THE DETERMINATION OF FREE ALKALI

OR FREE FATTY ACIDS IN SOAPS

A T h e s is
P re s e n te d to

t h e D ep artm en t o f C h e m istry

U n iv e r s ity o f S o u th e rn C a li f o r n ia

In P a r t i a l F u lfillm e n t

o f th e R e q u ire m e n ts f o r t h e D eg ree

M a ste r o f S c ien c e

By
W ern er 0. S ch u b ert

lu n e , 1939
 UMI Number: EP41519

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Th is thesis, w ri tt en by

W erner 0 . S ch u b ert
un der the direction of h.%3. F a cu lt y C o m m it te e ,
a n d a p p r o v e d b y a l l its m e m b e r s , has been
pr es e nt e d to and a c ce p te d by the C ou nc il on
G ra d u a te S t u d y and Resea rch in p a r ti a l fulfill­
m e n t o f th e r e q u i r e m e n t s f o r t h e d e g r e e o f

M a ste r o f S c ie n c e

Dean

Secretary

Date... - J u ly 19-3©

Faculty Committee

Chairman
 TABLE OF CONTENTS

PAGE

I. IMPORTANCE OF A RELIABLE ANALYSIS . . . . . . . . . . 1

D a n g er o f R a n c i d i t y o f t h e Soap . . . . . . . . I

W h ite S u r f a c e C o a tin g o f t h e Soap . . ..................... 1

T he M e th o d s i n U s e a r e U n s a t i s f a c t o r y ..................... 2

II. INVESTIGATION OF THE DIFFERENT M E T H O D S ...................... 3

E x a m i n a t i o n o f t h e M e t h o d s "by t h e S u b - C o m m i t t e e

o f P u b l i c - A n a l y s t s a n d o t h e r A n a l y t i c a l Chem­

ists ............................................................................................................. 4

S u g g e s t i o n s o f t h e M e th o d s by t h e S u b -C o m m itte e 5

III. DIFFICU LTIES IN DETERMINING FREE ALKALI AND FREE

FATTY A C I D S ........................................................ 7

In c o m p le te S a p o n if ic a tio n .................................................... 7

S o a p -b u ild e rs .................................................................................. 7

C arbon D io x id e A b s o r p tio n .................................................... 7

H y d r o l y s i s ............................................................................ 7

IV . PURPOSE OF INVESTIGATION AND ORGANIZATION OF WORK 8

S e l e c t i o n o f R e f e r e n c e S a m p le .......................................... 8

C o m p le te S a p o n i f i c a t i o n b y R e f lu x C o n d e n s in g . . 9

P r e p a r a t i o n o f S a m p l e .................................................................... 11

A n a l y s e s o f S a m p l e s ..........................................................................11

I n t e r p r e t a t i o n o f R e s u l t s .................................................... 14
New M e t h o d .................................................................................................14

V. SUMMARY...............................................................................................................16

V I . ' B IB L IO G R A P H Y .............................................................................................. 18
 L IS T OF TABLES

TABLE PAGE

I. S a p o n i f i c a t i o n V a l u e s o f Some F a t s a n d O i l s A f t e r

D i f f e r e n t P e r i o d s o f B o i l i n g ................................................ 10

II. C o m p ariso n o f R e s u l t s O b ta in e d b y F i l t e r i n g and

C e n t r i f u g i n g ........................................................................................ 13
 THE DETERMINATION OF FREE ALKALI OR

FREE FATTY ACIDS IN SOAPS

One i m p o r t a n t q u e s t i o n i n t h e s o a p i n d u s t r y i s t h e

p ro b le m o f t h e d e te r m i n a ti o n o f th e free a lk a li or free

f a t t y a c id s in soaps. C h e m ists have i n v e s t i g a t e d and w r i t t e n

m uch a b o u t t h e m e t h o d s e m p l o y e d , b u t n o n e o f t h e a n a l y t i c a l

p ro c e d u re s p ro p o sed has g iv e n s a t i s f a c t o r y r e s u l t s . It is

v e r y i m p o r t a n t t o know t h e a c c u r a te am ount o f f r e e a l k a l i ,

e s p e c ia lly in th e case o f h ard soaps, sin c e th e re i s danger

of s p littin g a sm a ll p a r t o f th e soap i n t o free fa tty a c id s

and f r e e a l k a l i , w h ic h g r a d u a l l y c h a n g e s i n t o a lk a li carbon ­

a te . The f r e e f a t t y a c i d s so l i b e r a t e d le a d t o r a n c i d i t y .

For t h i s reaso n th e soap m ust be s a p o n if ie d c o m p le te ly and

f i t t e d w i t h 0 . 1$ t o 0 . 2$ f r e e a l k a l i b e f o r e i t le a v e s th e

k e ttle . A c c o r d i n g t o K nigge^- 0 . 1 $ f r e e a lk a li i s fo u n d to

b e t h e m o s t f a v o r a b l e a m o u n t, w h i c h d o e s n o t p r o v e t o b e u n ­

p l e a s a n t f o r t h e consum er. The p e r c e n t a g e o f s o d i u m h y d r o x ­

id e lib e r a te d by h y d ro ly s is i s c o n sid e ra b ly la r g e r ( a few

t e n t h s o f 1$ ) t h a n t h e f r e e a l k a l i . .

K h i g g e re c o m m e n d s 0. 1$ b e c a u s e t h e b a s i c s o a p s u f f e r s

a d e f i n i t e l o s s i n f r e e a l k a l i w hen b e i n g p r o c e s s e d t o th e

f in is h e d cake (m o stly d u rin g d ry in g ) . I n som e c a s e s t h e

f r e e so d iu m h y d r o x id e c o n t e n t w as d i m i n i s h e d a lm o s t t o

n o th in g . B u t i f t o o m uch f r e e a l k a l i w as a d d e d , on t h e

K n ig g e, " D e te r m in a tio n o f F r e e A l k a l i i n S o a p s ,”
A m e ric an P e r f u m e r . 2 9 : 4 0 3 - 4 , O c to b e r , 1 9 3 4 .
 3

o t h e r h an d , t h e soap becam e c o a te d w i t h w h ite so d iu m c a r b o n ­

a t e on t h e s u r f a c e . The e x c e s s so d iu m h y d r o x id e h ad c h an g e d

in to so d iu m c a r b o n a t e .

