aa
.
,

B u r n ing i n , Ce n t r ifu g l f n s 5 2 9
a
.
,

B u rn s n d H ull 2 1 3 p ump s 552

a
.
, , .

B urt o n n d H ey 2 5 5 C e r e s in 4 5 5
a
.
, , .

But e 32 6 Ce r io p s 3 2 3
a
. .
, ,

B ut sc hl i 1 1 2 , 5 8 8 , 6 1 4 Ch in c o n v e y o r s 5 4 7
a a
.
, , .

aa
B u t yr ic c id 2 0 8 Ch r g e s o f c o l l o id s 1 1 0
a a
. .
, ,

B y r so n im , 3 0 5 . Ch e n l i e r e v p o r t o r 5 1 6 , .

By s t r o n 2 7 7 Ch e s t n u t 2 8 7
a
-

. .
, ,

Ch il c o b r k 3 2 4
aa a
.
,

Chl o ri n e s t n n in g g e n t 5 7 5
aa a a
.
,

C e s l p in i 32 7 in w t e r 8 0
a a a
.
, , .

C l c iu m b u t yr t e 1 8 Chl o ro f o r m f e rm e n t s
'

c t io n on
aa
.
, , ,

l ct t e 7 1

a a
, .

s u l p h yd r t e 1 87 Ch m ro l f ki d e c
49 2

a mb i a
-
.
, , .

C l f —k id 2 4 5 co ti 37 7 n o n s,
a ta a
.
, .

C ll it r is 2 8 4 g nn es,
a ba
.
,

C l o r ie 5 1 4 l iq i it y
uors, 69 s c 2
a
. .
, ,

C m b iu m 2 7 9
’

Bl
’
k y 68 oc e s, 2
a t a
.
, .

C m p b el l 2 0 7 t d 67
co n c en r e 2
a
. .
, ,

C mp ho r 3 1 d d by 80 re 67 u ce 2
aa a
2,
. .
,

C n ig r e 3 0 0 lt i ‘

69 s n, 2

a l l a
m
.
, .

C n dy 5 6 5 so e th 7 e er , 2 0
a a ta i g
.
, .

C n e su g r 1 6
aa aa
nn n

a
.
, ,

C p r o ss b r k 3 2 4 Ch m i m
ro lt f u s s o 2
a a
.
, , ,

C p e su m c h 3 0 4 Ch m p t i
ro o 3 ro e n s, 1 1
a a ba
.
, .

C p el f n 5 2 9 Ch k 3 9
a a
ur c o
k a
r 1

Cl a
.
, ,
.

C r b o l i c c id 2 1 2 c l v
55 v e s, 1
a Cl a
, , .

C r b o l in eu m 2 8 fli 7 656
n 20
a Cl a
.
, , , .

C r b o n d isu l p hi d e k 67 68
r
a a Cl a
, , ,
.

C r b o n ic c id 1 6 i g 5 3
a l a
,
. e r n ,
0 .

in w t e r 8 0 th
e 49 7 er s ,

a a Cl i t at h
.
, .

C r iss 31 8 e s 3 5 u s, o

p a
n

a a a
.
, .

C r m ic h e l 5 7 3 Clim b i g f l m t 4 8 ev

aa a a
n i or or, 0

a
.
, .

C r n ii b w x 4 5 1 Cl o v e s, O il f 3 o 1
C a
.
, ,

C rp e n t er P ro f G H 44 o l p h p w er 5 5 o r se o er , 1
a t ab l a
-
. . . .
, , .

C r r 3 82 k
’

aa
49 3
r c s,
-
. .
,

C sc l o t e 3 2 7 d 48 7
ia a lt t a
o o urs,
a ba
. .
,

C s e in 1 3 1 1 5 4 C t i i n s, 37
aa
, , . o ccu s c er n s -
s
C ss i 32 9 C kl
oc 46 e,

a l b a3 3
.
, .

b rk 4 9 8 C
aaa
o co o 0

t pa
.
, , .

C st n i 287 C lm 85
ah
o co n u 2
a
.
, , .

