The P e n n s y l v a n i a S t a t e C o l l e g e

T he G r a d u a t e S c h o o l

D e p a rtm e n t o f C e ra m ic s

S tu d ie s on th e H y d ra tio n o f C la y s

A T h e s is

By

A ugust C a rl S i e f e r t

S u b m itte d i n P a r t i a l F u l f i l l m e n t o f t h e R e q u ire m e n ts

F o r th e D egree o f D o c to r o f P h ilo s p h y

A u g u st, 1942

A pproved 2. O , 1942
By 'V ^ r y Z - " - _______
H e a d /o f t h e D e a p r t m e n t o f C e ra m ic s
 TABLE OF CONTENTS

I * CLAY-WATER RELATIONS

Im p o rta n c e o f C la y -W a te r R e l a t i o n s h i p s . 1

S t r u c t u r e o f C la y M in e r a ls 2

C o n cep t o f C la y s a s C o l l o i d a l E l e c t r o l y t e s 5

C auses o f Io n A d s o rp tio n 7

E f f e c t o f I o n i c S iz e and P o l a r i z a t i o n 8
T ypes o f B ase E xchange R e a c tio n s 12
R a te o f B ase E xchange R e a c tio n s IS

E q u ilib riu m o f B ase Exchange R e a c tio n s 15

F o rm s o f W a t e r i n t h e W a t e r H u l l 16

T h e o r ie s o f A d s o r p tio n o f W ater 16

The C o m p r e s s i o n T h e o r y 17

In flu e n c e o f s tr u c tu r e o f C la y M in e ra ls 18

P l a n a r W a t e r a n d B r o k e n B ond W a t e r 20

F a c to rs In flu e n c in g t h e C o n d i t i o n o f t h e Wra t e r
In th e H u ll 20

H y d ra tio n o f C a tio n s 20

E ffe c t of Io n ic S iz e and P o l a r i z a t i o n 24

The D onnan E q u i l i b r i u m 24

In d ire c t E ffe c ts o f A d so rb ed Io n s 25

M e th o d s f o r S t u d y i n g t h e H y d r o p h i l i c N a t u r e
o f C la y s 26

V isc o sity 27

V olum e C h a n g e s 29

V apor P r e s s u r e SI

A d s o r p t i o n o f W a t e r F ro m V a p o r P h a s e
 Page
F re e z in g P o in t 35

D e t e r m i n a t i o n o f Amount o f W a t e r W h ic h
D oes n o t A c t a s S o l v e n t 37

H eat C a p a c ity 37

X -R ay 37

S p e c tro sc o p ic 38

E nergy o f Rem oval o f L iq u id fro m S u r f a c e 38

H eat o f W e t ti n g , W ith I n f l u e n c e o f V a r io u s
F a c to rs 39

a. The N a tu r e o f t h e S u r f a c e 40

E f f e c t o f A dsorbed Io n s 40

b. The N a t u r e o f t h e W e t t i n g L i q u i d 44

c. The Amount o f S u r f a c e 44

c. The P e r m e a b i l i t y o f t h e S a m p le 45.

e. T he D e g r e e t o W h ic h t h e M a t e r i a l
h as b e e n F r e e d fro m W ater 45

f. The D e g r e e t o W h ic h t h e M a t e r i a l h a s
b een F re e d fro m A d so rb e d G a se s 46

g. T he H i s t o r y o f t h e M a t e r i a l 46

h. O th e r H eat E f f e c t s 46

R e l a t i o n o f H eat o f W e ttin g and A d s o r p tio n o f

W ater fro m t h e V apor P h a se 47

R e l a t i o n o f H eat o f W e ttin g and V i s c o s i t y 48

H e a t E f f e c t s When C l a y s a r e I m m e r s e d i n
E le c tro ly te s 49

G e n e r a l M e th o d s o f C a l o r i m e t r y 50

S p e c ia l C o n s id e r a tio n s i n H eat o f W e ttin g

D e te rm in a tio n s 52
 Page
R e v ie w o f M e th o d s u s e d i n D e t e r m i n a t i o n s
o f H eat o f W e ttin g 52

A p p ro a ch to th e P ro b lem 55

EXPERIMENTAL PROCEDURE

I d e n t i f i c a t i o n and P r e p a r a t i o n o f C la y 57

C la y s U sed i n t h i s In v e s tig a tio n 57

K a o lin 57

Wyoming B e n t o n i t e 57

A rizo n a B e n to n ite 58

D i f f e r e n t i a l T herm al A n a ly se s 59

In te rp re ta tio n o f t h e T h erm al- A n a l y s e s 60

S e d im e n ta tio n T e s ts w ith K a o lin 62

P a rtic le S iz e S e p a ra tio n o f th e K a o lin 63

S e d im e n ta tio n P ro c ed u re 64

V i s c o s i t y M easu rem en ts w i t h K a o lin 65

P r e p a r a t i o n o f H -K a o lin 66

T r e a t m e n t w i t h HC1 66

E le c tro d ia ly sis 67

R em oval o f O rg a n ic M a tte r 67

R e -e le c tro d ia ly se s 68

P r e p a ra tio n of H -b e n to n ite s 68

Rem oval o f O rg a n ic M a tte r 68

E le c tro d ia ly s is 69

M easurem en t o f B ase E xchange C a p a c i t i e s o f

The C l a y s U s e d 70

K a o lin 70
 Page
Wyoming B e n t o n i t e 71

A rizo n a B e n to n ite 71

C o n c lu s io n s R e g a rd in g M in e ra l C o m p o sitio n o f
T he C l a y s 72

K a o lin 72

Wyoming B e n t o n i t e 72

A riz o n a B e n to n ite 72

P r e p a r a t i o n o f Jtfa-, K-_, C a - C l a y s 73

P r e p a r a t i o n o f IMa-, K - , C a - K a o l i n s 73

P r e p a r a t i o n o f K a - , K - , C a-W yom ing

B e n to n ite s 73

P r e p a r a t i o n o f N a -, K -, C a -A riz o n a
B e n to n ite s 73

C a lo rim e try 74

G e n e ra l P ro c e d u re f o r H eat o f W e ttin g
D e te rm in a tio n s 74

P r o c e d u r e f o r D ry in g and E v a c u a tin g C la y 74

C o n s tru c tio n o f th e C a lo rim e te r 76

M e th o d o f W e t t i n g C l a y 77

T e m p e ra tu re M easurem ent 77

S tirrin g 77

P r e p a r a t i o n o f H e a tin g C o il 77

D e te rm in a tio n o f th e R e s is ta n c e of
The H e a tin g C o i l 78

I n s u l a t i o n o f C a lo r im e te r and T e m p e ra tu re
C o n tro l 79

P ro c ed u re f o r th e D e te rm in a tio n o f H eat o f
W e ttin g 80

D e te r m in a tio n o f T e m p e ra tu re I n c r e a s e
on W e ttin g C la y 80
 Page
P rocedure f o r E l e c t r i c a l C a lib r a tio n 81

C a l c u l a t i o n o f H e a t E v o lv e d i n W e ttin g 82

S o r p t i o n o f W a t e r F rom t h e V a p o r P h a s e 83

I n v e s t i g a t i o n o f W ater S o r p t i o n Phenom ena by

D i f f e r e n t i a l T h e r m a l M e th o d s 84

EXPERIMENTAL RESULTS AND DISCUSSION OF RESULTS

H eat o f W e ttin g 86

H e a t o f W e t t i n g o f K a o l i n s i n W a te r 86

H eat o f W e ttin g K a o lin s in A lk a lin e S o lu tio n s 36

B I-K a o lin i n A l k a l i n e S o l u t i o n s 86

H a - , and. K - K a o l i n s i n A l k a l i n e S o l u t i o n s 89

A d d itio n o f Q u a rts to C la y 91

H eat o f W e ttin g o f Q u a rtz i n W ater and

In A lk a lin e S o lu tio n 91

H eat o f W e ttin g K a o l in s , D i l u te d w i t h Q u a r tz ,
I n W ater 91

3 H eat o f W e ttin g K a o lin s , D i l u te d w i t h Q u a r ts

In A lk a lin e S o lu tio n s 92

H eat o f W e ttin g B e n t o n i t e s , D ilu te d W ith

Q u a r ts , i n W ater 92

H eat o f W e ttin g B e n t o n i t e s , D i l u t e d w i t h
Q u a rtz , i n A lk a lin e S o lu tio n s 93

C o n c lu s io n s i n R e g ard t o H eat o f W e ttin g

K a o lin s and B e n to n i t e s i n W ater 93

C o n c lu s io n s i n r e g a r d to W e ttin g K a o lin s
And B e n t o n i t e s i n A l k a l i n e S o l u t i o n s 96

S o r p t i o n o f W ater fro m V apor P h a s e 98

I n v e s t i g a t i o n o f W a t e r S o r p t i o n P h e n o m e n a by
D i f f e r e n t i a l T h e r m a l M e th o d s 101
CONCLUSIONS ' 104
I
 1

IMPORTANCE OF CLAY-WATER RELATIONSHIPS

T he c l a y - w a t e r s y s t e m i s o f fu n d a m e n ta l im p o rta n c e

to c e ra m ic s i n t h a t im p o r ta n t p r o p e r t i e s o f c l a y s ,

e .g ., p la s tic ity , v isc o sity , and d r y in g sh rin k a g e , de­

pend upon t h e r e l a t i o n s h i p o f th e c la y and w a te r.

The p l a s t i c p ro p e rtie s of c la y a re s a t i s f a c t o r i l y

e x p la in e d by th e concept of a film o f w a te r aro u n d th e

c la y p a r t i c l e s . I t is g e n e r a l l y a g re e d t h a t m ost c la y

m in e ra ls a re com posed o f f l a k e - s h a p e d p a r t i c l e s , th a t

th e se p a r t i c l e s i n th e c la y - w a te r s y s te m a r e e n c lo se d by

w a te r h u l l s , and t h a t th e s e w a te r h u l ls d e te rm in e to a

g re a t e x te n t th e p la s tic p ro p e rtie s o f th e sy ste m .

T he y i e l d v a l u e a n d m o b i l i t y o f a q u e o u s s u s p e n s i o n s

o f c la y a re lik e w is e in f lu e n c e d by th e e f f e c t o f th e c la y -

w a te r r e l a t i o n s h i p s . C l a y s u s p e n s i o n s d e p e n d o n tw o

fa c to rs fo r th e ir s ta b ility : (l) th e c h arg e o f th e

p a rtic le s, (2) th e h y d ra tio n o f th e p a r t i c l e s .

The d r y i n g p r o p e r t i e s of c la y s a r e , o f c o u rse,

d ire c tly re la te d to th e w a te r f i lm s w h ic h s u rro u n d th e

c la y p a r t i c l e s . The r e m o v a l o f t h e f i l m s o f w a t e r c a u s e s

t h e c l a y m ass t o s h r i n k , a f f e c ts th e s t r e n g th o f th e p ie c e s

d u rin g d ry in g , and u l t i m a t e l y le a d s to th e d ry s tr e n g th

of th e p ro d u c t.

The a d s o r p t i o n o f w a t e r by c l a y s i s n o t a sim p le

p ro cess. T he f o r m w h i c h t h e w a t e r a s s u m e s a s i t su rro u n d s

th e c la y p a r t i c l e s Is i n f l u e n c e d b y a c o m b i n a t i o n o f m any
 2

in te rre la te d fa c to rs. In c lu d e d i n th e s e a re th e ty p e o f

c la y m in e ra l p r e s e n t , t h e a d s o rb e d io n s on t h e c l a y

( t h e i r ty p e , h y d r a tio n , and c o n c e n t r a t i o n ) , th e p resen ce

o f o rg a n ic m a tte r , and th e p a r t i c l e siz e d is trib u tio n

o f th e c la y .

T he p u r p o s e o f t h i s w o r k i s to stu d y th e r e l a t i o n ­

s h ip o f c la y and w a te r , i . e . , th e h y d ro p h ilic c h a ra c te ris­

tic s of c la y s, by m eth o d s i n w h ic h t h e s e f a c t o r s are

know n o r c o n t r o l l e d . ______________________

THE STRUCTURE OF CLAY MINERALS

It i s now know n t h a t c l a y s a r e c o m p o s e d o f d i s t i n c t l y

c r y s t a l l i n e m a t e r i a l s a n d a r e n o t m ix e d h y d r a t e d o x i d e s

o f s i l i c o n a n d a lu m i n u m . It h a s b e e n sh o w n t h a t c l a y

m in e ra ls a re b u i l t up e s s e n t i a l l y of u n its o f a lu m in a

and s i l i c a . T he a l u m i n a u n i t , or g ib b site sh e e t, c o n sists

o f tw o s h e e t s o f c l o s e l y p a c k e d o x y g e n a to m s o r h y d r o x y l

g r o u p s h e l d t o g e t h e r b y a lu m in u m a t o m s i n s u c h a w ay

t h a t o n e a lu m in u m i s s u r r o u n d e d b y s i x o x 3?-gen a t o m s , or

h y d ro x y l g ro u p s , t h r e e from e a c h s h e e t . The s i l i c a u n it

c o n sists o f a s h e e t o f o x y g e n a.tom s h e l d t o g e t h e r b y

s i l i c o n a to m s. T he s i l i c o n a to m s a r e s u r r o u n d e d b y f o u r

oxygen a to m s, th re e in t h e sheet and one a b o v e . The o x ygen

a to m a b o v e t h e s h e e t l i n k s a s i l i c a u n i t to an a lu m in a

and s e r v e s a s one o f t h e s i x o x y g e n a to m s w h ic h s u r r o u n d

t h e a lu m in u m i n t h e a l u m i n a s h e e t .
 2a

T- 'M 'xr'bd'xr

*
7.2 A sp/‘ so/ Nir ^ 4 a i
1
C-AXIS *■■A ‘ / M s
p ' sc 4 0 * 2 p H )

1 1

b-AXIS-

KAOLINITE PH)bAI4S.4Oio

Schematic presentation of the crystal structure of kaolinite (Afteh Gruner) - Fig. A?

n N ,0
2 (OH)

i- 1 4 . 0 A 4 (OH)+ 2 0
4 AI
C-AXIS 4 (OH) - 2 0
2 Si
6 0
2 Si
2 (OH)
b-AXIS-

MONTMORILLON1TE
(0H)1.1AI4 Sie 0 (b-nH?0
Schematic presentation of the crystal structure of montmorijonite (Edleman)- Fiq. B*
*From Grim (I).
 Two m a i n g r o u p s o f c l a y m i n e r a l s a r e g e n e r a l l y

re c o g n iz e d . The k a o l i n g r o u p h a s a c r y s t a l l a t t i c e w h ic h

i s m ade u p o f o n e s i l i c a s h e e t to one a lu m in a s h e e t .