S in c e th e m a j o r it y o f so ap s a re d r i e d i n open con­

v ey o rs, th e c h e m ic a l t r a n s f o r m a ti o n s o c c u r r in g th e r e b y m ust

b e c o n s i d e r e d w hen d e t e r m i n i n g t h e f r e e a l k a l i c o n te n t b e fo re

and a f t e r d ry in g . The s o a p m a n u f a c t u r e r m u s t b e i n a p o si­

t i o n to d e te rm in e e x a c tly th e f r e e a l k a l i c o n te n t. But t h i s

w as n o t p o s s i b l e b y t h e m e th o d s u s e d so f a r . I n som e c a s e s

soaps c o n ta in in g f r e e a l k a l i w ere r e p o r te d to have f r e e

f a t t y a c id s.

A few o f t h e m o st g e n e r a l l y e m p lo y ed m e th o d s o f a n a l y ­

sis a re o u tlin e d as fo llo w s:

A c c o r d i n g t o t h e m e th o d o f t h e G erm an S o a p M a n u f a c ­

t u r e r s o f G e rm a n y t h e f o l l o w i n g p r o c e d u r e i s u s e d : 10 gm.

o f s o a p a r e d i s s o l v e d o n t h e w a t e r b a t h i n 100 gm. a b s o l u t e

a lc o h o l and s e p a r a te d b y f i l t e r i n g th ro u g h a h o t w a te r fu n n el

fro m t h e i n s o l u b l e m a t t e r , such a s f i l l e r s as a l k a l i carb o n ­

a te s . The f i l t r a t e i s t i t r a t e d w i t h N /1 0 HOI i n t h e p r e s e n c e

o f p h e n o lp h ta le in u n t i l th e re d c o lo r a p p ea rs. The f i l t e r

sh o u ld be co v ered w ith a w a tc h g la s s in o r d e r t o p r e v e n t th e

f o r m a tio n o f a l k a l i c a r b o n a te th r o u g h c a r b o n d i o x id e from

th e a i r .

T h is m e th o d , as w i l l be seen l a t e r , is not sa tis fa c ­

to ry , sin c e th e f i l t e r p a p e r does n o t o n ly a b so rb f r e e a l k a l i ,
 3

b u t a l s o a l k a l i w h ic h s h o u ld h a v e b e e n c o m b in e d . W a s h in g o f

th e f i l t e r , w h i c h i s n o t m e n t i o n e d h e r e , w o u l d n o t re m o v e

th is a lk a li.

S e v e r a l o t h e r m eth o d s w h ic h p r e s c r i b e t h e u s e o f

b a riu m c h lo r id e s o l u t i o n s a r e f r e q u e n t ly u se d . But h e re a

g r e a t e r r o r w i l l be i n t r o d u c e d , s in c e b a r y t soap h y d ro ly z e s

s l i g h t l y and a ls o a b s o r b s so d iu m h y d r o x i d e . F u rth e rm o re ,

th e b a riu m c a r b o n a te form ed from t h e c a rb o n a te s w i l l r e a c t

w i t h t h e N /1 0 HC1 a n d b a r y t ; s o a p w i l l b e p r e c i p i t a t e d w i t h

th e f i l l e r s .

S t i l l o t h e r m eth o d s d ep en d o n t h e p r i n c i p l e o f s a l t ­

i n g o u t w i t h so d iu m c h l o r i d e , b u t h e re to o h ig h r e s u l t s w i l l

be o b ta in e d . D r. D a v is o n 2 c la im e d t h a t h i s m eth o d g i v e s

good r e s u l t s . I n t h i s m eth o d , w h ic h h a s b e e n a d o p te d b y t h e

W iz o ff ( W i s s e n s c h a f tl i c h e Z e n t r a l s t e l l e f u r 01 u n d F e t t -

fo rsch u n g ), 3 t o 5 gm. soap a r e u s e d . T h is soap i s d isso lv e d

i n 50 t o 75 m l 9 8 $ n e u t r a l i z e d a l c o h o l w h i l e w a r m in g u n d e r a

r e f l u x c o n d e n se r and t i t r a t e d , w h e n c o o l , w i t h N /1 0 HC1. But

a ls o h e re i t i s n o t c o n s i d e r e d t h a t t h e p r e s e n c e o f so d iu m

c a rb o n a te w i l l i n t e r f e r e . T h is c a r b o n a te i s m o s tly p r e s e n t

in lo w e r g ra d e so a p s.

The A n a l y t i c a l M e t h o d s C o m m i t te e o f t h e S o c i e t y o f

% D a v i s o n , "T h e M e t h o d s o f D e t e r m i n i n g o f ''F r e e A l k a l i s '

and th e D e te rm in a tio n o f . t h e H y d r o l y t ic a l l y D is s o c ia te d A lk a li
i n S o a p s , " R a y o n a n d M e l l i a n d T e x t i l e M o n t h l y . Y o l . XYI,
Ja n u a ry , 1935, p . 55; F e b ru a ry , 1935, p . 43.
 4

P u b l i c A n a ly s ts and o t h e r A n a l y t i c a l C h e m is ts a p p o in te d a

S u b -C o m m itte e t o i n q u i r e i n t o t h e m eth o d s f o r t h e d e te r m i n a ­

tio n o f u n s a p o n if ia b le m a tte r in o i l s and o f u n s a p o n ifie d

f a t in soaps, a s w e ll a s th e d e te rm in a tio n of f r e e a l k a l i

and f r e e f a t t y a c i d s . T h is S u b -C o m m ittee h a s e x a m in e d th e

f o l l o w i n g m e th o d s f o r t h e d e t e r m i n a t i o n o f f r e e a l k a l i i n
<x
s o a p s f o r t h e p u r p o s e o f d e v e lo p in g a s a t i s f a c t o r y m e th o d ;

1. T he D e t e r m i n a t i o n o f TOTAL F r e e A l k a l i . V iz e rn and G u illo t.

(A nn. Chim . A n a l . 1934. 16, 4 4 6 .)