C s t in g o r p it c h in g l e c e s, Co c o s 2 8 5
a
.
,

C s t o r o il 4 4 1 Co d o il 4 4 5
aa a
.
, , .

C su r in e 2 8 5 Co l e 1 3 7
aa
.
, , .

C t l y sis 1 5 Co l e S W 1 5 5
a a a
.
, , . .
, .

C t e cho l t n s 3 3 9 C o l e n d On s l o w , 6 6 1
a a
.
, .

C t e ch u 3 3 0 Co ll g e n , 1 4 6
a a a
.
, .

C u s t i c so d 21 e qu iv l e n t w e igh t o f , 1 23
aa a
.
, .

C v ll in 2 5 6 Co l l in n d B e n o is t 2 6
a a
. .
, ,

Ce n o t h u s 3 2 6 Co ll o id s t t e 1 0 7
a
.
, , .

Ce b il b r k 3 3 4 Co l l o id s 9 4
aa
.
, , .

Ce l v in 32 9 , . em u l sio n , 1 1 0 .
 I ND EX

C o l l o i d s o r g n ic 1 1 0 a Da
cc a kip s 3 9 4 0
Da
.
, , .
, ,

Co l o r im e t ri c m e t h o d 1 0 3 kin 1 3 5 1 3 6 1 5 1
a Da
lt o n s l a
. .
, , , ,

w 85
’
Co l o u r b s e s 4 8 8
a Da
ma
. .
, ,

m e su r em en t 3 5 3 g e d hi d e s 4 2
Da
n i sh g l o v e l e a
. .
, ,

m ix in g 5 0 8 t h er
a
37 5, 37 7
Da
. .
, ,

r e c t io n s o f p r o t e in s 1 4 0 p h n e 30 4
a a
. .
, ,

Co l p o o n 3 0 4 D p h n o id e 3 0 4
a a a
. .
, ,

c o m p r e ss , 3 1 1 D ss e l p l g e 4 3
a
. .
,

Co l t 4 7 D vis 4 8 1
a aa a
. .
, ,

Co m b in t io n t n n g e s 2 5 3 3 7 5 D vy 3 4 8
aa aa
-
. .
, , ,

Co m b r e t c e , 3 2 0 De d f t 4 7
aa a
-
. .
,

Co m m e r c i l f c ilit ie s 5 3 9 D e c im l s y s t e m 5 8 0
aa a
. .
, ,

Co m p r t o r I O3 57 8 , D e c o l o r is in g o f e x t r c t s 4 0 3 40 4 , , .

663 D e f e c t s in d y e in g 5 0 2
a a
. .
,

Co m p r e s s e d ir 5 5 3 D eg r s 4 4 8 4 5 9
a
. .
, , ,

Co n d e n s e d w t e r 5 3 3 fo r m e r 4 5 0
a a
-
. .
, ,

Co n e m il l s 3 8 1 D e h y d r t in g e ff e c t o f s l t 2 2 2 3 4
a a
-
. .
, , ,

Co n n e c t iv e t is s u e 4 8 , . D e h y d r t io n b y l c o h o l 1 1 4 , .

fi
b res 5 8 D e kk e r 2 7 8 3 4 7
a a
. .
, , ,

Co n s t r u ct io n o f t n n e r i e s 5 3 8 D e l im in g wit h c id s 2 0 2
a
. .
,

Co n t c t b e d s D e Lo f 2 7 8 2 9 0
a a
.
, , ,

Co n v e y o r s 3 8 9 3 9 1 5 4 7 D e n t u r is e d s l t 2 3
aa
. .
, , , ,

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aa
. .
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a a
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, ,

C o p e r n ic c e r if e r w it h h yp o 2 38

a a
45 1
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a
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,

su l p h t e 2 7 f o r g l o v e ki d 2 5 0
aa D m a4 8 5
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a
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m yr t if o li D m t lp i
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31 1 er 4
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,

Co r iin 6 0 , . z t i i g 49
o s n , 2 .

Co r iu m 4 8 4 9 5 0 5 7 6 1 D iff i 9 5 363 3 7 3
D il t aid ad g l a
, , , , . us on , , , .