The m o n t m o r i l l o n i t e g r o u p h a s a n a lu m i n a s h e e t s a n d ­

w i c h e d b e t w e e n tw o s i l i c a sh e e ts. The k a o l i n m in e r a l s

in c lu d e k a o li n i te , n a c r i t e , d ic k ite , h a llo y s ite and o th e r s .

The m o n t m o r i l l o n i t e g r o u p i n c l u d e s m o n t m o r i l l o n i t e , b e i -

d e llite , p y r o p h y l l i t e , n o n t r o n i t e , and h y d ro u s m ic a .

A th ird g ro u p , th e i l l i t e s , has r e c e n t l y been de­

sc rib e d (l). T h e ir b a s ic s t r u c t u r e is s im ila r to th a t of

th e id e a l m o n tm o rillo n ite s t r u c t u r e , th a t i s , it c o n sists

of a g ib b site s h e e t jo in e d by s h a re d oxygens to a s h e e t

o f s i lic o n - o x y g e n t e t r a h e d r a on e a c h s i d e . A c o n sid e r­

a b l e num ber o f s i l i c o n a to m s i n th e s i l i c a sh e e ts, h ow ever,

a r e r e p l a c e d b y a lu m in u m a t o m s (l). Such a s u b s ti t u t io n

d e s tr o y s th e b a la n c e o f e l e c t r o n d i s t r i b u t i o n , re s u ltin g

in s ilic a s h e e ts c a rry in g a n e t n e g a tiv e c h a rg e . T hese

c h a rg e s m ust be b a la n c e d by p o s i t i v e io n s, and K io n s

g e n e r a l l y b a la n c e su c h a c h a rg e and a c t a s a b r id g e b e­

tw een a d j a c e n t u n i t s .

The s t r u c t u r a l u n i t s i n m o n tm o rillo n ite a re Iq o s e ly

h e ld to g e th e r in th e d ir e c tio n o f th e c - a x is , and w a te r

may e n t e r b e t w e e n t h e m , c a u s i n g th e l a t t i c e to expand.

G rim ( l ) in d ic a te d th a t th e s t r u c t u r a l u n i t A l^ S ig O g Q C O H )^

s u g g e s t e d b y H ofm ann e t a l . (2) fo r m o n tm o rillo n ite i s a

b a la n c e d u n i t and d o es n o t s a t i s f a c t o r i l y e x p la in th e sw e l­
 4

lin g in th e p resen c e o f w a te r, th e h i g h "base e x c h a n g e

c a p a c i ty , and th e l a r g e a d s o r p t i o n b e tw e e n t h e b a s a l p l a n e s .

A m o re s a t i s f a c t o r y e x p la n a tio n of th e se p r o p e r tie s is

p o s s i b l e i f we c o n s i d e r a s t r u c t u r e s u c h a s t h a t p r e s e n t e d

b y E d e lm a n a n d F a v e j e e (5 ) . T he s i l i c a sheet is c o n sid e re d

to have th e c o n f i g u r a t i o n o f c r i s t o b a l i t e . A c c o rd in g t o

th is schem e, th e fo rm u la o f th e s i l i c a s h e e t becom es

O^Si^PeCOH)^,; o f t h e w h o l e m i n e r a l (O H )-L gA l^ S igO ^ g .nH ^ O .

T he m i n e r a l s h o u l d t h e n c o n t a i n 3HgO p e r A lg O g w h e n n = 0 .

G rim ( l ) d e s c rib e d th e k a o li n i te s t r u c t u r e a s w o rk ed

o u t by G ru n er ( 4 ) . K a o lin ite is com posed o f a g i b b s i t e

s h e e t w ith a s in g le te tra h e d ra l s ilic a sh e e t* The l a t ­

tic e does n o t expand w ith v a ry in g w a te r c o n te n t, p ro b a b ly

becau se o f th e a t t r a c t i o n o f 0 a n d OH l a y e r s w h e n k a o l i n i t e

u n its a re s ta c k e d one above a n o th e r .

As m i g h t b e e x p e c t e d f r o m t h e d i f f e r e n c e s in stru c ­

tu re , th e g ro u p s have p r o p e r t i e s w h ic h a r e v e ry d i f f e r e n t .

The k a o l i n m i n e r a l s a r e o n l y s l i g h t l y h y d ra te d and have

re la tiv e ly lo w a d s o r p t i v e p r o p e r t i e s . M o n tm o rillo n ite ,

on th e o th e r h an d , is h ig h ly h y d ra te d and h as p ro n o u n ced

a d so rp tiv e p r o p e r tie s . C a tio n s and w a te r a re a d so rb e d

on th e in n e r s u r f a c e s o f m o n t m o r i l l o n i t e a s w e l l a s on

th e o u te r s u r f a c e s , a c c o rd in g to H e n d ric k s e t a l . (5 ).

As f o r i l l i t e , H auser (6 ) p o i n t s o u t t h a t K+ i s th e o n ly

one o f t h e io n s,c o m m o n ly fo u n d i n t h e s o i l , w h ic h i s so

la rg e th a t i t cannot p e n e tra te in to th e open h ex ag o n al

sp a c e s o f th e oxygen l a y e r o f th e s i l i c a sh e e t. The K
 5

"bond b e t w e e n t h e u n i t s of i l l i t e p r e v e n ts s w e llin g by

w a te r e n te r in g i n b e tw e e n t h e u n i t s , as i t d o e s i n m o n t-

m o rillo n ite s.

CONCEPT OF CLAYS AS COLLOIDAL ELECTROLYTES

O ver a p e r i o d o f m any y e a r s t h e c o n c e p t o f c l a y s a s

c o llo id a l e le c tro ly te s has been g r a d u a lly d e v e lo p e d .

The a d s o r p t i o n o f i o n s b y c l a y s h as b e e n c o n s i d e r e d by

som e p e o p l e t o b e l a r g e l y a p h y s i c a l p h e n o m e n o n , b y o t h e r s

to be l a r g e l y c h e m ic a l.

J. T . Way ( a b o u t 1 8 5 0 ) w a s o n e o f t h e f i r s t t o s t u d y

th e base exchange p r o p e r tie s o f c la y m in e r a ls . He f o r m u ­

la te d th e fo llo w in g e i g h t l a w s o f b a s e e x c h a n g e , su m m ar­

i z e d by W ie g n e r (7 ):

1. When a s o i l i s b rought in to c o n ta c t w ith fre e

a lk a lie s in so lu tio n , th e s e d is a p p e a r c o m p le te ly .

T o ta l a d so rp tio n ta k e s p la c e .

2. T o t a l a d s o r p t i o n t a k e s p l a c e a l s o w hen s o i l com es

in to c o n ta c t w i t h s u s p e n s io n s o f l i q u i d m anure.

3. I f s o i l i s b ro u g h t in to c o n ta c t w ith s a l t s , th e

w h o le o f t h e s a l t i s n o t ad so rb ed ; a c tu a lly a

sp littin g ta k e s p la c e . O n ly t h e p o s i t i v e p o r ­

i tio n i s r e t a i n e d ;* t h e a c i d —
u a r t re m a in s u n a l t e r e d

in s o lu tio n (b ase ex ch an g e). In th e p la c e o f th e

ad so rb ed p o s itiv e c o n s titu e n t th e re i s fo u n d

a fte r w a r d s i n th e s o l u t i o n an e x a ic tly e q u iv a le n t
 am ount o f a n o th e r p o s i t i v e c o n s titu e n t— g e n e ra lly

so d iu m o r c a l c i u m .

4. The s p e e d o f t h e a d so rp tio n i s v ery g r e a t.

5. The am o u n t o f s o i l a n d t h e am o u n t a d s o r b e d a r e

n o t p r o p o r tio n a l to one a n o th e r.

6. The a d s o r p t i o n r e a c h e s a n u p p e r l i m i t a t a c e r ­

ta in c o n c e n tra tio n .

7. The t e m p e r a t u r e has o n ly a s m a ll in f lu e n c e on

th e am ount o f a d s o r p tio n .

8. T h is b a se exchange i s c a u se d by com pounds o f

s ilic ic a c i d w i t h a lu m i n u m o n o n e h a n d a n d w i t h

s o d i u m a n d ammonium o n t h e o t h e r .

It is r e m a r k a b l e how l i t t l e t h e s e o r i g i n a l la w s

p r o p o s e d b y Tfifay h a v e b e e n c h a n g e d . Way a d v a n c e d a c h e m i c a l

e x p la n a tio n f o r th e p ro c e s s o f base exchange i n s p i t e of

th e a b n o rm a litie s o f sp eed of r e a c tio n , in flu e n c e of

te m p e ra tu re , e x is te n c e o f th e ly o tr o p ic se rie s, e tc .

A t t h e t i m e Way m ad e h i s o b s e r v a t i o n s , L i e b i g , n o t

k n o w in g t h e la w o f m ass a c t i o n , sa id t h a t W ay’ s c o n c l u ­

s i o n s w ere t h e o r e t i c a l l y im p o ssib le . L ie b ig ’ s id e a s

w ere s o h i g h l y c o n s i d e r e d th a t l i t t l e m ore w as d o n e o n

th e stu d y o f b ase exchange r e a c tio n s f o r m any y e a r s th e re ­

a fte r.

T he s t u d y o f t h e c a u s e s o f i o n a d s o r p t i o n a n d b a s e

exchange r e a c tio n s in c la y s has been g r e a t l y adv an ced by

s o i l c h e m is ts , i n c l u d i n g W ie g n e r (7 ), B ra d fie ld (8 )(9 ),

M a tts o n ( 1 0 ) , M eyer ( l l ) , B aver (1 2 ), and Jen n y (1 3 )(1 4 ).

 7

C auses o f Io n A d so rp tio n

The s t a b i l i t y o f c l a y s u s p e n s i o n s i s known t o d e p e n d

on th e io n w h ic h I s a d s o r b e d . The s t a b i l i t y of c o llo id a l

c la y s u s p e n s io n s d ep en d s on t h e c h a rg e o f th e p a r t i c l e s

and on t h e i r h y d ra tio n . T he k i n d o f i o n w h i c h i s ad so rb ed

by th e c l a y e x e r t s its i n f l u e n c e on b o t h o f t h e s e fa c to rs.

M ost c l a y p a r t i c l e s c a rry a n e t n e g a tiv e ch arg e,

w h ic h , if su ffic ie n tly g re a t, causes th e m t o r e p e l e a c h

o th e r. Jo h n s o n a n d N o rto n (15) have d is c u s s e d th e o rig in

of th is ch arg e, a n d h a v e s h o w n t h a t i t m ay b e d u e t o

p r e f e r e n t i a l a d s o r p t i o n o f OH i o n s o r t o d i s s o c i a t i o n o f

p o s i t i v e l y c h a rg e d io n s fro m t h e c l a y s u r f a c e . In e ith e r

case, c l a y p a r t i c l e s m ay b e v i s u a l i z e d a s c o l l o i d a l a n io n s

s u rro u n d e d by p o s i t i v e l y ch arg ed c a t io n s . In th is m anner

th e H e lm h o ltz d o u b le l a y e r i s fo rm ed . T he i o n s in th e

o u te r p a rt of th e H e lm h o ltz d o u b le l a y e r a r e th o s e w h ic h

a re re p la c e d in b ase exchange r e a c t i o n s .

In d isc u ssin g th e p ro b le m o f a d s o r p t i o n , H auser (6)

sta te d t h a t a l i m i t e d n u m b e r o f n e g a t i v e c h a r g e s may b e

ad so rb ed i n th e b ro k en edges o f th e s i l i c a a n d a lu m in u m

la y e rs. He f e l t t h a t in a s m u c h a s t h e S i an d A I a to m s a r e

em bedded i n c a v i t i e s f o r m e d b y t h e m u c h l a r g e r 0 o r OH

a to m s, t h i s ty p e o f a d s o r p tio n I s q u e stio n a b le . A d sorp ­

tio n o f OH I o n s f r o m t h e m ed iu m t h e n may b e c o n s i d e r e d t o

ta k e p la c e in th e b a s a l oxygen s h e e t b ecau se o f th e d ip o le

c h a r a c t e r o f th e 0H -, and a s a r e s u l t th e p a r t i c l e ta k e s
 o

a n e t n e g a tiv e c h a rg e . C a tio n s i n t h e d i s p e r s i o n m ed iu m

th e n fu n c tio n a s c o u n te rio n s i n th e fo rm a tio n o f th e

d o u b le l a y e r .

H auser f u r t h e r s t a t e d (6) th a t " a l l o f t h e a to m s

lo c a te d i n th e edges or c o rn e rs o f th e c r y s ta l s h e e ts

a re not s a tu ra te d . T h e r e f o r e , so m e a d s o r p t i o n o n t h e

broken edges w i l l ta k e p la c e . Even w i t h s m a ll c r y s t a l

fla k e s, ho w ev er, t h e a d s o r p t i v e c a p a c ity due to su c h edges

is s m a ll i n c o m p a ris o n t o a d s o r p t i o n on th e s u r f a c e o f th e

sh e e ts. In th e case o f k a o lin ite , a d s o r p tio n w i l l be

lim ite d c h ie f ly to th e exposed oxygen la y e r s o f th e b a s a l

silic o n -o x y g e n te tr a h e d r a . The s t r o n g OH-H b o n d b e t w e e n

th e c r y s t a l l i t e s (re s u ltin g i n c o m p a ra tiv e ly la r g e p ar­

tic le s) e x p l a i n s why t h e in d iv id u a l k a o lin ite p a rtic le or

a g g lo m e ra te s o f c r y s t a l l i t e s c a r r y a c o m p a r a tiv e ly w eak

n e g a tiv e ch arg e. T h is a ls o e x p la in s t h e lo w s t a b i l i t y of

k a o lin s u s p e n s io n s . ”

E f f e c t o f Io n ic S iz e and P o la r iz a tio n

A c co rd in g t o J e n n y (1 5 )(1 4 ), th e e n e rg y w i t h w h ic h

v a rio u s c a tio n s a re h e l d on t h e s u rfa c e o f th e c la y is

d e te rm in e d by th e e ffe c tiv e siz e o f th e io n . The e n e rg y

o f a d s o rp tio n d e te rm in e s th e p o t e n t i a l . o f th e p a r t i c l e

and th e s t a b i l i t y o f th e su s p e n s io n . A c c o rd in g to

C o u lo m b * s L aw , t h e f o r c e o f a t t r a c t i o n b e tw e e n an a d ­

so rb e d c a t io n and th e a n io n i n th e n e g a tiv e ly ch arg ed

in n e r la y e r i s : F = k e a » e c ___
+ r c )S
W h e re r aQ a n d r ~v* a r e t h e r a d i i o f t h e a n i o n a n d c a t i o n

re s p e c tiv e ly , and e a and e c a r e th e c h a rg e s on th e a n io n

and c a tio n r e s p e c t i v e l y . Thus t h e f o r c e o f a t t r a c t i o n

sh o u ld in c r e a s e as th e ra d iu s o f th e ad so rb ed c a tio n

d ecreases. Je n n y ’s e x p e rim e n ta l r e s u l t s in d ic a te d , how­

ev er, th a t io n ic exchange a c te d i n a m anner o p p o s ite to

t h a t r e q u i r e d b y C o u l o m b ’ s L aw . T hus, th e sm a ll L i io n

is h e l d w i t h m uch l e s s e n e r g y t h a n t h e l a r g e Cs i o n .