2 . The D e t e r m i n a t i o n o f F r e e C a u s t i c A l k a l i .

a. The m eth o d o f t h e B r i t i s h p h a r m a c o p o e ia . 1932.

b. T he s t a n d a r d m e t h o d o f t h e A m e r i c a n O i l C h e m i s t s '

S o c ie ty (O il and Soap. 1934, 11, .9 0 .)

c. T h e s t a n d a r d m e t h o d o f t h e G erm an S o a p M a n u f a c t u r e r s

A s so c ia tio n .

d . Y iz e r n an d G u i l l o t ’ s m eth o d ( l o c . c it.)

e . P o e t h k e 's m eth o d ( F e t t e h e m . U m sc h au 1 9 3 5 , 42. 180-2,

1 9 7 -2 0 1 .)

f. M e th o d s u s i n g b a r i u m c h l o r i d e , e .g ., R e p o r t No. T .G . 23.

G o v t. D e p t. S p e c ific a tio n s f. G en . S t o r e s . S oaps, 1929.

( 1 ) H e e rm a n n . (Chem. Z t g . , 1 9 0 4 , 28, 53 a n d 6 0 . )

(A b st. A n a ly s t 1904, 129. )

® A n a l y t i c a l M e t h o d s C o m m i t te e : S u b - C o m m i t t e e o n M e th o d s
o f S o a p A n a l y s i s , R e p o r t No. 3 , "T he D e t e r m i n a t i o n o f F r e e
A lk a li i n S o a p s / ' A n a ly s t. 6 2 :3 6 -4 1 , 1937.
 5

(2) Is m a ls k e y . (D e u ts c h e 01 u n d F e t t I n d . 1926,

46, 5 45-6, 5 6 2 -4 .)

(3 ) F ilin g , G o n in an d F l o r e n t i n e . (B u ll. Soc. Chim .

1914, 200. )

(4) H e t z e r . ( F e t t c h e m i s c h e U m sc h a u , 1 9 3 5 , 8 7 .)

g . M e th o d s d e p e n d in g on s a l t i n g o u t t h e s o a p , fo llo w e d

by t i t r a t i o n u sin g s i l v e r n i t r a t e as in d ic a to r.

(N e w in g to n , J . S . C . I . , 1916, 35, 9 5 .)

h. D a v iso n . (Chem. U m sc h a u , 1926, 2 7 3 .)

3. The d e t e r m i n a t i o n o f c a r b o n a t e . The p u b l i s h e d m e th o d s

d ep en d on t h e assum ed a lc o h o l i n s o l u b i l i t y o f t h e c a r b o n ­

a te and t i t r a t i o n o f th e re sid u e .

4. The M eth o d s o f S c o t t . ( S t a n d a r d M e th o d s o f C h e m ic a l A n a ly ­

sis, v o l. 2. )

5.. T h e M e th o d o f G r i f f i n . ( T e c h n i c a l M e th o d s o f A n a l y s i s ,

p. 3 7 1 .)

6. D a v i s o n ’ s M e th o d . (R a y o n a n d M e l l i a n d T e x t i l e M o n t h l y ,

16, I, 55. II, 4 3 .)

T he C o m m i t t e e r e c o m m e n d s t h e f o l l o w i n g p r o c e d u r e s :

1. D i r e c t t i t r a t i o n w ith o u t t h e a d d i t i o n o f b a riu m c h l o r i d e .

T he p r o c e d u r e i s as fo llo w s: To 1 0 0 m l o f r e d i s t i l l e d

i n d u s t r i a l a lc o h o l (9 4 .7 $ v o l . ) i n a 400 m l f l a s k , add

0 .5 ml o f 0 .5 $ a lc o h o lic p h e n o lp h ta le in s o lu tio n , a llo w to

c o o l t o 7 0 ° G. a n d n e u t r a l i z e a t ro o m t e m p e r a t u r e w i t h
 6

N /lO N a l c o h o l i c KOH s o l u t i o n , a d d 10 gm. o f t h e s o a p

i n t h i n s h a v in g s o r i n pow der and h e a t u n t i l i t is d is­

so lv e d . C o o l t o 7 0 ° C. a n d t i t r a t e a t t h a t te m p e ra tu re

w i t h N / 1 0 H2S 04 .

2. D ir e c t t i t r a t i o n w ith th e a d d itio n o f b a riu m c h lo r id e .

D i s s o l v e 1 0 gm. so ap i n 100 ml n e u t r a l i n d u s t r i a l a lc o h o l

c o n ta in in g 0 .5 ml o f 0 .5 $ p h e n o lp h ta le in s o lu tio n . Add

5 m l o f h o t n e u t r a l 10$ aq u eo u s s o l u t i o n o f b a riu m c h lo ­

r i d e i n a t h i n s t r e a m , m ix t h o r o u g h l y , and t i t r a t e w ith

N /1 0 HC1 a t 7 0 ° C. u n t i l t h e p i n k c o l o r d i s a p p e a r s *

T he m e t h o d s g i v e n i n S c o t t * s S t a n d a r d M e t h o d s o f

C h e m ica l A n a ly s is ^ a r e a s f o l l o w s :

F r e e A l k a l i o r F r e e F a t t y A c id

The m eth o d s o u t l i n e d w i l l n o t g i v e a b s o l u t e l y a c c u r a t e
r e s u l t s f o r f r e e a l k a l i , b u t w i l l g iv e r e s u l t s s u f f i ­
c i e n t l y a c c u ra te f o r c o n t r o l o r p r a c t i c a l soap a n a ly s e s .
T h e a c c u r a c y i s p r o b a b l y c l o s e t o - £ .0 1 $ NagO.