Co r k 2 8 0 ti 5 83
f m l a9 9
u e c s n e n,

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o k 293 D il t i u
D ip l a
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.

Co r n e u m 5 1 o i i g ff t r s n 3 e ec 1 1
a a ap 3 3 5
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Co r t e g i r o s s 2 83 D ip t er o c r u s,

a D i t —at i g p m p 5 5
. .
,

Co s t o f c id s f o r d e l im in g 2 0 9 r ec c u s, 1
D i i f t at
, . n .

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Di i t g a
, . s n ec n s, 2 1 .

Co u p e r u s 3 1 6 t 38
aa
, . s n e r ors, 2 .

Co u r t r i 3 2 4 D i p it y 5 7 8
a wa
ers
Di p a
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Cr e s o t e 2 8 l f 538
wa
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s os g o se

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,

Cr e o l in 2 8 Di s so c ti t o n co n s n or er , 6 60
D i t il l d t a
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Cr e so l s 2 8 i s e r ne, 0

a
s e 44
w l g a 439
. .
,

Cr e so t in i c c i d 2 1 2
aa
, . oo re se , .

Cr it ic l s t t e 8 7 D i t ib t i
s r b tw u l t on e e e n so v e n s, 93
f a
. .
,

Cr o sso s t yli s 3 2 3 i
a
, . o r,

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v v
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2

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-
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aa
, . o e rr n e n r ,
.

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a
g 5 22
D g la
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l a
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,

Cu ir e n t r ip e 5 0 th
e 37 5 37 6 er ,
aa a 58
. .
, ,

Cu p n i D
aad H ai 8
32 5 o nn n, 2
a
. .
,

Cu r in g Ski n s b y l u m 2 44 D rr s, 1 1

l a
o nn n n
D a
, . .

Cu r r yi n g 4 6 3 i i g d ro s, 5 5 0

a w g a
r n c e n n

D a
-
. .
,

Cu r t id o r b r k 3 1 9 i 36 1
a
, . r n r n, .

Cu r u p i b r k 3 3 4 D h
th a 447
5 4 0

aa
, . re er, .

Cu r v e o f v ri b l e e 6 3 4 , . D ik re ro n en r n, .

Cu t c h 3 3 0 D hi g 8 20 1 21
ta
ren c 4 n

a
.
, .
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b l c k 50 7 f m ti i 9 on n, 1

D pa a
-

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Cu t is 4 8 , . re p 3 7
noc r u s, 2 .
 P RI N C I P L E S OF LEA TH ER MA N UFA C T UR E
I

67 8

D r e s sin g l e a t her s 3 6 9 , . E n t e r o k in se 2 2 3 a ,
.

D r ie r s f o r o il s 4 4 3 E n t e r o l o b iu m 3 3 5
a
. .
, ,

D r u m d y e in g 5 o o ,
. z
En ym e b t e s 5 7 8 ,

st u f fi46 7 n g, h y d r o l y sis 1 3 6
a
. .
,

fo r w s hi n g , 1 6 5 z
En y m e s 1 5 1 6 1 2 6 20 0
a
. .
, , , ,

D r y hi d e s , s o kin g o f 1 5 9 , . fro m p u e r 2 2 1 , .

D r y in g fl e sh in g s 5 5 9 ,
. E p id e r m i s 1 3 1 9 4 8 4 9 5 o , , , , , .

h id e s 4 1 E p it h e l iu m 4 8
a
.
, , .

Of l e t her , 5 1 6 c ell s 1 3

a
'

. .
,

o f O il s 4 2 8 4 3 0 E qu il ib r i 87
a a
. .
, , ,

o f s t u ff e d l e t h e r , 4 66 _
io n i s t io n 1 0 1
a
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. .
,

p o w e r o f ir , 5 1 8 E r e c t o r p il i 5 3 5 4 5 5
a aa
. .
, , ,

so l e l e t h e r 3 6 5 E r ic c e 31 9
a a
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, ,

wit h h e t 5 2 1 E rn st n d Z w e n g e r 3 4 1
a a
. .
, ,

D r y s l t e d hi d e s so k in g o f , B r o d in 2 2 2
a
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.
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D u b b in g , 4 6 5 E s s e n t i l o il s 3 1 4 5 2
a a
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, ,