T h is a p p a r e n t r e v e r s a l was e x p l a i n e d on t h e b a s i s of th e

h y d ra tio n of io n s . The i o n s i n s o l u t i o n have a l a r g e r

e ffe c tiv e ra d iu s th a n in a c r y s t a l b ecau se o f th e w a te r

h u l l aro u n d th e io n i n s o l u t i o n . W a te r m o le c u le s a r e

a ttra c te d to ' th e io n by e l e c t r o s t a t i c fo rces. S m a ll io n s

a t t r a c t t h e l a r g e s t num ber o f w a te r m o le c u le s b e c a u s e t h e

a t t r a c t i o n v a rie s d i r e c t l y w ith th e ch arg e o f th e io n and

in v e rs e ly w ith th e ra d iu s of th e io n .

Jenny (1 4 ) f e l t t h a t p o l a r i z a t i o n m ust a ls o be con­

sid e re d . A d s o r p t i o n com pounds on t h e s u r f a c e s o f a lu m in u m

silic a te s ta k e an i n t e r m e d i a t e p o s i t i o n b e tw e e n s i n g l e

io n ic m o le c u le s and l a y e r l a t t i c e m o le c u le s . T he s u r f a c e •

io n s a r e n o t sy m m e tric a lly su rro u n d e d by e l e c t r i c ch arg es

of o p p o site s ig n . The c o o r d i n a t i o n n u m b er o f s u r f a c e io n s

is lik e ly to be l e s s th a n t h a t o f th e i n t e r i o r io n s and

c o n se q u e n tly th e io n ic r a d i i w i l l be som ew hat s m a l l e r .

In a tte m p tin g to c a lc u la te io n ic exchange e n e rg ie s on c o l­

l o i d a l a lu m i n u m s i l i c a t e s , i t w o u ld be n e c e s s a r y t o c o n sid e r
 t

10

t h e p o l a r i z a t i o n o f th e d e fo rm a b le s u r f a c e oxygen a n io n

i n th e p re se n c e o f e x c h a n g e a b le c a t i o n s . Such d e ta ile d

c irc u la tio n s have n o t b een m ade.

Jenny f u r t h e r b e lie v e d H+ t o b e m o s t s t r o n g l y a d s o r b e d ,

p ro b a b ly by c h e m ic a l a c t i o n w i t h 0 = . L i + a n d Na+ w e r e

c o n sid e re d to be a t t r a c t e d e le c tro sta tic a lly , p ro b a b ly

th ro u g h m o le c u le s o f w a te r . He a d v a n c e d t h e id e a th a t

w h en s m a l l e r i o n s a r e a d s o r b e d t h e r e i s m o re w a t e r i n t h e

sy s te m b e c a u se a g r e a t e r ^ h o le ” re m a in s to be f i l l e d w ith
°S
w a te r. F o r e x a m p le , t h e v o l u m e o c c u p i e d b y 1 Ca++ = 4 . 9 9 A ,

a n d t h a t o c c u p i e d b y 2 Na+ = 7 . 8 8 ^ . Jenny th e o riz e d

t h a t ad so rb ed io n s o s c i l l a t e irre g u la rly and exchange

o c c u r s w h en a n i o n i n s o l u t i o n s l i p s in to p o s i t i o n b e tw e e n

th e c r y s t a l s a l t and th e o s c i l l a t i n g io n .

B ar and T e n d e lo o (16) d i d n o t b e l i e v e in th e h ydra­

tio n th e o ry as an e x p la n a tio n f o r th e H o fm e is te r s e r i e s

b e c a u se th e y th o u g h t m ono- an d d i v a l e n t io n s c o u ld n o t

be com pared d i r e c t l y on th e b a s i s o f h y d r a tio n and th e y

p o in te d o u t t h a t th e am ount o f h y d r a tio n r e p o r t e d f o r io n s

v a rie s w ith th e in v e s tig a to r. They b e l i e v e d in th e in flu ­

ence o f v a le n c e and p o l a r i z a b i l i t y . They assum ed t h a t

t h e m o re s t r o n g l y a n i o n i s p o la riz e d , th e s tr o n g e r i t is

a ttra c te d by th e o p p o s ite ch arg e o f th e in n e r l a y e r . In

th e H o fm e iste r s e r i e s th e p o l a r i z a b i li t y ru n s p a r a l l e l

to th e ra d iu s o f th e io n , and t h e sam e s e r i e s is fo u n d a s

fo r h y d ra tio n . P o t a s s i u m was s a i d to exchange b e t t e r th a n

m ag n esiu m b e c a u s e i t i s m o re s t r o n g l y p o l a r i z e d . A C a-

c l a y w as s t a t e d t o b e m o re s t r o n g l y h y d ra te d th a n an N a -c la y .
 11

A c c o r d i n g t o G rim ( l ) , P a g e (17) h as show n t h a t

io n ic siz e is im p o rta n t in c a tio n re p la c e m e n t. A c co rd in g

to h is d a ta , io n s o f a s iz e p e rm ittin g th e m t o f i t c lo s e ly

in to th e c a v i ti e s in s id e o f th e hexagonal n e t o f oxygens

are th e l e a s t r e p la c e a b le j f o r e x a m p l e , K+ w i t h a d i a m e t e r

o f £ .6 6 A c l o s e l y f i t s th e c a v i t y w h ic h has a d ia m e te r o f

£ .8 A and i s tig h tly h e ld . T h is i d e a w o u ld r e q u i r e th e

c a tio n s to be h e ld a t th e c l a y m in e r a l s u r f a c e r a t h e r

t h a n a t som e d i s t a n c e f r o m i t , as th e d o u b le la y e r c o n c e p t

re q u ire s. As m e n t i o n e d p r e v i o u s l y , th e d o u b le la y e r con­

c e p t o f H auser (6) a n d J o h n s o n a n d H o r t o n (1 5 ) p i c t u r e s

th e c a tio n s a s b e in g s e p a r a t e d fro m t h e c l a y p a r t i c l e s

b y a n i n n e r l a y e r o f OH i o n s . G rim (l) b e lie v e s t h a t from

a s t r u c t u r a l v ie w p o in t t h i s h y p o t h e s i s d o e s n o t se e m

te n a b le , sin c e t h e c h a r g e s on t h e l a t t i c e a re m a in ly su c h

th a t p o sitiv e c h a r g e s w o u ld be r e q u i r e d to s a tis f y th em .

T he a d d i t i o n o f a l c o h o l h a s b e e n r e p o r t e d to re v e rs e

th e ly o tr o p ic s e r ie s (1 8 , p . £ 9 4)* The d e h y d r a t e d i o n s

are th e n ad so rb ed in th e o rd e r o f t h e i r tru e io n ic siz e ,

not th e ir h y d ra te d s i z e .

W ie g n e r ( 7 ) , M eyer (ll) and o t h e r s h a v e sh o w n t h a t

th e s t a b i l i t y o f c la y s u s p e n s io n s w h ic h a r e s a t u r a t e d w i t h

d i f f e r e n t c a tio n s , fo llo w s th e ly o tr o p ic , o r H o fm e iste r,

se rie s: L i> N a> K > R b> C s. The h i g h e r t h e h y d r a t i o n o f t h e

a d s o r b e d c a t i o n , t h e m o re s t a b l e th e s u s p e n s io n . D iv a le n t
io n s produce l e s s s ta b ility th a n m o n o v a len t i o n s ; triv a le n t

io n s , le ss th a n d i v a l e n t , and H p ro d u c e s th e m ost u n s ta b le

s y s te m .

In c o n sid e rin g th e cau ses of a d so rp tio n by c la y s ,

W ie g n e r f u r t h e r p i c t u r e s th e io n ic exchange as o c c u rrin g

in th e m ic e lle s o f t h e c l a y a n d sh o w e d t h a t t h e io n s o f

t h e o u t e r sw arm a r e t h o s e w h i c h u n d e r g o e x c h a n g e . T he

io n s of th e in n e r la y e r w ere s a id to be in c a p a b le o f

exchange s in c e th e y a re h e ld by a u x i l i a r y v a le n c e f o r c e s ,

c ry sta l la ttic e fo rces, e tc . He a p p a r e n t l y p i c t u r e d , fo r

e x a m p l e , Mg a s f o r m i n g w i t h OH o n t h e c l a y a l e s s so lu b le

com pou nd t h a n C a , S r , or B a. T h e r e f o r e , Mg w o u l d b e

le ss e a s ily d isp la c e d th a n th e s e . W ie g n e r c o n s i d e r e d

H+ a d e h y d r a t e d i o n a n d s h o w e d i t re p la c e d a l l o th e r io n s

m ost e a s i l y .

T ypes o f B ase E xchange R e a c tio n s

W ie g n e r (7 ) n o t e d f o u r t y p e s o f b a s e e x c h a n g e r e a c t i o n s _

as fo llo w s:

"1. C l a y X Na + KC1 = C l a y - K + H a C l

T he l y d r a t i o n o f t h e i o n s p l a y s a n i m p o r t a n t r o l e

h ere, as th e d o u b le l a y e r and th e s o l u t i o n a r e

e q u a lly d i s s o c i a t e d b e fo re and a f t e r th e exchange.

2. C l a y X Ca ( o r B a ) + 2 K C l = C l a y X Kg + C a C l 2 ( o r B a C lg )

The l y d r a t i o n o f t h e i o n s d o e s n o t p l a y s o i m p o r t a n t

a ro le h ere as b e fo re (C a i s m ore t i g h t l y bound

t h a n Ba) b e c a u s e t h e d i s s o c i a t i o n or io n ic

a c tiv itie s in th e d o u b le l a y e r a re n o t th e sa m e a s
f o r t h e Ba c l a y .
 3. C l a y X H + KX = C l a y X K + HX

The h y d r a t i o n o f t h e io n s p la y s a l e s s im p o rta n t

ro le t h e m o re t h e d i f f e r e n c e in th e d is s o c ia tio n

o f th e s o lu tio n b e fo re and a f t e r th e exchange,

th a t i s , th e le s s th e a c i d HX i s d isso c ia te d in

c o m p a r i s o n t o t h e s a l t KX. In g e n e ra l, th e a c t i ­

v ity o f th e io n s in th e d o u b le l a y e r w i l l be

a lte re d by th e t r a n s i t i o n from HX t o KX.

4. C l a y X H + KOH = C l a y X K + Hg 0

H ere t h e h y d ra tio n o f th e io n s p la y s no p a r t ,

sin c e H a n d OH i o n s f o r m u n d i s s o c i a t e d w a t e r

m o le c u le s In th e s o lu tio n . T he i o n i c a c tiv ity

i n th e d o u b le l a y e r is a ls o a lte re d , sin c e in

p la c e o f th e u n d is s o c ia te d and w e a k ly s t a b i l i z ­

i n g XH g r o u p t h e m o r e s t r o n g l y d i s s o c i a t e d and

s t a b i l i z i n g XK o c c u r s , as th e e le c tr o k in e tic

p o te n tia l of th e a c id p a r t i c l e s is in c re a se d

by th e n e u t r a l i z a t i o n . One w o u l d n o t e x p e c t

th a t in n e u tra liz in g a c la y a c id w ith a h y d ro x id e

th e h y d r a t i o n s e r i e s w o u ld p l a y a n i m p o r t a n t p a r t

R a te o f B ase E xchange R e a c tio n s

A c c o rd in g to m ost i n d i c a t i o n s , th e r a t e o f base

exchange r e a c t i o n s is v ery f a s t . As m e n t i o n e d b e f o r e ,

Way i n c l u d e d th is o b se rv a tio n in M s la v /s o f b a s e e x c h a n g e

G e d r o iz , w hose w ork i s su m m arize d b y P ag e (1 9 ), sh o w e d

t h a t th e v e lo c ity o f th e exchange r e a c t i o n by s o i l s and

n e u t r a l s a l t s w as v e r y f a s t , ta k in g p la c e i n from f i v e

seconds to th r e e m in u te s.

The r a t e o f t h e r e a c t i o n w o u ld h e e x p e c t e d to v a ry

w ith th e ty p e o f c la y m in e r a l p r e s e n t . In th e case of

k a o lin ite t h e r e a c t i o n w o u ld he e x p e c te d t o - b e v e r y r a p i d

as a ll th e e x c h a n g e a b le io n s a r e l o c a t e d in th e o u te r

l a y e r o f t h e H e lm h o ltz d o u b le l a y e r . In th e case o f.

m o n t m o r i l l o n i t e , w h e r e a b o u t 8 0% o f t h e e x c h a n g e a b le i o n s ,

ac c o rd in g to H e n d ric k s et a l. (5), a r e l o c a t e d b e tw e e n t h e

in d iv id u a l u n its t h e r e a c t i o n w o u ld be e x p e c t e d t o ta k e

p l a c e m ore s l o w l y .

T he r a p i d r a t e o f r e a c t i o n m ay b e v i s u a l l y d e m o n s t r a t e d

by th e sudden change in ap p aren t v is c o s ity of an H a -c la y

s u s p e n s io n , w h ic h i s d e flo c c u la te d a n d f l u i d , w hen e n o u g h

H io n s a r e added to form an H -c la y . T he s u s p e n s i o n

im m e d ia te ly becom es f l o c c u l a t e d a n d m o re v i s c o u s . It

is q u ite a p p a re n t t l i a t th e m ajo r p a r t o f th e r e a c t i o n

ta k e s p la c e in a v e ry s h o r t p e rio d o f tim e , a l t h o u g h so m e

w ork i n d i c a t e s th a t f in a l e q u ilib riu m m ay b e a t t a i n e d

m u c h m o re s l o w l y .

A fa c to r t o be c o n s i d e r e d i n th e r a t e o f th e r e a c tio n

is th e c o n d i t i o n o f t h e c l a y when t h e e le c tro ly te Is

added. If th e c la y i s in th e d ry s t a t e it m ig h t be e x ­

p e c te d t h a t th e r a t e o f r e a c t i o n w o u ld b e s lo w e r t h a n i f

th e c la y p a r t i c l e s w ere a l r e a d y h y d r a t e d . T he r a t e w o u ld
be p a r t i c u l a r l y slo w i n t h e case of a m in e ra l such as

m o n tm o r illo n ite w here a f i n i t e tim e i s r e q u i r e d to p e rm it

th e p e n e t r a t i o n o f t h e w a te r b e tw e e n th e i n d i v i d u a l

la ttic e la y e rs. T he t i m e r e q u i r e d f o r t h e p e n e t r a t i o n o f

Y^ater i n t o th e l a y e r s w o u ld i n tu rn , d e p en d o n t h e ty p e o f

a d s o r b e d i o n s p r e s e n t b e tw e e n t h e l a y e r s . If th® i o n s w e r e

of s u c h a n a t u r e a s t o fo rm a b r id g e b e tw e e n th e l a y e r s ,

th e e n t r a n c e o f w a te r w o u ld be r e t a r d e d or p re v e n te d .