(a) When " B u i l d e r s " ( o r F i l l e r s ) A r e Low i n A m ount a n d

A r e N o t D e t e r m i n e d , — W e ig h a 20 gm. s a m p l e ( . 0 5 ) r a p i d l y
and t r a n s f e r t o a 500 m l. E rle n m e y e r f l a s k c o n t a i n i n g
1 0 0 m l. o f h o t , n e u t r a l 9 5 $ a l c o h o l . Cover th e f l a s k w ith
a w a tc h g l a s s an d d i s s o l v e t h e soap a s r a p i d l y a s p o s s i b l e
b y h e a t i n g on th e ste a m b a t h . Add a f e w d r o p s o f p h e n o l -
p h t h a l e i n a n d t i t r a t e r a p i d l y w i t h N / 4 HgS04 w i t h o u t
filte rin g . Take t h e f i r s t e n d p o in t , d i s r e g a r d i n g a n y
subsequent re tu rn o f c o lo r. C a l c u l a t e t o f r e e NagO ( o r
NaOH) o r KgO ( o r KOH) a s t h e c h a r a c t e r o f t h e s o a p i n d i ­
c a te s. I f th e a lc o h o lic s o lu tio n i s a c id to p h e n o lp h th a le in ,

^ S c o t t *s S t a n d a r d M e t h o d s o f C h e m i c a l A n a l y s i s . N. H.
F u r m a n , e d i t o r , F i f t h E d i t i o n , (New Y o r k : D. Van N o s t r a n d
C om pany, I n c . , 1 9 3 9 ) , V o l . I I , p p . 2 0 3 2 - 3 .
 7

t i t r a t e w i t h N / 1 0 NaOH a n d c a l c u l a t e t h e p e r c e n t a g e o f
f r e e f a t t y a c id as o le ic a c id , o r la u r ic a c id i f coconut
soap. Save th e s o l u t i o n f o r d e te r m in a tio n o f c a r b o n a te s .

( b ) When ’’B u i l d e r s " A re D e t e r m i n e d . — ?7eigh a 1 0 . 0 2 gm.

s a m p l e a n d d i s s o l v e i n 200 m l . o f h o t , n e u t r a l 9 5 $ a l c o h o l .
F i l t e r t h r o u g h a 9 cm. f i l t e r p a p e r i n t o a 5 0 0 m l . I r l e n -
m eyer f l a s k and w ash th e r e s i d u e t h r e e tim e s w ith h o t,
n e u t r a l 95$ a lc o h o l. P r o t e c t f r o m CO2 a n d o t h e r a c i d
fum es d u r i n g f i l t r a t i o n . I f th e soap c o n ta in s b o ra x , o r
p h o s p h a t e s , i t c a n b e w ashed w i t h a l c o h o l i n d e f i n i t e l y
w i t h o u t rem o v in g th e a p p a r e n t a l k a l i n i t y . C over th e f la s k
w ith a w a tch g l a s s and h e a t t o i n c i p i e n t b o i l i n g . T itra te
w i t h N / 4 H2SO4 a n d r e p o r t a s " f r e e Na20 ( o r NaOH)" o r
" f r e e K2O T o r KOH)" a s t h e c h a r a c t e r o f t h e s o a p i n d i c a t e s .
I f t h e a l c o h o l i s n o t p i n k , t i t r a t e w i t h N /1 0 NaOH a n d
re p o rt " fre e f a t t y a c id " as o le ic a c id .

As l o n g a s t h e a n a l y s i s d e a l s w i t h p r o p e r l y s a p o n i f i e d

soaps w ith o u t f i l l e r s , and w ith so a p s i n w h ic h t h e r e a c t i o n

h a s gone to c o m p le tio n , t h e e r r o r seem s t o be s m a ll, but in

s o a p s n o t c o m p l e t e ly s a p o n i f i e d o r c o n t a i n i n g l a r g e am o u n ts

o f a lk a lin e c a rb o n a te s, o r s o a p b u i l d e r s s u c h a s so d iu m p h o s ­

p h a te , so d iu m s i l i c a t e , b o r a x an d so d iu m s u l p h a t e , th e e rro r

w i l l be g r e a t, even i f e q u i v a l e n t a m o u n ts o f so d iu m and f a t t y

a c id io n s a re p r e s e n t. The u n c o m b i n e d s o d i u m i o n s w i l l t a k e

u p c h l o r i n e i o n s f r o m N /1 0 HC1 a n d s o i n t r o d u c e h i g h r e s u l t s .

A f u r t h e r d isa d v a n ta g e i s t h a t th e a lc o h o lic so lu tio n

o f so d iu m h y d r o x id e a b s o r b s c a r b o n d i o x i d e r e a d i l y fro m t h e

a ir, e s p e c i a l l y w hen t h e s o l u t io n i s w eak and i s c o o lin g .

E x c lu sio n o f a i r in t h i s r e s p e c t i s e s s e n tia l to p re v e n t th e

in tro d u c tio n o f t h i s erro r.

S o ap s w h ic h a r e s a l t s o f w eak a c i d s and s t r o n g b a s e s

h y d ro ly z e a c c o rd in g to th e d e g re e o f d i l u t i o n and te m p e ra tu re
in to fre e f a tty a c id s and a l k a l i h y d ro x id e s. T he f i r s t

h y d r o l y s i s com ponent u n i t e s i n a q u eo u s s o l u t i o n a t ro o m t e m ­

p e r a t u r e w i t h t h e n o n - io n iz e d soap m o le c u le s t o fo rm a c i d

s a l t s w h ic h th e n s e p a r a t e o u t. It is fo r th is reaso n th a t

soap s o lu tio n s r e a c t a lk a lin e , because th e lib e r a te d fa tty

a c i d i s u s e d 'u p f o r t h e f o r m a tio n o f a c id soaps. The sam e

p r in c ip le u n d e rlie s th e s o lu tio n o f soaps in a lc o h o l to som e

e x te n t. T he a c t u a l a l k a l i n i t y o f t h e s o a p i s c a u s e d b y

h y d ro ly sis, b u t th e fre e a l k a l i n i t y c o n s is ts o n ly o f th e

excess fre e a lk a li.