D y e b t h s r e u s in g 5 0 2 E u c l yp t u s 3 2 4
a a a
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D y e in g l u m e d l e t h e r s , 4 9 5 Eu c o u p i 336
‘

a
.
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c hr o m e _ le t her 2 9 4 E u d e r m in 2 8
a
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d e fe c t s 4 9 7 Eu g e n i
aa
32 5
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o il l e t h e r s 4 9 6 Eu p ho rb i c e
‘

30 5
a a a
-

. .
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in t w o t r y s 5 0 1 E v p o r t io n 5 1 2
a a a
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, ,

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a a
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D y es n d d y e in g 4 8 7 in Op e n p n s 5 1 5
a a
.
, .
,

fo r l e t h e r 6 40 in v c u o 5 1 5
a a
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D yé t ri l s 5 1 1 , . o f e x t r c t s 40 5 , .

t h eo ry o f 5 1 2
a
.
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1 90
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a a a a a a
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E u d e j v el l e 5 7 5 , . E x t r c t io n o f t n n in g m t eri l s ,

E b e rl e 2 0 8 2 2 4 2 6 5
E t a g ab
, , , .
39 2 .

E c o n o m ise r s 525 , . x t r f c o rs o r su r -
e et , 40 2 .

E ff ro n t 2 0 8
a Fa
.
,

E gg — l b u m in 1 3 1 d i g b y ligh t 4 9 8
Fa
, . n , .

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r on, 2
F a—
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n r n 20
Fa a
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1 7 9 21 6 2 59 261 2 62 263, d 97
Fa
r

ada
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2 66 2 68 2 69 272 273 2 88, y 47 9

Fa
, , , , , r ,
.

3 7 6 4 4 5 4 46 4 4 9 , 460 , 470 t ll ce 6 s, 2 2 , 1

a fi
-
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a
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g l ad
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a
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a
.
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0 .
5 , .

c u rren t s 85 so l ven t s 42 8

aa
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d r i v in g 5 4 3 , . F t s n d Oil s 4 2 5 ,
.

o sm o se , 1 0 9 in c u r r yin g
ai a a
.
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t nn ng, 1 09 F t t y c id s 4 2 5
a
.
.
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aa
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, ,

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a
.
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57 8 F e r m e n t t io n 1 5
a
.
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.

E l e i d in 5 1 Fe r r i c o x id e 2 2
a a a a
. .
, ,

E l e p h n t o r r h iz in p l c e o f P r u ss i n b l u e 4 8 5
a a a a
335 , .
,

El l gi c c i d 3 4 1 F il o b r k 2 8 5
a a
. .
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E m u l s ifi c t io n 4 6 5 F il t e r p r e ss in g g r e s e 5 5 9
a
-
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,
.
,

E m u l s io n c o ll o id s 1 1 0 Fil t e r s f o r w t e r 7 8
a a
.
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,

E m u l s io n s 9 1 4 7 2 F il t r t io n o f s e w g e 5 6 5
a a a
, , .
, ,

E n m el l e d l e t h e r 4 7 5 , . F in i s h in g s o l e l e t h e r 3 6 5 ,
.

E n g in e p o sit io n o f 5 4 2
, , . Fir e ri s k 3 8 8 5 40 5 4 6 , , ,
.
6 80 P R I N C I P L E S OF L EA TH E R MA N UFA C T UR E
G r e en l e t her 3 7 7 a H i d e s So u t h A m e r i c n 4 2 a
a a aa i
.
, , , .

Gr e en o k , 2 9 2 H igh sp e e d m c hin e r y b l
aa
.
-

, n c ng,
G r e e n s , s g e n d Ol iv e , 5 1 0 5 45
a
.

G r e e n s t iffn e ss 1 79 H is t o r i c l n o t ic e , 1
a
. .
,

G r e v il li 30 3 H o fm e i s t er , 1 2 9 , 1 4 7 , 6 2 4 , 6 2 5
a
.
,

G r i e ss m y e r , 3 4 1 H o l b r o o k syst e m , 3 9 5
a a
. .