I t is a l s o w e l l known t h a t t h e r a t e of re a c tio n is

s l o w w h en a n e l e c t r o l y t e is added to a p l a s t i c c la y . In

th is case e q u ilib riu m is re a c h e d slo w ly b ecau se o f th e

d iffic u lty o f 11w o r k i n g i n ” t h e e l e c t r o l y t e in s u c h a way

th a t a ll th e c la y p a r t i c l e s are exposed to it.

E q u ilib riu m o f B ase E xchange R e a c tio n s

The n e q u i l i b r i u m ” o f a b a s e e x c h a n g e r e a c t i o n is

re a c h e d a lm o st im m e d ia te ly (if th e su s p e n s io n i s su ffic ie n t­

ly d ilu te to p e rm it m o b ility of th e io n s). Many a t t e m p t s

(b y V a g e le r and A l t e n (2 0 ) , J e n n y , and o t h e r s ) have been

m ad e t o s e t f o r t h t h e c o n sta n ts o f b ase exchange r e a c tio n s ,

but a ll e q u a tio n s f a i l beyond a v e ry l i m i t e d f i e l d of

a p p lic a tio n . U s u a lly a g iv e n e q u a tio n can be u sed fo r th e

in te rp re ta tio n of a re a c tio n o n ly u n d er th e c o n d itio n s

u s e d by t h e i n v e s t i g a t o r . It a p p e a rs t h a t no s i n g l e equ a­

t io n or s e t o f e q u a tio n s can s a t i s f y th e m u ltitu d e of

c o n d itio n s p re s e n t in base exchange r e a c tio n s .

 16

H y s te re s is has o f te n b een n o te d i n base exchange

re a c tio n s. The e q u i l i b r i u m d e p en d s on th e d i r e c t i o n of th e

re a c tio n . F o r e x a m p le , t h e sam e s t a t e o f e q u ilib riu m is

n o t a tta in e d if th e fo llo w in g r e a c tio n i s a p p ro a c h e d from

th e r ig h t o r th e l e f t :

C l a y OH Na + KC1 = C l a y OH K + N a C l

Thus t h i s is n o t a tru e e q u ilib riu m . No r e a l e x p ­

la n a tio n of th is h y ste re sis has been o f f e r e d . it has

m e re ly been s a i d th a t i t is due to t h e ’’n a t u r e o f th e s u r ­

fa c e .” V a n se lo w (21) fo u n d t h a t m o n o v a le n t i o n s p ro d u c e d

h y ste re sis, b u t d iv a le n t io n s d id n o t. S c lia c h tsc lia b le (2 2 )

fo u n d t r u e e q u ilib riu m o n ly i f th e c h a r a c t e r i s t i c s o f th e

tw o i o n s i n t h e e x c h a n g e w e re s i m i l a r , i.e ., Mg++ a n d C a + + .

He o b s e r v e d i n t e r f e r e n c e e f f e c t s w h e n tw o o r m o re i o n s

w ere p r e s e n t i n th e s o lu tio n . F o r e x a m p l e , K+ a n d NH^+

w ere a d so rb e d i n e q u a l a m o u n ts fro m a m i x t u r e , b u t Na+

was o n l y s l i g h t l y a d s o r b e d i n t h e p r e s e n c e o f K+.

FORMS OF WATER IN THE WATER HULL

T h e o r i e s o f A d s o r p t i o n o f W ater

The s t a t e o f th e w a te r in th e e n v e lo p e a ro u n d c la y

p a rtic le s in th e p re se n c e o f w a te r i s som ew hat u n c e r t a i n .

B ehrens (23) lis te d th e fo llo w in g th e o rie s in reg ard

to a d s o rp tio n o f w a te r:

1. The c o m p r e s s io n t h e o r y , w h ic h h o l d s t h a t t h e

w a te r on th e s u r f a c e is co m p ressed .
 17

2. The c a p i l l a r y c o n d e n s a tio n th e o r y i n w h ic h th e

flu id is c o n sid e re d to be r e t a in e d in th e p o res

as a consequence of i t s su rface te n s io n .

3 .' O th e r t h e o r i e s i n w h ic h t h e w a te r i s c o n sid e re d

to be h e ld by:

a. e le c tro sta tic fo rces.

b. v a le n c e f o r c e s .

The C o m p re s s io n T h e o ry

T h e c o m p r e s s i o n t h e o r y l ia s b e e n f r e q u e n t l y c o n sid e re d

in s tu d ie s o f th e r e l a t i o n o f w a te r to c o ll o i d s . S ev eral

in v e s tig a to rs have c o n s id e r e d th e w a te r e n v e lo p e a s b e in g

b u i l t up o f la y e r s o f u n if o r m ly o r i e n t a t e d d i p o l a r m o le ­

c u le s. S lip p a g e w i t h i n th e w a te r f i l m w as s a i d to ta k e

p la c e in th e p la n e s of th e d ip o la r ends. The w a t e r o f t h e

e n v e lo p e im m e d ia te ly a d ja c e n t to th e c la y - p a r t ic l e su rface

has b e en c o n s id e r e d a s h a v in g a h ig h e r d e n s i t y th a n o r d i­

n a ry w a te r due to th e c lo s e p a c k in g o f th e in n e r-m o s t l a y e r s

o f d i p o le s and a l o o s e r p a c k in g f a r t h e r fro m th e s u r f a c e

o f th e p a r t i c l e .

C hapek (24) m e a su re d t h e d e n s i t y o f w a te r a d s o rb e d

on s o i l s u r f a c e s and r e p o r te d 1 .7 f o r th e f i r s t p o rtio n

ad so rb ed . T h is w a te r he c o n s i d e r e d t o b e u n d e r a p r e s s u r e

o f s e v e r a l h u n d red th o u sa n d a tm o s p h e re s ; th e re fo re he

reaso n ed , it c a n n o t be fro ze n - o r f u n c t i o n a s a s o l v e n t .

Some a u t h o r s have c o n c lu d e d t h a t i f th e h e a t o f w e t­

tin g a p p e a rs o n ly a s a c o n seq u en ce o f th e c o m p re ssio n o f

w a te r on th e s u r f a c e o f th e m a te r ia l, th e h e a t o f w e ttin g

m u st be n e g a t i v e if it is c a rrie d o u t a t te m p e ra tu re s

b e lo w 4 ° C ., a t w h ic h t e m p e r a t u r e w a t e r h a s i t s g re a te st

d e n sity . Jan ert (25) c a rrie d o u t e x p e rim e n ts a t 1° and

3°C » a n d f o u n d t h a t a l t h o u g h t h e h e a t o f w e t t i n g w as l o w e r ,

it w as n o t n e g a t i v e . He c o n c l u d e d t h a t t h e d e n s i t i e s of

w a te r a t n o rm al p r e s s u r e s a re n o t c o n s id e r a b le com pared

to th e in c r e a s e s in d e n s ity due to c o m p re ssio n c a u se d

by s u r f a c e a d s o r p tio n . P a t r i c k a n d F . V. G rim (26) stu d ie d

th e h eat o f w e ttin g of s i l i c a g e l and fo u n d a p o s i t i v e

h e a t o f w e ttin g b e tw e e n 0° an d 4 °C . w h ic h t h e y b e l i e v e d

p re se n te d c o n sid e ra b le e v id e n c e a g a i n s t th e c o m p re ssio n

th e o ry o f h e a t 'o f w e ttin g . They c o n c lu d e d t h a t th e heat

o f w e ttin g is c au sed by ch an g es o f s u r f a c e en erg y a lo n e .

G rim (l) sta te d th a t r e c e n t id e a s o f th e s tr u c tu r e s

o f th e w a te r f ilm do n o t a g r e e w i t h t h e co n cep t of c lo s e

p ack in g o f w a te r m o le c u le s im m e d ia te ly a d ja c e n t to th e

su rface of th e p a r t i c l e . F o r e x a m p le , H o u w in k ( 2 7 )

s ta te d t h a t t h e r e i s no i n c r e a s e d v i s c o s i t y a s w o u ld b e

e x p e c te d i n c lo s e p a c k in g , and N i t z s c h (28) lia s i n d i c a t e d

t h a t th e f i r s t w a te r added to d r ie d c la y m a t e r i a ls assum es

a d e n sity le s s t h a n 1 a n d t h a t a s m ore w a t e r i s added th e

d e n sity g ra d u a lly r is e s to 1 .

In flu e n c e of S tru c tu re o f C la y M in e ra l

The s t r u c t u r e o f th e w a te r in th e film s has been

e x t e n s i v e l y s t u d i e d by. H e n d r i c k s a n d h i s c o lle a g u e s ( e) ( 2 9 )

and i s p a rtia lly s u m m a r i z e d b y G rim ( l ) . H e n d ric k s c o n -

 19

s id e re d a w a te r la y e r to be com posed o f w a te r m o le c u le s

jo in e d in to h e x ag o n a l g ro u p s o f an e x te n d e d hexagonal n e t.

Vllien t h e s u r f a c e o f t h e c l a y m i n e r a l c o n t a i n s h y d ro x y l

groups a s in th e c a se o f k a o l i n i t e , th e o x y g e n a to m s i n

th e w a te r la y e r a re th e n th o u g h t to he bound th ro u g h hyd­

ro g en to som e o f t h e h y d r o x y l s o n t h e s u r f a c e o f th e c la y

m in e ra l.
It is not d iffic u lt to e x p la in th e p re se n c e o f w a te r

w here b o n d s h a v e b e e n b r o k e n , f o r e x a m p le , a t th e edges

of k a o lin ite fla k e s; but i t i s m o re d i f f i c u l t to e x p la in

its p resen ce on t h e p l a n e s w here no b ro k e n b o n d s e x i s t .

I n m o n t m o r i l l o n i t e t h e b a s a l p l a n e s a r e m ade u p o f o x y g e n

a to m s w i t h o u t a n y u n s a t i s f i e d c h arg es and t h ic k film s o f

w a te r c an n o t be v is u a liz e d as e n c lo sin g su c h a s u r f a c e .

S u b s t i t u t i o n s w i t h i n th e m ass m ig h t d e v e lo p c h a r g e s w h ic h

a re s a tis f ie d b y a d s o r b e d c a t i o n s a n d t h e s e c a t i o n s m ay

o r may n o t b e t h e s o u r c e o f a t t r a c t i o n f o r w a t e r d e p e n d ­

in g upon w h e th e r th e s e io n s a r e c a p a b le o f h y d r a t i o n .

S t r a y f o r c e s may a c c o u n t f o r som e s m a l l a m o u n t o f a d s o r b e d

w a te r. A c c o rd in g to H e n d ric k s, o rie n te d l a y e r s o f w a te r

c a n d e v e l o p o n l y w hen t h e s u r f a c e o f t h e f l a k e s carry

p ro je c tin g (OH) i o n s . In m o n tm o rillo n ite , sw e llin g is

s a id to occur because th e u n its o f th e c la y m in e ra l a re

p u sh ed a p a r t by s h e e t s o f w a te r w h ic h a t t a c h th e m s e lv e s

to th e p ro je c tin g (OH) i o n s o f t h e b a s a l s h e e t s . K a o lin ite

w o u ld n o t , a c c o rd in g to t h i s v ie w , d e v e lo p s u c h a s h e e t o f

w a t e r b e tw e e n u n i t s b e c a u s e it does n o t have p r o je c tin g

(OH) i o n s .
 20

P l a n a r W a t e r a n d B r o k e n B ond W a t e r

K e lle y and h is c o lle a g u e s (30) have p o s t u l a t e d tw o

ty p e s o f a d so rb e d w a te r i n c l a y s . One t y p e , " p la n a r w a te r"

c o a ts th e p la n e s u r fa c e s o f th e f la k e s and i s lo o se ly

h e ld . The o t h e r t y p e , "b ro k en -b o n d w a te r ," i s m o re t i g h t ­

ly h e ld a t th e edges of th e s h e e ts . G rim ( l ) p o in te d o u t

t h a t w h ile p la n a r w a te r c o u ld w e ll have th e c o n f ig u r a tio n

d e s c r i b e d by H e n d r ic k s , b r o k e n - b o n d w a t e r w o u ld be e x p e c te d

to be l e s s r e g u l a r l y o r ie n ta te d *

FACTORS INFLUENCING THE CONDITION

OF THE WATER IN THE HULL

H y d ra tio n o f C a tio n s

As G rim ( l ) p o i n t e d o u t , m an y i n v e s t i g a t o r s , in c lu d ­

in g W ie g n e r (7), h av e c o n s i d e r e d t h a t th e ad so rb ed c a tio n s

are h y d ra te d and t h a t th e u n io n o f th e s o l v a t i o n h u lls

form s th e w a te r e n v e lo p e a ro u n d c la y p a r t i c l e s . T hus,

t h e a d s o r b e d c a t i o n s w o u ld d i r e c t l y d e te rm in e th e c h a ra c ­

te ris tic s o f th e w a te r e n v e lo p e . G rim s t a t e d th a t th is

i d e a h a s becom e t o o p r e v a l e n t w i t h o u t a c r i t i c a l s t u d y o f

th e e v id e n c e f o r and a g a i n s t i t .

As s h o w n i n T a b l e I , th e re is a c o n sid e ra b le d i f f e r ­

ence in th e v a lu e s su g g e ste d , and even d i f f e r e n c e s in th e

o rd er o f h y d ra tio n o f th e c a tio n s . G rim s t a t e d , "A tte m p ts

to m easu re th e d e g re e o f h y d r a tio n o f th e c a t i o n s , th e re fo re ,

have n o t p ro v id e d s tr o n g e v id e n c e t h a t th e c a t io n s a re

a c tu a lly h y d ra te d ."
21
21 (To face 22)

TABLE I

I o n ic Radix ir. Angstrom s

D ehydrated H ydrated

A- D'>' C D E F

I-I - 0 .3 5 5.4 ~

Li 0 ,6 3 0,7 3 0 .7 8 10 ,0 3 3 .7 120

Ka 0 .9 8 0 .9 8 0 .9 S 7 .9 0 2 Pj
< . C 66

K 1 .3 3 1.33 1 .3 3 5.32 1 .9 17

Nil* 1 .43 1 .4 3 5 .3 7 -
16

Rb 1 .49 1 .4 8 5.09 l.S 14

Gs 1.6.5 1 .6 5 5 .0 5 l.S 13
Eg 0 .8 9 0 .7 8 0 .7 8 - 5 .4 -

Ca 1 .1 7 1 .0 6 1 .0 6 - 4♦8 -

Sr 1 .3 4 1 .2 7 J.. * { - 4 .8
Fa \ 1 .4 9 1 .13 1 .4 3 - /+ .4 „

Al+-i-+ \ 0 ,7 9 0 .5 7 0 .5 7 - - -
Fc a - M - - - 0 .S3 -
Fs -m- - ■J * 1 ...