C o n s id e rin g th e a b o v e -m e n tio n ed d i f f i c u l t i e s and d e f i ­

c i e n c i e s o f th e d i f f e r e n t m e th o d s, t h i s i n v e s t i g a t i o n w as

c a r r i e d o u t w ith th e p u rp o s e of t r y i n g to d e v elo p a b e t t e r

p ro c e d u re o f a n a ly s is f o r th e d e te rm in a tio n o f th e f r e e a lk a li

or free f a tty a c id s in s o a p s — a p r o c e d u r e w h ic h i s r a p i d and

w h ic h g i v e s s u f f i c i e n t l y a c c u r a t e p r a c t i c a l r e s u l t s . The

m e t h o d s c h e c k e d w e r e t h e m o s t co m m o n ly u s e d m e t h o d s : th e

m eth o d a d o p te d b y t h e W iz o f f ( W i s s e n s c h a f t l i e h e Z e n t r a l s t e l l e

f u r 01 u n d F e t t f o r s c h u n g ), t h e m eth o d g i v e n i n S c o t t ’ s S ta n d a r d

M e th o d s o f C h e m ic a l A n a l y s i s , V o l. II, and t h e m eth o d i n

G r i f f i n ’ s T e c h n i c a l M eth o d s o f A n a l y s i s , p. 371.
44
I v o r y s o a p , m ade b y P r o c t o r a n d G a m b le , 99T0U $ p u r e ,

was u s e d a s s t a n d a r d . I v o r y soap c o n s i s t s o f 25$ ta llo w , 25$

o f c o c o n u t . o i l ^ . and 50$ h a rd e n e d f i s h o i l s . . T h i s _ s o a p _is_.m ore. _

d i f f i c u l t t o d i s s o l v e t h a n s o a p s m ad e o f l o w t i t e r o i l s , w h ich
m o s tly in c lu d e o i l s o f lo w e r m o le c u la r w e ig h ts and a r e , a ls o ,

s t i l l m ore d i f f i c u l t t o filte r. The s o l u t i o n s e t s im m e d ia te ly

t o a g e l on t h e c o ld f i l t e r p a p e r . For th is rea so n i t had to

be f i l t e r e d th ro u g h a h o t w a te r b a th .

T h is so a p w as fo u n d to h a v e , a c c o rd in g to th e W iz o ff

and S c o t t ’ s 'm e th o d s , 0 .0 2 4 $ f r e e a lk a li. T h is a n a l y s i s w as

r e p e a te d by b o i l i n g f o r 5 m in u te s u n d e r th e r e f lu x eo n d en ser,

f o r th e re a s o n g iv e n l a t e r , and t h e so ap was fo u n d t o c o n ta in

0 .0 2 $ f r e e a l k a l i . A ll f u r t h e r c a l c u l a t i o n s and e x p e rim e n ts

w e re b a se d on t h i s re s u lt.

It is im p o rta n t, f o r th e rea so n s a lre a d y s ta te d , to

in su re first c o m p le te s a p o n i f i c a t i o n o f t h e sa m p le b e f o r e

titra tio n o f th e e x c e ss a l k a l i . T h is i s r e a d i l y a c c o m p lish e d

by b o ilin g i t u n d er th e r e f lu x condenser in a lc o h o l. D r.

H e tz e r h a s d e te rm in e d s a p o n i f i c a t i o n v a lu e s o f d i f f e r e n t

o ils and f a t s , such as ta llo w , p a lm k e rn e l o i l , a ra c h id o il,

soyabean o i l , c o tto n se e d o i l , and h a rd e n e d f i s h o i l . He

b ro u g h t th e m ix tu re , c o n sistin g of fa t, a lc o h o l and a lc o h o lic

p o ta sh s o lu tio n , t o b o i l i n g and t i t r a t e d it im m e d ia te ly . For

th is 2 1 /2 m in u te s w ere u se d . N ext h e d e te rm in e d th e s e

v a lu e s a t i n te r v a l s a t 5, 10, 20 a n d 3 0 m i n u t e s a n d f o u n d

t h e v a lu e s a s in T a b le I .

® D r. H e t z e r , "The S a p o n i f i c a t i o n R a te o f F a t s and
O i l s a n d i t s ' S i g n i f i c a n c e " , f o r t h e " D e t e r m i n a t i o n o f t h e " T re e ""
A l k a l i i n S o a p ,” S e i f e n s i e d e r Z e itu n g . 2 3 :4 6 3 , Ju n e 5, 1935.
 10
TABLE I

SAPONIFICATION VALUES OF SOME FATS AND OILS

AFTER DIFFERENT PERIODS OF BOILING

1' ' "■

A c id S a p o n if ic a tio n v a lu e a f t e r :
M a te ria l V a lu e In itia l 5 m in . 10 m i n . 20 m in . 30 m in .
B o ilin g B o ilin g B o ilin g B o ilin g B o ilin g

T a llo w 1 .8 142 193 198 198 196

0 .9 $ 72$ 98$ M ean : 1 9 7
100$ 100$ 100$

P a lm -
k ern el 1 1 .6 17 2 218 242 244 244
O il 4 .8 $ 70$ 89$ 99$
100$ 100$

Peanut
F a tty 1 2 0 .5 1 80 192 193 193 193
A c id s 63$ 93$ 9 9 .5 $
100$ 100$ 100$

Soyabean
O il 19 12 9 184 190 190 1 8 9 .5
10$ 68$ 97$
100$ 100$ 100$

C o tto n ­
seed 2 .7 169 196 197 197 19 7
O il 1 .4 $ 86$ 99$
100$ 100$ 100$

C oconut
O il 0 .7 218 25 2 259 25 7 258
0 .3 $ 84$ 98$ M ean: 2 5 8
100$ 100$ 100$

H ardened
F ish 5 .9 140 17 9 183 185 185
O il 3 .2 $ 76$ 97$ 99$
100$ 100$
 11

From t h i s , o n e c a n s e e t h a t 10 m i n u t e s b o i l i n g are

s u f f i c i e n t to in s u r e 100$ s a p o n if ic a tio n . B ut s i n c e th e soap

in th e s a m p le i s a l r e a d y s a p o n i f i e d a n d t o p r e v e n t l o s s e s b y

a c tio n on th e g l a s s , 5 m in u te s* b o i l i n g w as assum ed t o be

su ffic ie n t fo r th is e x p e rim e n t.