G r in d in g s m p l e s , 3 4 7 H ol de n f t 4 3 9
a a a a
. .
,

t n n in g m t e r i l s , 3 80 H oll n d er 1 9 0
a
. .
,

G r o u n d in g 2 4 4 Ho o ke s l w, 6 3 4
’

a
“

. .
,

G u m m in g o f e l st ic it y 1 1 9
aaa
20 , .
, .

G um t r g c n t h, 50 8 H o o p er 2 7 8 , 3 2 3
a a
. .
,

G u n n er H o p kin s n d Co l e , 1 4 0
aa
324
a
. .
,

G u n n er c e e 3 2 4 , . n d Pin k u s 1 41 , .

H o r n s 5 60
Ha
ma a
.
,

ti
e 56 n H o r se f t , 4 3 8
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-

.
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m gl b i ; 3 p o we r 5 1 5
a fi
e o o n 1 1
a
-
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.
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H ir 5 5 5 H o t ir s t u f n g d r um , 4 6 7
a a
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. .
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m u sc l e 4 9 5 3 5 4 5 5 , , , ,
-
w t e r h e t in g 5 3 3 , .

— o re s 6 1 H u gh e s 2 9 1
p
a
.
, .
,

—sh e t h s H u m in n it r o g e n , 1 4 3
5 , 5 . .

st r u c t u r e o f ; 52 H u m m el 2 5 7
a
.
,

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a a a
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H l o ge n s c t io n o n p r o t e in s 1 46 H u r wit Me y e r n d Ost e r b e r g 6 6 1
z ‘

a a
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H m p shir e B 1 67 H y l in e 5 6 4 9 1
a
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H n dl e r s 3 5 8 H y d r i c s o d ic s u l p hi t e 2 5
a a a
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H r d ”g r e s e s i n s t u ffi n g 4 6 8 s o d iu m su l p h t e 2 2
wa a
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, ,

t ff t 74er , e ec s, H y d ri o n c o n c e n t r t io n I O 3 1 0 6
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-
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d d g f 67 rees o H y d r o g e n t io n 4 3 2
aa
r n e ss , e , .
, .

ff t hi d 8 H y d r o l ys is l k lin e o f p r o t e in s 1 3 5
f wa
e ec on es, 1 .
, , , .

o t 66 67 er , b y e n ym e s 1 3 6 z
p ma t 7 6 a
. .
, ,

er n en c o n st n t , 1 0 2
ay 6 7 a
-
.
,

t mp e or r e qu t i o n 1 02

H ai a
-
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, ,

r r so n 3 569 1 0, f o r g e l t in 6 1 8
H aff a
. .
, ,

u 21 2 o f p r o t e in s b y c id 1 34
H ama
. .
, ,

us 43 o f p r o t e in s 1 2 8 , 1 3 2
H Cl ad g l a
nn, 1 .
, .

ti H y d r o qu in o n e 5 7 3
H a l a a
n 59 e n , 1 .
,
.

e d P t n 57 ro c er, 2 H yp h e 1 4
H a
. .
,

e t ff t eft i g h id H yp o u s e s o f 2 3 8
a
ec o n so en n e s, I 59
by t a
.
, .
, ,

gi ve n m p ip 5 4 s e es, 2 H y p o d e r m b o v is 4 3 4 4 , 4 5
aa
. .
, ,

l th
o ss gh f 5 3 ro u ro o 2 l in e t 44
wa
. .
, ,

ll 5 3 s, 2

a a
.

f evti 87 5 5 I m m is c ib l e s o l v e n t s 9 3
a
o p or on, 1
f t ha
. .
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wi g i I n d i n c u r e O i k ip s 3 9
'

q a
o 5 5 n ce, 1 .
, .

t it y f 5 4
u n o 1 ki p s 1 6 0
q i d t wa m a a
. .
, ,

re u re i 5 o r r, 20 I n d i c t i n g e n g in e s 5 4 2
H a ti g l a a
. .
,

h I n d ic t o r s 1 0 3
‘

f ha
e c 00
a
n 4 e e s,
m i l a
. .
,

c th 45 8 o s t b l e o f, 6 6 2
a
o e er ,
f l a
. .

o th e er, 20 . In g 334 .