S i +-m-> - 0 .3 1 - -

la 1 .3 0 1 .,22 ~ w- — —
C ite d b y Grim (1)

A '- '- K. Z a c h a ria s s e n , Z e it s c h r . K r i s t . 50, 137 (1931)

Ed" V. G0 Id s c hmi d t . V id . D ors k, Akad. O sl c , S k r. l a t h . - n n t’,.1r v , k l . 7

8 (1923, 1 9 2 7 )’

C ite d in (IS )

IE Jen n y , J o a r . Fh;,rs . Chen, 2217-53 (1932)

E, K' P allm an n , Eodenk, P o rsch 6 , 22 (L?38) (Mote: G rin c i t e s P allrnann,

o a t e r r s in g iv in g f ig u r e s as r a d iu s w hich Pallm ann gave as d ia m e te r.
 I

H y d ratio n F o la riz a b i
(Hole liaO) d . 10-24

G* H* J
.-K
- J-* p

tw
l

12 *6 10. 15 1 1 -1 3 0 .0 7 5

8 .4 5. 8 9 *"11 0 .2 1

4 .0 1. 4 Ju
< 0 .8 7

-
-1
i-*M
- f
~ -

- 0 .5 ~ ’ - 1 .3 1

- 0 .2 _ 2 .7 9

1 3 .3 33. 21 20-73 0 ,1 2 .

1 0 .0 22. 28 19-22

3 .2 m
■
ii* -

4 .1 -L
/. 14 13-20 -

- - 57 - 0 .0 6 5
_

0 .0 4 3

F E ite l (2 4 )

G*- H. Remy, Z e i t s e h r . P’n y s . Cheau A b t. A. 3 9 , 467 (1915)

I* II* 3r i n t a i n e r and C • Ra ta n a r a t , Z e it s e h r . a n o rg . a llg e m . . chem.

7 7 1 > 119 r"i q 3 ^ )

J-if- F . B ourdon, 2 . Ron ye r and 0 . Han, Go".pt, re n d ,A c a d .so l . 2 5 ,

*r v i-7 - w 7

C ite d in (18) p . 314

 It s h o u ld be n o t e d t h a t o n ly one v a lu e f o r th e degree

of h y d ratio n of th e hydrogen io n i s in clu d ed in th e above

tab le, a n d many w r i t e r s h a v e c o n s i d e r e d H+ a s a d e h y d r a t e d

ion (W eigner, H auser). It s h o u ld a l s o be p o i n t e d o u t t h a t

th e v a lu e s in th e ta b le r e p r e s e n t th e degree of h y d ra tio n

of th e ions i n f r e e s o l u t i o n and t h e r e i s no a p r i o r i

reason fo r b eliev in g th a t th ese v alu es are any in d ic a tio n

of th e s t a t e of h y d ratio n of th e i o n s when t h e y a r e a d s o r b e d

on th e s u r f a c e of th e c lay p a r t i c l e s .

Jenny (13) s ta te d th a t th e e ff e c tiv e v a lu e of the

io n ic ra d iu s i n c o l l o d i a l sy stem s i s p r o b a b l y som ewhere

b etw een th e c r y s t a l l a t t i c e r a d i u s and th e hydrodynam ic

rad iu s. He a l s o in d ic ate d th at H+ a c t s m o r e e n e r g e t i c a l l y

i n c o l l o i d a l sy stem s t h a n a n Hs O - i o n w o u l d , ( T h e H^O i o n

is o f t e n c o n s i d e r e d t o be t h e a d e q u a te f o r m u la f o r t h e

H Ion).

H o u w in k ( 2 7 ) sta te d th a t th e th ic k n ess o f th e w ater

/ 2 3°\
film (10 - 1 0 A) i s too g r e a t t o be a c c o u n te d f o r by t h e

h y d ratio n of adsorbed c a tio n s , and S p e i l (37) thought t h a t

s o l v a t i o n o f th e ad so rb ed c a t i o n s c a n n o t be th e e n tire

e x p la n a tio n f o r th e w ater f ilm s .

Grim c o n c l u d e d t h a t th ere I s no j u s t i f i c a t i o n f o r the

g e n e r a l assu m p tio n t h a t a l l th e common a d s o r b e d c a t i o n s a r e

h y d r a te d and t h a t so m e o t h e r c a u s e f o r th e developm ent o f

the w a ter f ilm aro u n d th e c la y p a r t i c l e s m ust be s o u g h t.

 E ffect o f I o n ic S iz e and P o l a r i z a t i o n

Jenny (13)(14) a ttrib u te d th e d if f e r e n c e s i n th e w ater

film to d if f e r e n c e s in tlie s i z e of th e adsorbed io n s.

F o r exam ple, if a larg e io n w ere a d s o rb e d , t h e r e w ould

rem ain a s m a lle r sp ace f o r w a te r m o lecu les th an i f a sm all

i o n w ere a d s o r b e d . Jenny a ls o b eliev ed th a t the p o la r iz ­

in g e f f e c t of th e adsorbed c a tio n s on t h e w a t e r w ould

a f f e c t th e w ater h u ll. The p o l a r i z i n g effect is stro n g er

th e g r e a te r t h e charge a n d t h e sm aller th e r a d iu s .

B av er and H orner (31) found t h a t the w ater c o n te n t

o f v a rio u s c la y sy stem s i s in v e rs e ly p ro p o rtio n a l to th e

volum e o c c u p ie d by t h e e x ch an g eab le c atio n s. Baver (32)

sta te d th a t alth o u g h h y g ro sco p icity , i.e ., a d so rp tio n of

w ater vapor, in c re a s e s w ith exchange c a p a c ity (using v a r i ­

ous c la y s ) th e r e l a ti o n s h i p i s n o t a sim p le one. F o r ex­

am ple, t h e amount o f w a t e r a d s o r b e d p e r m i l l i e q u i v e l a n t

o f e x ch an g eab le H io n s in cre ased w ith decreasin g exchange

cap acity .

B usw ell and D u d e n b o stel (33) co n sid ered an i n t e r e s t ­

in g ex p la n atio n fo r th e d iffe re n c e in h y d ra tio n b a sed upon

th e id e a s o f L in u s P a u lin g i n r e g a r d to isom orphous r e p l a c e ­

m ent. T h is e x p l a n a t i o n w ould p e r m i t t h e r e p l a c e m e n t o f

2 Na+ + 2 Ha 0 b y Ca++ + 3 H2 0 .

The Dorman E q u i l i b r i u m

Meyer (ll) u s e d th e Donnan e q u i l i b r i u m (see also

M a t t s o n ( 1 0 ) ( 3 4 ) (J2?0 t o e x p la in th e w ater o f osm otic

 .25

im b ib itio n and s ta te d t h a t bound w a te r i s h eld by th e io n

atm osphere s u r ro u n d in g th e c la y p a r t i c l e . The D o n n a n

eq u ilib riu m e q u a tio n i s m erely a m ath em atical r e p r e s e n ta ­

t i o n w h ic h shows t h a t t h e am ount o f im b ib e d w a t e r d e p e n d s

on t h e H o fm e is te r series and t h e amount o f e l e c t r o l y t e in

th e in te r m ic e lla r so lu tio n . Meyer s t a t e d , ,TA d e c r e a s e o f

io n ic c o n c e n tra tio n o f th e adsorbed ions (Z) cau sed by a

su b stitu tio n o f an io n low er i n th e H o fm eister s e r i e s

(e .g ., calcium ) for one h ig h e r i n t h e s e r i e s (e .g ., sodium ),

o r an i n c r e a s e in th e io n ic co n ce n tra tio n of th e catio n s

and o f th e a n io n s on th e in te rm ic ellar so lu tio n (x) w i t h

(Z) c o n s t a n t . . . w ould r e d u c e t h e amount o f im b ib ed w a te r

per u n it surface of the p a r t i c l e . ”

In d ire c t E ffects o f A dsorbed Io n s

It,Is g e n e ra lly agreed t h a t t h e a d s o r b e d i o n s may

have a more o r l e s s in d ire c t e f f e c t on t h e h y d ratio n of

m o n tm o rillo n ite. C a-m o n tm o rillo n ite does n o t expand, for

ex am p le, b e c a u s e o f t h e b r i d g i n g a c t i o n o f t h e Ca i o n ,

vfhile N a - m o n t m o r i l l o n i t e e x p an d s g r e a t l y because of th e

lack of a b rid g in g effect. Grim ( l ) p o in ted out th a t hyd­

rogen should be e x p e c t e d t o e x e r t no b r i d g in g a c tio n In

m o n tm o rillo n ite, y e t an H -m o n tm o rillo n ite does n o t s w e ll.

He e x p l a i n e d t h i s phenomenon by assu m in g t h a t b e f o r e a l l

t h e a d s o r b e d c a t i o n s a r e r e p l a c e d b y H, s o m e A1 i s rem oved

from' t h e l a t t i c e to occupy exchange p o s i t i o n s . T h i s A1

supp o sed ly e x e r ts a b rid g in g actio n . T his e x p la n a tio n

 26

m ay b e t r u e , b u t i t w ould be h a r d t o e x p l a i n t h e easy

r e p l a c e m e n t o f A1 b y t h e a d d i t i o n o f N a , e s p e c i a l l y when

Na i s n o t a d d e d i n e x c e s s s u f f i c i e n t t o c a u s e a mass a c t i o n

rep lacem en t. It i s w e l l known t h a t H - m o n t m o r i l l o n i t e may

be c o n v e r te d r e a d i l y to N a -m o n tm o rillo n ite , w hich th e n s w e lls

re a d ily .

It is apparent th a t a l l th e p ro p e rtie s of clay s can­

n o t be e x p la in e d s o l e l y on th e b a s is of th e degree of

h y d ratio n of th e adsorbed c a tio n s , b u t any s tu d y w hich

c a n throw, m ore l i g h t on t h e p ro b le m o f a d s o r b e d c a t i o n

h y d ra tio n m ust c o n tr i b u te to a b e tte r u n d erstan d in g of th ese

p ro p erties.

METHODS FOR STUDYING THE HYDROPHILIC NATURE OF CLAYS

The f o l l o w i n g types o f m easurem ents have b e e n u s e f u l

in o b tain in g in fo rm atio n reg ard in g th e n a tu re o f th e

rela tio n sh ip betw een c o l l o i d a l m a t e r i a l s and t h e medium

w h ic h s u r r o u n d s them :

(1) V isco sity

(2) Volume c h a n g e s

(5) Vapor p r e s s u r e

(4) A d s o rp tio n from th e v ap or phase

(5) F reezing p o in t

(6) D e t e r m i n a t i o n o f amount o f w a te r w h ic h w i l l

w ill n o t a c t as so lv en t

(7) Heat c a p a c i t y

(8) X -ray
 27

(9) S p ectro sco p ic

(10) E nergy of rem o v al o f l i q u i d from s u r f a c e

(11) Heat o f w e ttin g

F ollow ing is a d iscu ssio n o f th e m ethods l i s t e d above,

w i t h a r e v i e w o f t h e w ork w h ic h has b e e n done on c l a y s .

V isco sity

V i s c o s i t y m e a s u r e m e n t s may be. u s e d t o s t u d y t h e hydra­

tio n c h arac teristics of c la y s. As m e n t i o n e d p r e v i o u s l y ,

th e a p p a r e n t v i s c o s i t y o f a c la y s u s p e n s io n depends on

th e charge of the c la y p a r t i c l e s and t h e i r h y d ratio n .

In th e case of c lay m in erals of th e k a o lin group, th e charge

of th e p a r t i c l e s is th e dom inant f a c t o r w h ich g o v e rn s th e

v isc o sity . For m in erals of th e m o n tm o rillo n ite group,

the h y d ratio n of th e p a r t i c l e s is p r o b a b l y t h e more im p o r­

tan t in flu e n ce . V i s c o s i t y m e a su re m e n ts by th e m s e lv e s

c a n n o t answ er th e q u e s tio n s concerning th e n a tu r e of th e

h y d ra tio n of c la y m in e ra ls . In c o n ju n c tio n w ith charge

m e a s u r e m e n t s , v i s c o s i t y d e t e r m i n a t i o n s may c o n t r i b u t e m u c h

in fo rm a tio n .

Henry and T a y l o r (3 5 ), Baver (72) and o t h e r s show ed

th at th e v i s c o s i t y of a su sp en sio n i s d e p e n d e n t on th e

re la tiv e volum es o f s o l i d and l i q u i d , in a d d itio n to th e

ch arg e on th e p a r t i c l e s . The v o l u m e t r i c i n t e r f e r e n c e of

th e p a r t i c l e s Is i n c r e a s e d by a n y p r o c e s s w h ic h r e d u c e s

th e a v a ila b le suspending liq u id . I n th e c la y - w a te r system

t l i i s may b e a c c o m p l i s h e d b y t h e h y d ratio n of th e c lay

p a rticle s th ro u g h th e fo rm a tio n o f w ater film s a ro u n d them ,

by s w e llin g of th e p a r tic le s th em selv es, o r by t h e enm esh-

ment o f w a te r b etw een th e p a r t i c l e s w hich c o n s t i t u t e

ag g reg ates. In cre asin g th e charge of th e p a r t i c l e s , in

th e c a s e s w here i n t e r n a l s w e llin g does n o t o c c u r , rem oves

th e e n tra p p e d w a te r and t h e r e f o r e decreases th e v is c o s ity .

Most i n v e s t i g a t i o n s have n o t d i f f e r e n t i a t e d betw een

th e e ff e c ts o f c h a rg e and h y d r a t i o n . It is d o u b tfu l th a t

th e effects of the two v a r i a b l e s a re in s e p a ra b ly co n n ected .

C e ram ists a re n o t s u f f i c i e n t l y aw are t h a t h igh d is p e rs io n

d o e s n o t n e c e s s a r i l y mean lo w v i s c o s i t y , because a h ig h ly

d isp ersed s y s t e m may a l s o b e a h i g h l y h y d r a t e d o n e , s o

i
th at the e f f e c t s of th e h y d ra tio n ov erb alan ce th e e f f e c t s

of charge.

F or ex am ple, Baver found t h a t h ig h ly c h a rg e d L i -

and N a - c l a y s w e re more v i s c o u s th a n Ca- and M g-clays b e ­

cause the hig h h y d ra tio n o f th e form er e f f e c t i v e l y in c re a s e d

th e s i z e o f th e p a r t i c l e s , and t h e r e f o r e in c re a se d the

v isc o sity of the su sp en sio n . The c l a y B a v e r u s e d was

c h ie fly b e id e llite .