To c h e c k t h e e f f e c t o f a l k a l i c a r b o n a t e s o n t h e a n a l y ­

s i s ■when f i l t e r i n g is re q u ire d , and from t h e f a c t t h a t I v o r y

soap i s a p u r e s o a p , s e v e r a l s a m p l e s c o n t a i n i n g 1$ s o d i u m

c a r b o n a te w ere p r e p a r e d , t o w h ic h d i f f e r e n t am o u n ts o f so d iu m

h y d ro x id e w ere added t o p ro d u c e th e f r e e a lk a lin ity . The

f r e e a l k a l i c o n te n t in th e so ap t h u s p r e p a r e d w as 0 .0 5 $ , 0 .1 $ ,

0 .2 $ , 0 .3 5 $ f r e e a l k a l i . T h is was o b t a i n e d s im p ly b y a d d in g

t h e p r o p e r d i f f e r e n c e o f so d iu m h y d r o x id e i n t h e fo rm o f

N /1 0 NaOH s o l u t i o n t o t h e s o a p a n d v a r y i n g t h e a m o u n t o f t h e

soap. T he f r e e a l k a l i c o n t e n t , i n o t h e r w o rd s, w as r a i s e d

in th e seco n d e x p e rim e n t b y 0 .3 $ , in th e t h i r d by 0 .0 8 $ , in

th e f o u r t h b y 0 .1 8 $ , e tc . T h is r e l a t i v e c o m p a riso n , I b e lie v e ,

is s u f f i c i e n t l y a c c u ra te to p o in t o u t th e d e fic ie n c y o f any

m e th o d w h ic h em p lo y s f i l t e r i n g , because th e f i l t e r ab so rb s

so d iu m h y d r o x id e . ( M i l l a r d a n d H a r k i n s a l s o m ade d e t e r m i n a ­

tio n s of su rface te n s io n by r e la tiv e c o m p a r i s o n , u s i n g com m er­

c i a l s o a p s t o w h ic h d i f f e r e n t s a l t s h ad b e e n a d d ed , and not

b y s t a r t i n g w ith c h e m ic a lly p u re s o a p s .)

The s i x d i f f e r e n t s a m p l e s o f s o a p w e r e a n a l y z e d a c c o r d ­

in g to t h e m eth o d s o f S c o t t , u sin g f i l t e r i n g , and s ix o th e r

 la
sa m p le s th e n w e re a n a ly z e d by s e p a r a t i n g t h e i n s o l u b l e r e s i ­

due b y c e n tr if u g in g . The r e s u l t s t h e n w e re c o m p a re d .

T h e m l N /1 0 NaOH w e r e a d d e d t o 95 m l p r e v i o u s l y b o i l e d

and n e u tr a liz e d a b s o lu te a lc o h o l i n th e p r e s e n c e o f 0 .5 ml

0 .5 $ p h e n o lp h th a le in s o l u t io n . The s o l u t i o n t h e n w a s m ad e u p

t o 100 m l w i t h w a t e r a n d a d d e d t o a w e i g h e d p r o p e r a m o u n t o f

so ap i n a 150 ml b e a k e r. T h e s a m p l e now c o r r e s p o n d e d t o

e x a c t l y 5 gm. o f s o a p . T h is w as d i s s o l v e d u n d e r h e a t i n g i n

th e b e a k e r and th e n t r a n s f e r r e d im m e d ia te ly t o a 300 ml

E rle n m e y e r f l a s k . A r e f l u x c o n d e n se r f i t t e d w ith a c a lc iu m

c h l o r i d e tu b e w as a t t a c h e d , an d t h e m ix tu r e was b o i l e d f o r

5 m in u te s and f i l t e r e d a t o n c e t h r o u g h a 9 cm f i l t e r p a p e r ,

in s e r te d in a h o t w a te r fu n n e l, a n d w a s h e d w i t h t h r e e 50 m l

p o r t io n s o f 95$ h o t n e u t r a l e th y l a lc o h o l.

T h is e x p e r im e n t was t h e n r e p e a t e d , w i t h th e e x c e p ti o n

t h a t t h e soap w as n o t f i l t e r e d as b e fo re , b u t po u red i n to a

100 m l c e n t r i f u g e t u b e k e p t w arm i n a h o t t e m p e r a t u r e w a t e r -

b a t h , . and p l a c e d i n t o t h e c e n t r i f u g e and t h e in s o lu b le m a tte r

was th ro w n o f f . The c l e a r r e d l i q u i d w as p o u r e d o f f i n t o a

2 5 0 m l w arm ed E r l e n m e y e r f l a s k a n d i m m e d i a t e l y t i t r a t e d at

7 0 ° C. T he r e s i d u e w a s s h a k e n w i t h a b o u t t e n 2 0 m l p o r t i o n s

o f h o t n e u t r a l a lc o h o l u n t i l i t w as c o l o r l e s s and p o u re d i n to

a 2 50 m l E r l e n m e y e r f l a s k , kept in th e w a te rb a th , and co v ered

w ith a c a lc iu m c h lo r i d e tu b e . T h is t h e n a l s o was t i t r a t e d at

7 0 ° C. The t o t a l m l o f N /1 0 NaOH ? / e r e r e c o r d e d i n T a b l e I I .
 TABLE I I