H eb n er 6 7 , . I n ks 4 9 4 , .

I s in z e r l in g 2 5 6 I n so l u b l e s
aa
351
a
. .
, ,

H el v e t i l e t h e r 4 5 9 I n t e r f c e s l iqu id 9 0
a a
. .
, , ,

H eml o ck b rk 2 82 In t e r n l p r e ss u r e 8 8
a
. .
, ,

H e n n ig , 4 8 0 I n t ro d u ct o ry sk e t c h of l e t h er
a a
.

H en ry T 6 8 m n u f c t u r e s, 3 7
“

a a
. . .
, , ,

H id e c o l l o id e ll y 1 1 6 j In ve rt se I 6
a a a a
.
, ,
.

fi b r e c i d n d b si c , 4 9 0 I n v o l u n t r y m u s cl e 5 5
aa a
-

. .
,

m ill 1 6 3 1 6 4 I o d in e s t n n in g g e n t 57 5
a
-
. .
, , ,

p o wd e r 5 7 9 ,
. v lue 42 8 ,
.

p ro c e ss 3 49 o f o il s 4 3 4
a a
. .
, ,

H id e s m r kin g w e igh t
, , 32 . Io n i s t io n , 9 7 ,
 I NDEX 68 1

a a
I o n is ti o n c o n s t n t s , 9 9 Ko r n e r 1 1 4
a a a
. .
,

o f w t er 1 0 1 1 06 Kr m e r i 3 0 5
aa
. .
, , ,

o f we k c id s 6 5 7 Kii h n e 1 3 7
a
. .
, ,

Iro n l u m 2 7 6 Ku n d t 1 1 4
a
-
. .
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b l cks, 4 9 1 4 9 3 K y r in s 1 3 2 1 3 3
a
-
. .
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b l u e s n d b r o wn s 4 9 2
La aid 8 7
.
,

in b l o o d 3 8 c t ic
a ahy d id
, . c , 1 , 20 .

in w t e r , 7 9 n 8 r e, 20
— f m ta
. .

l iqu o r 5 0 6 ti
er 8
La
en on 1
la i a3
,
.
7 , .

p yr o l ig n it e 5 0 6 g un cu r 22
a La
. .
, ,

s l t s o f, 25 4 . mb 74 3 48 7 4 88
. 2 , 1 0 . . , 49 8. 5 7 1 .

S o l u t io n s 5 0 6 64
aa La l i
-

, . 0 .

t n n ge s 2 7 5 no 439 n e,
La
. .
,

I so e l e c t ri c p o in t 1 1 1 , 1 1 8 , i r x8 2 2
a La s 3 3
.
, ,

o f c o l l g e n 20 1 u ru 0

a La
. .
, ,

o f g e l t in 6 6 3 w
a La
, , 2
It ch
za L a
33 359 er s,
, .
y .

I l 28 e h b tt m 39 3
at i g mahi 3 9 9
, . c o o s, .

]a ab ak 3 L a
c s c ne,
ad p ip 5 4 9
n .

m h
L a
ro s r 21 e c es n e s,
Jap af l a
. .
,

th hi g 3 9
a
n
444 or e ers, e c n 2

p pa ba
. .
,

ti re f 47 8 tt i
d bl a
r on o 395 er e s ,

Japa l a L a
.
,
;
th 46
n e se h 49
pa d l a L a
e er , 1 e e c 2
Ja
. .
,

th 47 5 dw t 3 4
p a i g Am i a 4 8 L a
nne e ers, e or 0

Ja
. .
,

l a
d y ll w
'

nn n er c n, 1 e e o s,

it a L a
.
,

th bl 47 6 f ti l 8
Japa a
e ers su

p p li a a
e, e cu c e s, 2 1
L a
-

. .

ti n s, th
L y t hi d a a3 4
47 7 c on , . e p 57 e r scr -

,
0 .

c u r r yin g , 47 6 . ec ce , 2 .

d r yi n g 47 7 L y t hi 3 4
ec

ha i i g ma
, s, 2 .