On t h e o t h e r han d , N o r to n and .Jo h n so n show ed t h a t

w ith very d i lu t e k a o lin ite su sp en sio n s th e v i s c o s i ty be­

h av io r i s l a r g e ly a r e s u l t o f th e charge of th e p a r t i c l e s .

A p p a r e n t l y t h e y f o u n d 110 d i f f e r e n c e in th e charge of v a rio u s

a lk a li-c la y su sp en sio n s, b ecau se th e y r e p o r te d no d i f f e r e n c e

in th e ir v is c o s ity b eh av io r.
 29

Volume C h a n g e s

The a t t r a c t i o n o f a c l a y f o r w a t e r may h e m e a s u r e d

by s o r p t i o n o r s w e llin g m easu rem en ts, i n w hich th e in tak e

o f w a te r from a f r e e w a te r s u r f a c e is d eterm in ed .

S w e l l i n g may o c c u r b e c a u s e o f f ilm s o f w a te r around

the p a rticle s of c la y , or because o f p e n e tr a tio n o f w ater

b etw een th e u n i t s of the c lay s tr u c tu r e itse lf. Baver (32)

show ed t h a t f o r Putnam c l a y (b eid e llite ) sw ellin g v aried

in th e fo llo w in g order:

L i >Na> Ca>Ba >H >K.

T h u s K+ b e h a v e d l i k e th e d i v a l e n t io n s and l i k e H+. For

b e n to n ite th e fo llo w in g s e r i e s was f o u n d :

Wa^Li>K>Ca=Ba > H .

Baver thought t h a t d eh y d ra tio n of K -s a tu ra te d c la y s

causes an i r r e v e r s i b i l i t y of th e sy stem . The K i o n s

a p p a r e n tly hold th e s h e e t - l i k e p articles to g eth er w ith

more e n e r g y t h a n do L i+ o r Na+. Baver s ta te d t h a t any

e x p la n a tio n o f th e effect of d if f e r e n t i o n s on h y d r a t i o n

m ust ta k e i n t o c o n s id e r a tio n n o t o n ly th e o rien tin g ten d ­

ency o f th e io n s f o r w ater m o le cu le s, t h e number and k i n d

o f io n s p r e s e n t and t h e i r a c tiv itie s, but a lso th e a t t r a c ­

t i v e 'p o w e r o f t h e i n n e r la y e r fo r w ater as i t may b e a f f e c t e d

by io n ic ad so rp tio n .

Grim (l) r e v i e w e d t h e w o r k o f H o f m a n n a n d K. G i e s e ,

who f o u n d t h a t C a - m o n t n o r i l l o n i t e s w e l l s m o r e t h a n

m o n t m o r i l l o n i t e , a n d t h e w o r k o f H o f m a n n a n a B i l k e who s t a t e d

t h a t m o n t m o r i l l o n i t e w i t h e i t h e r N a + , G a + + , o r H+ s w e l l s a b o u t
t h e same s m a l l am ount a t low v a p o r p r e s s u r e s , but th at

at h ig h er vapor p re s s u re s N a -m o n tm o rillo n ite s s w e l l much

m ore t h a n t h e o t h e r s . Grim c o n c l u d e d t h a t in general

L i + a n d Na+ f a v o r g r e a t s w e l l i n g , w h e r e a s C a + + , Mg++,

A 1 + + + , H+, F e + + + , a n d K+ t e n d t o r e d u c e it.

Grim (l) sta te d t h a t alum inum c a n be rem oved fro m

th e m o n tm o rillo n ite l a t t i c e by a c i d l e a c h i n g u n til th ere

is a ratio o f o n ly 1 .7 Ai to 4 S i b e fo re the l a t t i c e stru c­

tu re is d estro y ed . He b e l i e v e d t h a t A1+++ i s r e m o v e d f i r s t

to exchange p o s itio n s b e fo re going i n t o so lu tio n .

G rim b e l i e v e d t h a t th is r e m o v a l o f A1+++ t o the ex­

c h a n g e p o s i t i o n s may b e r e s p o n s i b l e f o r th e n o n -sw ellin g

ch aracteristics of electro d ialy zed b en to n ite, w hich sh o u ld

be an H - b e n t o n i t e , b u t may b e i n r e a l i t y an A l-b e n to n ite

to a c e r ta in ex te n t.

It is in te restin g to n o te th a t sw ellin g is rep o rted

to be a l w a y s a c c o m p a n ie d b y a vo lu m e c o n t r a c t i o n o f t h e

t o t a l sy stem , a lth o u g h th e so lid p h a s e i t s e l f may i n c r e a s e

in siz e. T his i s a fu rth er i n d ic a tio n o f th e com pression

o f w a ter around th e s u r f a c e of the p a r tic le s .

Bouyoucos (36) m e a su re d , by means o f a d i l a t o m e t e r ,

t h e volum e c h a n g e s o c c u r r i n g when s o i l s w e re m ixed w i t h

w ater. In o rd er to d is p la c e a l l the a i r , t h e s o i l was

f i r s t m ixed w i t h c a rb o n t e t r a c h l o r i d e ; w a t e r was t h e n a d d e d

on t o p o f t h e l a y e r o f c a r b o n t e t r a c h l o r i d e . The w a t e r a n d

s o i l w ere b r o u g h t i n c o n t a c t by t i p p i n g the d ila to m e te r.

 31

It was f o u n d t h a t a h i g h c o l l o i d c o n te n t or a high o rg an ic

c o n te n t gave th e g r e a te s t c o n tra c tio n .

R u ssell (37) stu d ied th e in te r a c tio n of c lay w ith

w a te r and o rg a n ic l i q u i d s by m e a s u rin g s p e c i f i c volum e

changes. He f o u n d a r e d u c t i o n i n s p e c i f i c volum e w h ic h

was p r o p o r t i o n a l t o t h e number o f e x c h a n g e a b le io n s p r e s e n t

and to t h e mean d e n s i t y o f t h e i r s u r f a c e charge. The

red u ctio n of s p e c ific volum e, in d ecreasin g order of e f­

f e c t i v e n e s s , w as; Mg, C a , H, N a , K . T h is o r d e r was i n d e ­

p e n d e n t o f t h e l i q u i d s u s e d p r o v id e d no c h e m ic a l a c t i o n

to o k p la c e b e tw ee n th e e x c h a n g e a b le c a t i o n and th e l i q u i d .

Mg i o n s o n c l a y v f e re r e p o r t e d to have a b o u t s e v e n , and

Ca a b o u t t h r e e m o r e m o l e c u l e s o f w a t e r o f h y d r a t i o n t h a n

Na a n d K i o n s . T he i n t e r a c t i o n o f c la y w i t h w a te r and

organic liq u id s c o n ta in in g a p o la r group cau sed a c o n tr a c ­

tio n of liq u id volum e, w h ic h f o r n h o m io n ic " c l a y s , satu rated

t o pH 7 w i t h b a s e , is n early p ro p o rtio n a l to t h e number

a n d mean d e n s i t y o f t h e e x c h a n g e c a t i o n on t h e s u r f a c e .

(3 ) Vapor P r e s s u r e

B riggs (38) u s e d v a p o r p r e s s u r e m easurem ents t o s t u d y

w ater r e la tio n s h ip s in p ro te in s. He c am e t o t h e c o n c l u ­

sio n t h a t a t low v a p o r p r e s s u r e the p a r t p lay e d by th e

c o llo id itse lf i n b in d in g th e w ater i s m ore i m p o r t a n t

t h a n ' t h a t p la y e d by th e bound I o n s ; as th e a c t i v i t y of the

w ater approaches 1 .0 th e e f f e c t of th e c o llo id becomes

 0#C /

i n s i g n i f i c a n t a s com pared to t h a t r e s u l t i n g from t h e io n s

w h i c h a r e "bound h y s a l t v a l e n c i e s t o the c o l l o i d . W ith

io n s in eq u ilib riu m w ith w ater, th en , th e degree o f hydra­

tio n of the c o llo id is d eterm in ed l a r g e l y , if not e n tire ly ,

by t h e number o f c a t i o n s o r a n i o n s w h i c h may b e i o n i z e d

from i t , y e t h e ld by s a l t v a l e n c i e s , and by t h e a c t i v i t y of

t h e w a t e r a g a i n s t w h i c h i t may b e i n e q u i l i b r i u m .

(4) A d s o r p ti o n o f W ater fro m Vapor P h ase

When a s a m p l e o f dry clay is p la c e d i n an atm o sp h ere

o f w ater vapor w ater m o lecu les a re adsorbed u n t i l an

eq u ilib riu m is reached. The a m o u n t o f w a t e r a d s o r b e d i n ­

c re a s e s w ith th e s p e c if ic surface o f the c la y , th e vapor

p r e s s u r e o f th e w a te r and w i t h d e c r e a s in g tem p eratu re.

M itsc h erlic h (59) trie d to calcu late the s u r f a c e

a r e a o f c l a y assum ing t h a t t h e w a t e r was p r e s e n t i n a

m onom olecular l a y e r . By u s i n g t o l u e n e a n d w a t e r he

a t t e m p t e d t o d i s t i n g u i s h b e t w e e n ’’i n n e r s u r f a c e " and " o u t -

er su rfa c e ." The t o l u e n e was t h o u g h t t o b e a d s o r ^ d only

on th e o u te r s u r f a c e w h ile th e w a te r m o lecu les p e n e tr a te d

e o ^ th e pores. He d e f i n e d h y g ro sc o p ic ity as th e m o istu re

c o n t e n t a t w h ic h a s o i l no l o n g e r e x h i b i t s heat of w ettin g .

Baver (52) in d icated th a t a h y steresis e f f e c t m ust

be c o n s i d e r e d i n v a p o r p r e s s u r e m axim a. A c lay th a t has

a p p a r e n tly re a c h e d e q u ilib riu m w ith a g iv e n atm osphere

b y d r y i n g down f r o m a h i g h e r m o i s t u r e c o n t e n t c o n t a i n s

m ore w a t e r t h a n one w h ic h h as r e a c h e d e q u i l i b r i u m by a d ­

so rb in g m o istu re.
 Thomas (40) and o t h e r s found S -sh ap e d c u rv e s r e l a t i n g

vapor p ressure to m o istu re c o n te n t w ith an i n f l e c t i o n

p o i n t a t a b o u t 50$ r e l a t i v e h u m id ity . They show ed t h a t

a t low v a p o r p r e s s u r e s v e r y s m a l l am ounts o f w a te r w ere

adsorbed, a n d a s t h e v a p o r p r e s s u r e w a s i n c r e a s e d m u ch

larg er am ounts o f w a t e r w e re r a p i d l y a d s o r b e d , and th e n

as t h e v a p o r p r e s s u r e became v e r y h i g h , o n ly a l i t t l e m ore

w a t e r was a d s o r b e d . I t was s u g g e s t e d t h a t the f l a t p o si­

t i o n o f t h e c u r v e a t low m o i s t u r e c o n t e n t s is due to th e

f a c t t h a t th e w a ter m o lecu les a re tig h tly bound and have

a low v a p o r p r e s s u r e . The s u c c e e d i n g l a y e r s o f w ater

cause la rg e in creases in th e vapor p ressu re u n t il f in a lly

larg e am ounts o f w a t e r a r e r e q u i r e d to produce a change

in vapor p re ssu re .

Thomas a l s o s t u d i e d the effe cts of rep laceab le bases

on h y g r o s c o p i c i t y and fo u n d t h a t K -, N a - , and N H ^ - s a t u r a te d

so ils adsorbed le s s w a ter th a n th e H- a n d C a - s a t u r a t e d

sam ples a t low v a p o r p r e s s u r e s . At h ig h vapor p r e s s u r e s ,

th e N a -s a tu ra te d s o i l s adsorbed th e l a r g e s t amount o f w a t e r .

He a t t r i b u t e d th is b e h av io r of th e N a -s o il to th e g r e a te r

d is p e r s io n and s w e llin g at higher m o istu re c o n te n ts and

th e p o s s i b i l i t y of the ex isten ce of h y d rates of th e c o l­

lo id a l m ateria ls p resen t.

Baver (32) sh o w ed t h e s e same g e n e r a l t e n d e n c i e s f o r

P u tn a m cla-y ( b e i d e l l i t e ) . At a r e la tiv e hu m id ity o f 9 9 .8 $

th e h y g ro s c o p ic ity fo llo w ed th e o rd e r:
 Li> Na> H>Ba> Ca> K .

At a r e l a t i v e h u m id ity o f 7 4 .9 $ th e o r d e r w as:

H> Ca> Li> N a> B a>K .

K uron (41) found s i m i l a r effects and a t t r i b u t e d th ese

resu lts to th e h y d ra tio n o f th e ex ch an g eab le c a t io n s .

T h e p e c u l i a r b e l i a v i o r o f t h e Na+ w a s e x p l a i n e d o n t h e

b asis th at a t low v a p o r p r e s s u r e s th e deh y d rated N a -clay

c o n t a i n s a l a r g e number o f p o re s t h a t a r e to o s m a ll f o r the

e n tran ce of w ater m o le c u le s. C a - c la y on th e o t h e r hand •

i s m ore o p e n a n d i s a b le to a d s o r b m ore w a t e r . At h ig h e r

vapor p re s s u re s , th e N a -c la y s w e lls and a d so rb s g r e a t e r

am ounts o f w a te r t h a n t h e C a - c l a y .

M a tts o n (10) b e l i e v e d t h a t m o le c u l a r ly a t t r a c t e d w a te r

is r e p r e s e n t e d by h y g ro s c o p ic w a te r and i s m a n if e s te d by

h e at of w ettin g and c o n t r a c t i o n o f volum e. He c o n s i d e r e d

th ese e f f e c ts a r e s u l t o f th e s u rfa c e and n o t o f th e

exch an g eab le io n s .

The h y g r o s c o p i c i t y o f H - c l a y t r e a t e d w i t h v a r i o u s

i o n s w as g i v e n by A l t e n an d K u rm ies (18) in th e fo llo w ­

ing o rd er of d ecreasin g h y g ro sco p icity :

L i , N a , K, C a , B a .

These r e s u l t s a r e o p p o s e d t o t h o s e g i v e n by B a v e r (32),

who s t a t e d t h a t Na+ a n d K+ d e c r e a s e d th e hygroscopic

c o efficien t.