COMPARISON OP ACID VALUES OBTAINED BY FILTERING AND CENTRIFUGING

E x p e ri­ F ree ml T o ta l F i l t e r M e th o d C e n t r i f u g e M e th o d
m ent A lk a li N /1 0 F ree m l I1/10 P e rc e n t­ P e rc e n t­ m l 1tylO P e rc e n t­ P e rc e n t­
(1 ) C o n t e n t NaOH A lk a li - (E>) age o f age o f («3) age o f age o f
i n N /1 0 a d d e d in HC1 INaOH C o r r e s ­ C o rres­ HC1 NaOH C o r r e s ­ C o r r e s ­
NaOH i n (3 ) S a m p le p o n d in g p o n d in g p o n d in g p o n d in g
O rig in a l (4 F ree
A lk a li
F ree
F a tty -
F ree
A lk a li
F ree
F a tty
Soap
(2) (6) A c id a s (9) A c id a s
O le ic O le ic
A c id A c id
(7) ( 10)

1 0.02 0.00 0.02 0.20 0 .1 0 .2 5 0.020

2 0 .4 0 0 .0 5 0.20 0 .1 0 .2 5 0.020

3 1.00 0.10 0 .2 5 0 .1 4 1.10 0 .0 8 8

4 2 .3 0 0.20 0 .3 0 0 .0 2 4 2.20 0 .1 8

5 3 .5 0 0 .3 0 0 .6 0 0 .0 4 8 3 .4 0 0 .2 7

6 4 .2 5 0 .4 0 1.00 0 .0 8 0 4 .0 5 0 .3 2

1 m l N /1 0 NaOH = 1 m l N /1 0 HC1 = .0 2 8 2 g O l e i c A c id = . 0 0 4 g NaOH

 14

P ro m t h i s t a b l e we c a n s e e a n d p r o v e t h a t f i l t e r i n g

o f t h e w eak a l k a l i n e a lc o h o lic soap s o l u t i o n in t r o d u c e s g r e a t

e rro rs. A c o m p a r is o n o f c o lu m n s 3 , 5 , a n d 8 sh o w s t h a t

N / 1 0 NaOH w a s l o s t w h e n t i t r a t e d back. C o lu m n s 4 , 6 /7 , and

9 /1 0 g iv e in f o r m a tio n o f t h e l o s s in f r e e a l k a l i . T he d i f ­

f e r e n c e m u st h a v e b e e n a b s o rb e d b y t h e f i l t e r p a p e r , w h ic h

r e ta in s th e in so lu b le a lk a li s a lts and f i l l e r s . For th is

r e a s o n m eth o d s w h ic h p r e s c r i b e f i l t e r i n g sh o u ld be abandoned;

c e n tr if u g in g sh o u ld be s u b s ti t u t e d f o r i t . Even i f th is does

n o t g iv e th e d e s ire d s a t i s f a c t o r y r e s u l t s , a t le a s t q u ite

u s e f u l v a lu e s can th u s be o b ta in e d .

A new m e t h o d m a k i n g u s e o f t h e c e n t r i f u g e w i l l b e

g iv e n . T h i s m e th o d w i l l s e r v e t o d e te r m i n e f r e e a l k a l i an d

f r e e f a t t y a c id s in h ard soaps, so ap -p o w d ers, and o th e r so ap s

i n w h ic h b u i l d e r s a r e p r e s e n t , b y m eans o f o n l y one m eth o d .

I t w i l l e l i m i n a t e t h e n e c e s s i t y o f tw o m e t h o d s , as i s re q u ire d
6
i n S c o t t ’ s S t a n d a r d M e th o d s o f C h e m i c a l A n a l y s i s .

The m e t h o d i s a s fo llo w s: M easu re o u t i n a 400 m l

b e a k e r 95 m l e t h y l a l c o h o l , add 0 .5 ml 0 .5 $ p h e n o lp h th a le in

so lu tio n , h e a t on th e e l e c t r i c h o t p l a t e to b o i l i n g and n eu ­

t r a l i z e w i t h N /1 0 NaOH s o l u t i o n . D is s o lv e im m e d ia te ly w ith

t h i s n e u t r a l i z e d h o t a l c o h o l a 5 gm. sa m p le o f t h e so a p on

th e hot p la te and b o i l u n d e r a r e f l u x c o n d e n se r f o r 2 l / £

m in u te s. Four th is s o lu tio n in to a 100 ml c e n t r i f u g e tu b e

^ ££• a n t e . PP* 6 -7.

 15

which h a s b e e n k e p t w arm i n a w a t e r b a t h , t o s e p a r a t e t h e
in so lu b le m a tte r. Pour o ff th e s u p e rn a ta n t l iq u i d and

titra te w i t h N / 1 0 NaOH o r N /1 0 HC1 t o t h e e n d p o i n t a t 7 0 ° C . ,

h e a tin g a g a in i f n e c e ss a ry . Shake o u t th e r e s id u e w ith

SO m l p o r t i o n s o f h o t n e u t r a l a l c o h o l , c e n trifu g in g each

tim e , and p o u r th e c l e a r s u p e r n a ta n t l i q u i d o f f i n to a

2 5 0 m l E r l e n m e y e r f l a s k w h i c h i s k e p t a t a p p r o x i m a t e l y 7 0 ° C.

and f i t t e d w ith a c a lc iu m c h lo r id e tu b e . When a t l e a s t t e n

20 m l p o r t i o n s o f h o t n e u t r a l a l c o h o l . h a v e b e e n c o l l e c t e d ,

o r w h en t h e s o l u t i o n i s c o lo rle ss, as in th e case o f fr e e

a lk a lin ity , titra te a g a in a t 70° C . , and add t h e r e s u l t i n

ml to th o s e found in th e f i r s t titra tio n , c a lc u la te , and

rep o rt as fre e so d iu m h y d r o x i d e o r f r e e f a t t y a c i d s .
 16
SUMMARY

The d e t e r m i n a t i o n o f t h e f r e e a lk a li and f r e e f a t t y

a c id s in soaps is an im p o r ta n t q u e s tio n , beeause i t e n a b le s

t h e soap m a n u f a c tu r e r t o c o n t r o l th e am ount o f f r e e a lk a li

w h ic h s h o u ld b e p r e s e n t t o p r e v e n t r a n c i d i t y i n soaps.

D e s p ite th e v a s t am ount o f l i t e r a t u r e e s t a b l i s h e d and th e

e f f o r t s m ade b y t h e m any i n v e s t i g a t o r s , t h i s p ro b lem

re m a in e d one o f t h e o b s c u r e f a c t s in soap in d u s tr y .