J el l i e s , 1 1 2 L id g
e en hi un r n c n e, 1 92
]e t t m a
. .

263 2 7 7 L ti l
en 8 c e s, 2 1
ad G a
r , , . .

]e y e s fl u id 2 8 L p t it D l l f
’
e e o us n u s s er , 3 42 .
ju n gh a
, .
,

n s 485 ,
. Le u c o d e n d r o n 3 0 4 , .

Ju n ip e r u s , 2 84 . Le u c o sp er m u m 3 0 4 , .

L e v it e s 1 4 3
a aa
.
,

K hu b r k 3 2 1 L e wk o w it sc h , 4 2 5 , 4 4 6
a a
. .
,

K run d 3 1 8 Lie b e r k ii h n s e l l y 1 3 2
‘ ’
j
a a
. .
, ,

K sp in e l e t h e r 4 5 9 Li e b ig 1 2 6
aa a
. .
, ,

K t p h o r e s is 1 0 9 Li e t z m n n 4 6 1
a
. .
, ,

K th 331 L im e 2 1
a a
, .
, .

K t ho de 9 7 c t i o n o f o n hi d e s 1 7 3
a aa
. .
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K t h r e in e r F 5 6 2 5 2 3 4 6 n l y sis 1 7 1
aaa
. . .
, , , , ,

Ke n t 3 7 5 3 7 6 3 7 8 v il b l e , 1 72
a
.
. . ,

Ke r t i n s 1 3 4 1 5 3 l iqu o r s 1 3 4
,

a aa
.
, , .
,

Ke r m e s o k 2 9 4 l k l in it y 6 6 7
a a a
. .
, ,

Ke s t n er e v p o r t o r 4 0 8 s l k in g 1 6 9

a
. .
, ,

Kil o gr m m e t e r s 5 1 5 , . s o l u b il it y 1 7 0 , .

Ki n o 3 2 6 p it s 5 4 8
a a
-
. .
, ,

Kip s I n di n 1 6 0 w t e r m e t ho d 6 6 5
aa a
-
.
, , .
,

Kir i t o t o 2 84 w t e r t e st 3 5 7
a a a
- - -
. .
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Kit t su b s t n g 6 0 , . Lim e s b c t e r i in , 1 7 8
, .

Kl e m m 4 6 0 Li m i n g 1 6 8
a a
. .
, ,

Kn p p 1 1 5 2 4 3 2 5 6 2 6 4 2 7 6
, , , , , ,
f e r m e n t t i o n in , 1 9 .

575 in su sp e n sio n , 1 7 4
a
.

Kn o p p e r n , 2 9 8 Li n o l e n i c c i d 4 3 0
a
. .
,

Kn o t t e d t r e e , 3 0 4 . Lin s e e d m u c il g e 5 0 8 , .

Ko c h 2 8 8 o il , 44 2
a
. .
,

K o e n ig 5 7 0 Liqu id st t e 8 6
a
.
, .
,

Ko e r n e r 3 2 3 , . Liqu o r t n k s , 3 9 7 , 5 5 1 .

K OIIik e r 5 1 ,
. t r o u gh s , 3 9 9 .
68 2 P RI N C I P L E S OF L EA TH ER M A N U FA C T UR E
Liqu o r v al ve s 3 9 7 Me r c u r ic c h l o r id e , 2 1 26
Liqu o r s r a
550
a
. .
, , ,

is in g b y c o m p r e ss e d i
r, i o d id e , 26
Me r c u r y l a
.
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684 P RI N C I P L ES OF L EA TH ER MA N UF A C T UR E
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6 86 P R I N C I P L ES OF L EA TH ER MA N U FA C T UR E
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CH EMI CA L I ND USTR I ES

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A LL INQ UIRI E S MA DE OF US AR E CHEER

F ULLY A ND CA R EF U L LY A N S W E R E D
.

A ND COMPL ET E CA T A LOG S A S WELL AS

SP ECIAL LI ST S S ENT F R EE ON R EQ U EST

D VA N NOSTRAND COMPA NY
.

P ublis he rs adn Bo o kse lle rs

8 WAR REN STR EET NEW Y OR K