The a p p a r e n t c o n t r a d i c t i o n c a n p r o b a b l y be e x p l a i n e d

by th e f a c t t h a t n e i t h e r a u th o r d e fin e d the c la y m in e ral

 55

p resen t. I n th e c a s e w here th e a l k a l i e s in creased th e

h y g ro sco p icity , t h e r e was p r o b a b l y a . m i n e r a l o f t h e

m o n tm o rillo n ite ty p e p r e s e n t , w hich s w e lle d w ith th e a l ­

k a lie s, w hile i n th e c a se where a l k a l i e s d e c re a s e d th e

h y g ro sco p icity , t h e m i n e r a l s p r o b a b ly w ere o f t h e n o n ­

sw ellin g ty p e. The e f f e c t o f o r g a n i c m a t t e r on h y g r o s c o p i ­

c ity is a n unknown v a r i a b l e . E ith er e f f e c t c o u ld be c a u s e d

by o r g a n i c m a t t e r , w h ic h m ig h t (l) sw ell or (2 ) a c t a s a n

in h ib ito r to p rev en t sw ellin g .

Oden ( 4 2 ) fo u n d no c o r r e l a t i o n b e tw e e n t h e amount o f

surface, as d e te rm in e d by s e d im e n ta tio n m ethods, and t h e

amount o f h y g ro sc o p ic w a te r .

S in c e th e a d s o r p t io n o f w a ter from th e v ap o r p h ase

is a rela tiv e ly slow p r o c e s s , th e amount o f tim e t h a t th e

sam ples a r e exp o sed to a n a tm o sp h e re havin g a c e r t a i n

re la tiv e hum id ity i s p ro b ab ly an im p o rta n t f a c t o r in the

v alu es o b ta in e d . I t w ould be e x p e c te d t h a t c e r t a i n ty p es

o f a d s o r b e d i o n s vrould g r e a t l y a f f e c t t h e r a t e of w ater

a d so rp tio n . For th is reason, c o m p ariso n s o f w a te r a d s o r p ­

t i o n v a l u e s o b t a i n e d b y v a r i o u s w o r k e r s c a n n o t b e m ade

w ith o u t a d e t a i l e d know ledge o f th e h is to r y of th e m a te r ia l,

as w e ll as its m in e ra l c o m p o sitio n and th e ty p e o f a d so rb e d

ion.

(6) F reezin g P o in t

Bouyoucos (45) c l a i m e d t h a t t h e r e was a c l o s e r e l a ­

tio n sh ip b etw een th e h e a t o f w e ttin g and th e w a te r w hich

 36

failed t o f r e e z e when s o i l s w e re s u b j e c t e d t o lo w t e m p e r a ­

tu res. " F r e e " w a t e r was f o u n d t o f r e e z e r e a d i l y when

su p erco o led to -1 .5 °C . C a p i l l a r y a d s o rb e d w a te r was fo u n d

to f r e e z e from - 1 .5 ° to - 7 8 ° C . , w h i l e com bined w a t e r

(w ater o f h y d ra tio n p lu s w a te r o f " s o l i d s o lu tio n ”) d id

not freeze a t -78°C .

B u e h r e r and R osenblum (44) m ea su re d bound w a t e r i n

so ils by t h e u s e o f a d i l a t o m e t e r a n d a f r e e z i n g m ethod

and r e p o r t e d t h a t even s e a sand caused l e s s w a te r to f r e e z e

th an in th e absence of th e s o lid phase.

Jo n e s and G o rtn e r (45) u s e d a d i l a t o m e t r i c m ethod i n

th e m easurem ent o f bound w a te r i n s i l i c a g e ls and g e l a t i n .

A l e x a n d e r a n d Sh aw ( 4 6 ) used d i e l e c t r i c co n stan t

changes to stu d y th e f re e z in g process in order to calcu late

th e a c tiv ity o f w ater in c o l l o i d a l sy stem s.

A n o th e r m ethod i s th e c a l o r i m e t r i c m ethod, u se d by

R obinson ( 4 7 ) , i n w h i c h t h e s y s t e m i s m a i n t a i n e d a t so m e

low t e m p e r a t u r e u n t i l a l l th e w a te r w hich w i l l f r e e z e

has been f r o z e n . T hen t h e a m o u n t o f h e a t n e c e s s a r y t o

m elt th e ic e is fo u n d , and from t h a t th e amount o f i c e

w h i c h was p r e s e n t i s c alcu lated .

The w o rk o f K i s t l e r (48), how ever, t h r o w s much d o u b t

on t h e v a l i d i t y o f any w ork w i t h f r e e z i n g m ethods, b ecau se

th e s y s te m m u st be i n e q u i l i b r i u m in order fo r the r e s u lts

to be tr u s tw o r th y . K i s t l e r showed t h a t i s o l a t e d drops o f

w a t e r may n e v e r f r e e z e (even though th e y a re n o t " b o u n d " ).

Thus f o g s r e m a in as w a t e r a t tem p eratu res f a r belo w f r e e z i n g .

 37

(6) D e t e r m i n a t i o n o f Am ount o f W a t e r W h i c h d o e s n o t

Act as S o lv e n t

Much w o r k h a s b e e n d o n e o n b o u n d w a t e r o n t h e b a s i s

o f t h e f a c t t h a t some w a t e r d o e s n o t a c t a s a s o l v e n t a n d

th at, th erefo re, t h i s w ater i s co n sid ered bound. For

in stan c e, sucrose has been added t o a s o l and th e co n cen ­

tratio n of s u c ro s e d eterm in ed i n th e f r e e s o l u t i o n .

T iiis c a n be d o n e v e r y s i m p ly by a r e f r a e t o m e t r i c tech n iq u e,

s u c h a s t h a t u s e d b y Kulman a n d G o l o s o v a (49). From t h e

d ifferen ce in th e c o n c e n t r a t i o n o f th e s u c r o s e fo u n d , and

t h a t w hich i t sh o u ld be i f a l l t h e w a te r w ere f r e e it

was p o s s i b l e t o calcu late how m u c h w a t e r d o e s n o t a i d i n

th e s o lu tio n of th e sucrose.

Kuron ( 4 1 ) , how ever, b e l i e v e d th a t n o t o nly th e c a p i l­

la r y w ater, but th e adsorbed w ater i s free to d is s o lv e

sa lts, a l t h o u g h he s h o w e d t h a t a l l th e w ater does n o t a c t

as a so lv en t u n t i l th e c o n c e n tra tio n o f th e added s o lu te

i s v e ry high.

(7) .H e at C a p a c i t y

A ndrianow (50) determ in ed th e heat c a p a c ity of hygroscop­

ic or bound w a te r o f v a r i o u s so ils to be 0 .7 0 c a l o r i e s per

gram .

(8) X -r a y

H e n d ric k s and J e f f e r s o n (.29) s h o w e d t h e r e l a t i o n

betw een t h e s t r u c t u r e of c la y m in erals and t h e i r c a p a c ity to -

adsorb w a te r.
 (9) S p ectro sco p ic

B usw ell and D u d e n b o stel (35) stu d ied the catio n

h y d ra tio n i n m o n tm o rillo n ite using th e in frared sp ectro sco p e.

They arranged th e s a l t s in th e fo llo w in g order of c atio n

hy d ratio n ?

Ca = M g » L i ^ K > B a » H ; W d »NH4

These r e s u l t s show a g o o d g e n e r a l a g r e e m e n t w i t h

th o s e o f H en d rick s and M s c o lle a g u e s (5), d isc u sse d be­

low . The n o t a b l e d i f f e r e n c e b e t w e e n t h e two s e t s of r e ­

su lts is th e s h i f t o f H+ f r o m o n e e n d o f t h e s e r i e s at

low h u m id ity to th e o th er a t h ig h h u m id ity . A t 5 and 10$

h u m id ity , H+ i s found (by H e n d ric k s) b e t w e e n Ba++ a n d N a + .

It i s n o t u n t i l 25$ hum id ity I s re a c h e d t h a t th e clay

acid exceeds th e Ba- and L i- c la y sa lts in w ater u p ta k e .

(10) E nergy o f Removal o f L iq u id from S u rfa c e

H en d rick s e t a l . (5) stu d ie d the h y d r a t i o n m echanism

of m o n tm o rillo n ite s a tu r a te d w ith v a rio u s c a t i o n s by t h e

u se o f X -ra y and d i f f e r e n t i a l th erm al m ethods. H is e v i ­

dence p o in te d to th e f a c t th at th e exchange c a tio n s are

lo cated betw een t h e s i l i c a t e lay ers of th e m in e ra l.

A ccording to H en d rick s, i n t h e m agnesium and a l k a l i n e

earth s a lts , th e f i r s t step of w ater s o r p tio n i s the

h y d ra tio n of the c a tio n w ith s i x m o lecu les of w a te r, w hich

is f o llo w e d by c o m p le tio n o f a w a te r l a y e r hav in g an

hexagonal ty p e of s t r u c t u r e . A second la y e r of sim ila r

stru c tu re is t a k e n up a t hig h er r e l a t i v e h u m id ity , i.e .,

 39

when s u f f i c i e n t w a t e r i s av aila b le. Three m o le c u le s a r e

req u ired fo r h y d r a tio n o f L i+ . I n N a -,'K ~ , and C s - s a l t s

the c a t i o n a p p a r e n t l y was n o t h y d r a t e d . T ills was a l s o tru e

for th e hydrogen io n o f th e c la y a c i d . Thus, th is recent

i n v e s t i g a t i o n seem s t o in d ic ate t h a t so m e c a t i o n s such as

Na+ w h i c h w e r e f o r m e r l y t h o u g h t t o h e h i g h l y h y d r a t e d may

n o t be h y d r a te d a t a l l *

H en d rick s? r e s u l t s in d icated th at the hydrogen io n

is p r o b a b l y im bedded i n t h e s i l i c a t e la y e r a t the s i t e

of th e effectiv e charge. T h e re was n o i n d i c a t i o n o f h y d r a ­

tio n of th e p ro to n w ith fo rm atio n of th e hydronium i o n , H30 + .

( l l ) Heat o f W e ttin g , W ith I n f lu e n c e

of V ario u s F a c to r s

T he h e a t a c c o m p a n y i n g t h e w e t t i n g of a m a t e r i a l by

a liq u id is a r e p r e s e n ta tio n of th e energy o f a d s o rp tio n

of th at liq u id b y t h e m a t e r i a l b e i n g w e t t e d . The e v o l u ­

tio n of energy occurs as a r e s u l t of th e l o s s of k in e tic

energy of th e m o lecu les o f th e liq u id during ad so rp tio n .

The a m o u n t o f e n e r g y e v o l v e d d e p e n d s o n t h e f o l l o w ­

ing f a c t o r s :

(a) The n a t u r e of the su rfa c e . In th e case of c la y

th is In clu d es th e m in e ra l co m p o sitio n of th e

c la y and th e type of ad so rb ed io n .

(b) The n a t u r e o f t h e w e t t i n g liq u id , i.e ., w hether

it is p o la r or n o n -p o la r, th e s iz e of i t s m o lecu les,

etc *
 40

(c) The am o u n t o f s u r f a c e b e i n g w e t t e d .

(d) The p e r m e a b i l i t y o f t h e s a m p le , i.e ., the r a te

a t w hich w e ttin g c a n taice p l a c e .

(e) The d e g r e e t o w h i c h t h e m a t e r i a l t o be w etted

has b een f r e e d from w a te r , or o th er liq u id s .

(f) The d e g r e e to w hich th e m a t e r i a l to be w etted

has b e e n f r e e d from a d s o r b e d g a s e s .

(g) The h i s t o r y o f th e m a t e r i a l t o be w e t t e d , e .g .,

its p rev io u s heat treatm en t.

(h) O ther h e a t e f f e c t s , su c h as th o se w hich m ight

occur in r e a c t i o n of th e m a te r ia l w ith th e w et­

tin g liq u id , o r in th e d i s s o c i a t i o n w h ich m ig h t

be e x p e c te d i n c l a y s i f we c o n s i d e r t h a t an Na-

clay d is s o c ia te s i n w a t e r t o f o r m Na i o n s a n d

c o llo id a l c la y an io n s. . ,

X a} The N a tu re o f th e S u r f a c e

M a lh o w e r , Shaw an d A l e x a n d e r (51) im plied th a t base

ex ch an g e c a p a c i t y and h e a t o f w e t ti n g a r e d e t e r m i n e d more

by th e stru c tu re and c h em ic al c o m p o s itio n o f th e c o llo id

surface t h a n by i t s area.

E f f e c t o f A dsorbed Io n s

.P a te (52) stu d ied the heat of w ettin g of so ils satu rated

v.ri t h v a r i o u s b a s e s u s i n g n o r m a l s o l u t i o n s of th e c h lo rid es.

He f o u n d t h a t m o n o v a l e n t b a s e s d e c r e a s e d t h e h e at of w et­

tin g and a t t r i b u t e d some o f t h e d e c r e a s e to a lo s s of

organic m atter du rin g th e leach in g process.

 41

Ja iie rt (25) (55) found t h a t electro d ialy zed so ils have

a low er heat of w e ttin g than b e fo re e le ctro d ialy sis. He

rep o rted th a t the heat of w ettin g is p ro p o rtio n a l to th e

base exchange c a p a c ity and t h a t th ere is a c lo se r e la tio n

b etw een th e heat of w ettin g and th e t o t a l heat of hydra­

tio n of the ad so rb ed io n s . He s t a t e d tlia t th e heat of

h y d r a t i o n .d iv id e d by t h e heat of w ettin g is a co n stan t

for a ll so ils, and t h a t the r a t i o ' d i f f e r e d fo r v ario u s

c atio n s according to th e in te n sity of th e ir b in d in g .

Dum anski and C hapek (54) c ritic iz e d Jan erth s co n clu ­

sio n th a t the heat of w ettin g is caused e x c lu s iv e ly by t h e

h eat o f h y d ra tio n of the adsorbed io n s, sin ce the a ttra c ­

tio n of flu id s for a ll ad so rb en ts c a n h a r d l y b e c a u s e d by

adsorbed io n s. They s t u d i e d the h eats of w ettin g of car­

bon, p erm u tite, and s i l i c a g el w ith v ario u s adsorbed ions

and fo u n d n o r e l a t i o n betw een t h e heat of w e ttin g and

h y d ratio n . They c o n c lu d e d t h a t th eir re su lts in d ic ate d

th e adsorbed io n s n o t to be h y d r a te d a s much a s f r e e io n s,

V a g e le r.a n d A lton (20) gave th e h eat of h y d ra tio n of th e

m ain s o i l c a t i o n s as fo llo w s: (The u n i t s arc c alo rie s per

e .e , of c a tio n .)

, H Ha K M g /2 C a/2

247 94 75 £ 2 9 .5 1 7 4 .5

The h e a t s of h y d ra tio n of gas io n s arc sum m arized i n

T ay lo rfs t r e a ti s e (75) as fo llo w s (p. 557):

 42

Ion From C alc. C a lc .

sin g le p o te n tia l (Born) (Webb)

H+ 268 2 4 9 .6
L i+ 150 110 ------
Na+ 1 17 103 9 9.0
K+ 97 82 8 1 .9
Rb+ 92 73 76 .9
Cs+ 86 74 71.5

These v a lu e s a g ree v/ell w ith th o se g iv e n by V ag eler

and A l'te n , whose v a l u e s are a ll somewhat l o w e r . C ounter

to th ese fig u re s is the s t a t e m e n t o f W iegner (7) and o t h e r s ,

th at hydrogen i s a dehydrated io n (and sh o u ld t h e r e f o r e n o t

be e x p e c te d to sh o w a h e a t o f h y d r a t i o n ) .