Many m e t h o d s h a v e b e e n r e c o m m e n d e d b a s e d o n s e p a r a t ­

in g th e a lc o h o l i n s o l u b l e m a t te r by f i l t e r i n g or p re c ip ita t­

in g th e c a r b o n a te s w ith b a riu m c h lo r i d e , o r sa ltin g out of

th e soap and th e n s u b s e q u e n t t i t r a t i o n . But i t i s im p o ssi­

b le to o b ta in r e l i a b l e r e s u l t s by any one o f th e su g g e ste d

m eth o d s f o r s e v e r a l r e a s o n s : t h e s o a p m ay n o t b e c o m p l e t e l y

sa p o n ifie d , th e soap h y d r o ly z e s , carbon d io x id e i s absorbed

by th e h o t a lc o h o lic a lk a lin e so lu tio n , and f i l t e r p a p e r

ab so rb s fre e a lk a li.

C o n sid e rin g th e s e d i f f i c u l t i e s , th is in v e s tig a tio n

was c a r r i e d o u t w i t h t h e p u r p o s e o f d e v e lo p in g a b e t t e r p r o ­

c e d u re o f a n a l y s i s w h ic h i s r a p id and g iv e s r e l i a b l e p r a c ­

tic a l re s u lts .

I v o r y so ap was c h o s e n a s c o m p a r a tiv e s t a n d a r d . D if­

f e r e n t a m o u n ts o f f r e e a l k a l i w ere added to tw e lv e d i f f e r e n t

sa m p le s, a n d t h e s e w e r e a n a l y z e d b y two m e t h o d s . S ix w ere
 17
a n a l y z e d b y t h e m e th o d g i v e n i n S c o t t ’ s S t a n d a r d M e th o d s o f

C h em ical A n a l y s i s , u s i n g f i l t e r i n g , and th e o t h e r s i x by a

m eth o d e m p lo y in g c e n t r i f u g i n g fo r th e se p a ra tio n o f th e

in s o lu b le m a tte r. A c o m p a riso n o f t h e d a t a o b ta in e d sh o w e d

t h a t t h e f i l t e r m e th o d g a v e i n a c c u r a t e r e s u l t s . In th re e

c a s e s ev en f r e e f a t t y a c i d was fo u n d i n s t e a d o f f r e e a lk a li.

On t h e o t h e r h a n d , c l o s e r r e s u l t s w ere o b ta i n e d b y c e n t r i ­

fu g in g . The f i l t e r p a p e r a b s o r b s f r e e a lk a li to a la rg e

e x te n t.

A new m e t h o d b a s e d o n s e p a r a t i n g o f t h e a l c o h o l

i n s o l u b l e m a t t e r b y c e n t r i f u g i n g w as d e v e lo p e d .
BIBLIOGRAPHY
 BIBLIOGRAPHY

A llg e m e in e 01 und F e t t Z e itu n g . 3 8 :4 0 9 (1 9 3 5 ). T h. R u e m le ,

" F re e and A c t u a l Soap A l k a l i . ”

A m e ric an P e r f u m e r . 2 9 : 4 0 3 - 4 , O c to b e r , 1 934. K n i g g e ," D e t e r m i ­

n a t i o n o f ’F re e A l k a l i ’ in S o a p s.”

A n a ly s t. 6 2 :3 6 -4 1 , 1937. A n a l y t i c a l M e t h o d s C o m m i t te e : S u b ­
c o m m i t t e e o n M e t h o d s o f S o a p A n a l y s i s , R e p o r t No. 3 ,
"T h e D e t e r m i n a t i o n o f F r e e A l k a l i i n S o a p s . "

J o u r n a l A m e ric a n C h e m ic a l S o c i e t y . 5 9 :2 6 4 4 -7 (1 9 3 7 ). A. R.
O l s o n a n d R. S . H a l f o r d , "T h e R a t e a n d M e c h a n is m o f
H y d ro ly s is o f T e r t i a r y B u ty l C h l o r id e .”

K o llo r d B e ih e f te , 4 5 :2 5 3 -3 0 2 (1 9 3 7 ). L o t t e r m o s e r an d G hose,
’• P o t e n t i o m e t r i c T i t r a t i o n s o f S o d iu m S a l t s o f F a t t y A c i d s .

R a y o n a n d M e l l i a n d T e x t i l e M o n t h l y . V o l . XV I, J a n u a r y , 1 9 3 5 ,
p . 55; F e b r u a r y , 1935, p . 43. D a v is o n , "The M e th o d s o f
D e te rm in in g o f ’ F re e A lk a lis .’ ”

S e i f e n s ie d e r Z e itu n g . 6 2 :4 6 3 -4 (1 9 3 5 ). D r . H e t z e r , ”T h e
S a p o n i f i c a t i o n R a te o f F a t s and i t s S i g n i f i c a n c e f o r t h e
D e te rm in a tio n o f th e f r e e a l k a l i in S o a p s ."

S e i f e n s i e d e r Z e itu n g . 6 1 :7 7 2 -3 (1 9 3 4 ). G. E n i g g e , ”The
D e te rm in a tio n o f F re e A lk a li in S o a p s .”

T ra n s . F a rad a y S o c i e t y . 3 1 :1 5 3 -6 4 (1 9 3 5 ). M. E. L a i n g ,
M c B a ln , d e l a t i o n o f l l e c t r o k i n e t i c a n d E l e c t r o l y t i c
M o v e m en t, a s I l l u s t r a t e d b y t h e T r a n s p o r t o f E l e c t r i c i t y
th r o u g h Soap A c i d s . ”

Z e i t s c h r i f t f u r A n a l y t i s c h e C h e m i e . 105 B a n d , 7 u n d 8 H e f t ,
p . 269. H. B a g g e s g a a r d - R a s m u s s e n , " T i t r a t i o n s c h w a c h e r
S a u re n und B asen in W a s s e r-A lc o h o l-G e m is c h e n .”