Janert (25) (53) p o in ted out th a t such ra th e r th eo ret­

ic a l fig u res are v a lid only f o r a b so lu te ly fre e io n s.

A dsorbed io n s a re bound, and J a n e r t b e lie v e d t h a t only a

c e r t a i n p o rtio n of th e t o t a l h eat of h y d ra tio n appeared

when a s o i l was w e tte d * In o th e r w ords, he f e l t th at

th e heat- o f w e t t i n g w a s s i m p l y a m a n i f e s t a t i o n of th e

h e a t o f h y d r a t i o n o f th e bound I o n s . He c o n c l u d e d t h a t

th e in te n sity of th e b in d in g of the io n s d e term in ed th e

fra c tio n , shown b e lo w , of heat of h y d ra tio n re tu rn e d as

h eat of w ettin g *

H M g /2 C a/2 K Na

8 ,7 % 1 1 ,1 % 1 4 .3 $ 1 9 . 6/o . 2 0 .4 $

The o r d e r o f d e c r e a s i n g in te n sity of b in d in g , th erefo re,

w as:

H>Mg> C a > K ; N a .
 45

Baver (52) a lso rep o rted a sim ilar s e r i e s . , w i t h Na+ a n d K+

d ecreasin g th e heat of w e ttin g .

The h e a t o f w e t t i n g for one m i l l i e q u i v a l e n t o f a n

e x c h a n g e a b l e c a t i o n was r e p o r t e d (25) as fo llo w s?

• Na 1 6 .8

IC 8 .8
Mg 1 9 .4

Ca 2 2 .0

Harman (5 6 ) m e a s u r e d the heat of w ettin g of about

ten d if f e r e n t clay s hav ing exchange c a p a c i t i e s v arying

from a p p ro x im a te ly 4 m .e. to 90 m . e . p e r h u n d re d gram s o f

clay , and fo u n d th e b a se ex ch an g e c a p a c i t y t o be p r o p o r ­

t i o n a l to th e heat of w ettin g . He u s e d t h e m e t h o d o f

Ja n ert, a n d came t o t h e same c o n c l u s i o n t h a t J a n e r t d i d ,

nam ely, th at th e -heat of w e ttin g is a fra c tio n of the heat

of h y d ratio n of th e adsorbed c a tio n . H a rm a n b e l i e v e d t h a t

th e m ost i m p o r t a n t u s e o f h e a t o f w e ttin g is th e p re d ic tio n

of th e behavior o f u n trie d catio n s in c la y -w a te r sy stem s.

He a t t e m p t e d to calcu late th e amount of hydrogen io n is e d

f r o m a n H - c l a y a n d t h e pH o f t h e s u s p e n s io n and found t h a t

by assum ing th at 8.7% o f t h e hydrogen i s a ctiv e (J a n e rt!s

c o n c lu sio n ( a v alu e c lo ser to th e o b s e r v e d v a l u e was o b t a i n e d .

Harman a t t r i b u t e d d ifferen ces in th e p r o p o r tio n a lity

b etw een h e a t o f w e t ti n g and b a se exc-iange c a p a c i t y to

org an ic m a tte r, in sp ite of th e f a c t th a t a m in eral such

a s m o n t r a o r i l l o n i t e w ould h a r d l y be e x p e c t e d t o show t h e

same p r o p o r t i o n a l i t y th at k a o lin ite does. In a la te r paper,

 4.4

Harman a n d F r a u l i n i (41) rep o rted a facto r d iffe re n t than

8.7?o r e p o r t e d b y J a n e r t b u t d i d n o t i n t e r p r e t th e d if f e r e n c e .

(b) T he N a t u r e o f t h e W e t t i n g L i q u i d

B ehrens (23) stu d ied th e heat of w ettin g of p ern iu tite

k ao lin , and s o i l s w ith, w a t e r , a n ilin e, o liv e o il, to lu en e,

and p a r a f f i n o il, and showed r e g u l a r d e c r e a s e s in th e above

order, i.e ., th e heat of w ettin g decreased as the i n t e r ­

f a c i a l te n s io n w ith w ater in c re a s e d . He a l s o obtained a

q u a litativ e v e rifica tio n of th e th eo ries of P a tric k and

Grim w h e r e i n t h e f l u i d a d s o r p t i o n and t h e h eat of w ettin g

are re la te d to th e su rfa c e ten sio n .

Janert (53) showed t h a t p o l a r l i q u i d s produced a M g h e r

heat of w e ttin g .. T he p o l a r a d s o r p t i o n s h o u l d b e c l o s e l y

c o r r e l a t e d w ith th e ex ch an g eab le b ases h e ld by th e so il,

and c o n s e q u e n tly th e r e s h o u l d b e some r e l a t i o n b e t w e e n t h e

h e a t of h y d ra tio n of th e ad so rb ed c a tio n s and th e heat of

w ettin g o b tain ed w ith a p o la r liq u id .

( c) T he A m o u nt o f S u r f a c e

The h e a t o f w e t t i n g depends, of co u rse, on t h e amount

o f s u rfa c e b ein g w e tte d .

B a r t e l l and Fu (58) sta te d th at the h e a t of w e ttin g

rep re se n ts the d ecrease of t o t a l su rfa c e energy w itM n th e

sy s te m and t h a t th e heat of w ettin g is therm odynam ically

p ro p o rtio n a l to th e s u rfa c e a r e a .

B ehrens (23) found t h a t th e heat of w ettin g in calo rie s

p e r gram m u l t i p l i e d by 3 . 6 i o 5 approxim ated th e s u r f a c e

 45

in s q u a re c e n t i m e t e r s per gram . His c a l c u l a t i o n s in d icated

t h a t th e average th ic k n e s s of th e w ater la y e r is 0 .3 8 r n illi

m icro n s or l.B m o le c u la r d ia m e te rs .

M i t s c h e r l i c h and h is c o -w o rk ers (39) a l s o showed th e

im p o rtan ce of s p e c i f i c surface.

Bouyoucos (59) u s e d h e a t o f w e t t i n g a s a means o f

estim atin g th e c o llo id co n ten t of s o i l s .

H a rm a n a n d F r a u l i n i (57) frac tio n a te d a k a o l i n and

found th e b ase exchange c a p a c i t y to be p r o p o r t i o n a l to the

heat of w ettin g . The b a s e e x c h a n g e c a p a c i t y w a s , i n turn.,

in v e r s e ly p ro p o rtio n a l to the p a r t i c l e size.

Kapp (60) show ed t h a t q u a r t z p a r t i c l e s larg er th an

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

frac tio n s of s o ils above 20 m ic r o n s showed a h e a t o f w e t ­

tin g .

( d) The P e r m e a b i l i t y o f t h e Sam ple

I n c a se s w here th e w e ttin g of th e s o l i d by th e l i q u i d

may b e a s l o w p r o c e s s , as in some m o n t m o r i l l o n i t e s , the

m easurem ent o f th e h e a t e v o l v e d on w e t t i n g becom es more

d iffic u lt. For th is reason, th e p e rm e a b ility o f th e sam ple

is a facto r governing th e v a lu e s o b ta in e d in h e a t o f w et­

tin g m easurem ents.

(e) The D e g r e e t o W h i c h t h e M a t e r i a l lia s b e e n F r e e d f r o m

W ater

M i t s c h e r l i c h and h is co-w orkers (39) stu d ied th e

rela tio n sh ip b etw een m o is tu re c o n te n t and h e a t o f w e ttin g

and o b s e rv e d a g r a d u a l lo w e r in g of th e h e a t ev o lv ed as th e

s o i l c o n t a i n e d more o r i g i n a l m o i s t u r e .
 46
R odew ald (61) fo rm u lated th e fo llo w in g eq u atio n fo r

th e r e l a t i o n of heat of w ettin g to m o istu re c o n te n t:

ccvv = ios<v1) dpi) >

w here r q and rp a re the c a lo rim e tric h eats of w e ttin g of

th e so lid c o n t a i n i n g Wq a n d W-,^ m o i s t u r e * resp ectiv ely *

i m easures th e e x t e n t to w hich th e cohesive fo rc e s of th e

sw ellin g so lid are overcom e and i s o p p o site in sig n to r*

and c i s a p ro p o rtio n a lity co n stan t. A n d ria n o v (71) re­

garded i i n th e above e q u a tio n as th e a d s o r p tio n o f energy

req u ired to d is p e r s e th e w ater over th e su rface of the

adsorbing so lid . The c o n s t a n t c i s in v ersely p ro p o rtio n a l

to th e a ctiv e s u rfa c e of the a d s o r b e n t.

(f) T he D e g r e e t o W h i c h t h e M a t e r i a l h a s b e e n F r e e d f r o m

Ad s o r b e d G a s e s

Dumanski and C hapek (54). fo u n d t h a t a d s o r b e d a i r

low ered th e heat of v e ttin g a re la tiv e ly s m a ll am ount.

The i n c r e a s e in heat, o f w e t t i n g u p o n e v a c u a t i o n w as p r o p o r ­

tio n a l to t h e amount o f s u r f a c e c o v e r e d by t h e a i r .

( p) The H i s t o r y o f t h e Ma t e r i a l

Iloseh (6£) stu d ied the effect of d iffe re n t heat tre a t—

m ents on th e heat of v e tt i n g « He f o u n d a maximum, i n heat

of w ettin g from o 0 0 -4 0 0 °C . to z e r o a t 500°C.

P a rm e le e and F r e c h e t t e (6?) u se d h e a t o f ’r e t t i n g to

stu d y th e changes in c la y s d u rin g f i r i n g ’ and r c h y d r a t i o n .

( h) O t h e r H e a t E f f e c t s

W a d sw o rth (64) found th e heat of w ettin g t o be much

i n f l u e n c e d b y t h e t e m p e r a t u r e a t v.diich t h e d e t e r m i n a t i o n s
 47

v;ere m ade. At h i g h e r t e m p e r a t u r e s low er heats of w e ttin g

were f o u n d .

P u r i a n d Hoon ( 6 5 ) co nsidered t h e low h e a t o f w e t t i n g

of L i - and i l a - s o i l s to be e x t r a o r d i n a r y i n view o f t h e i r

rep o rted h igh h y d ra tio n . They th o u g h t a p o s s i b l e ex p lan a- -

tio n of t i l l s d i f f e r e n c e m ig h t l i e in th e fact th a t th e

m onovalent b a ses a re io n ised to a g r e a te r e x t e n t on t h e

so il s u r f a c e and th e n e g a t i v e h e a t, o f i o n i z a t i o n w o u l d

c o rr e s p o n d in g ly low er th e heat, o f w e t t i n g . They s t u d i e d

th e e f f e c t o f sodium o l e a t e so lu tio n s on h e a t o f n e t t i n g

and f o u n d t h a t i n sp ite of the low er s u r f a c e ten sio n the

h e a t o f v a s t t i n g was t h e same a s i n w a t e r * They c o n c lu d e d

th at surface te n s io n as such plays l i t t l e p a rt in d eterm in ­

in g the heat of w e ttin g .

Harman and F r a u l i n i (57) sta te d t h a t u n p u b lish ed

data in d ic a te d th a t the h e a t of v iettin g v a r i e s w ith d i l u ­

tio n (as does heat of s o l u t io n ) «

R e l a t i o n o f H e a t o f Vie t t i n g a n d Ad s o r p t i o n o f W a t e r f r o m

The Vauor P h a s e

A l t e n and K urm ies (66) r e p o r t e d t h a t th e h e a t of

w ettin g a n d h y g r o s c o p i c ! t y •w e r e n o t p a r a l l e l w i t h v a r i o u s

adsorbed io n s. The s e q u e n c e f o r heat of w ettin g in d e crea s­

ing o r d e r v:as C a , H g , H a , I'h For h y g ro sco p ieity it was

H a , K, Mg, C a .
Baver (52) found a c l o s e r e l a t i o n betw een th e hygro-

scopic c o e f f ic ie n t over su lp h u ric acid and th e h e a t of

w ettin g .. B o t h Na+ an,& K+ w e r e f o u n d to reduce th e a c t i v i t y

o f th e c o llo id a l m a te ria l; K+ e x e r t e d th e g r e a te r d im in ­

ish in g in flu e n ce .

It has been r e p o r t e d (25) th a t the heat of w ettin g

a v e r a g e d 32 c a l o r i e s (50-88) f o r one gram o f h y g r o s c o p i c

w ater,

A nderson (67) m e a s u re d t h e heat of w ettin g and a d ­

s o r p tio n of w ater of c la y s s a tu ra te d w ith v ario u s c atio n s»

He s t a t e d th at t h e a d s o r p t i o n o v e r oO/i s u l p h u r i c acid

show ed w id e ly d i f f e r e n t r e s u l t s w ith various c atio n s in

c o n tr a s t to ap p ro x im ate ly e q u al a d s o rp tio n s o f w a te r from

s a tu r a te d atm o sp h eres. The d e c r e a s i n g series f o r w ater

a d s o r p t i o n and h e a t o f w e t t i n g w as: C a , Mg, N a , H, K,

m ethylene b lu e .

He f o u n d i t d iffic u lt to in te rp re t th e low er heat of

w ettin g a n d h y g r o s c o p i c i t y w i t h K+ a n d b e l i e v e d th at lo ss

of organic m a tte r in th e p r e s e n c e o f K+ m i g h t a c c o u n t f o r

th e low er v a lu e s . The v a r y i n g effects of the c a t i o n s w ere

a ttrib u te d to d iffe re n c e s in so lu b ility and d i s s o c i a t i o n

ten d en cies of Lhe c o l l o i d - c a t i o n c o m b in a tio n s and th e r e ­

su ltin g d ifferen ces i n t h e d e n s i t y and d i f f u s i v i t y of th e

H elm holtz d o u b le l a y e r of t h e c o llo id a l m icelles.

R e l a t i o n o f Heat o f W ettin g and V i s c o s i t y

Baver (32) rep o rted th e fo llo w in g series for heat of

w ettin g o f Putnam c l a y s s a tu ra te d w ith v ario u s catio n s:

C a y B a > H > L i = Na>K

and f o r the h y d ratio n of b e n to n ite , calcu lated form v i s ­

c o sity d ata:

H>Ba>Li>Ca>Na^K

He f o u n d i t d iffic u lt to ex p lain , on th e b a sis of pure

h y d ratio n , why Mg- a n d C a - c l a y s c o n t a i n e d m o r e w a t e r t h a n

N a-clays* The f a c t th at H - c la y a p p e a r e d m ost h i g h l y hy­

d r a t e d was e v e n m ore d i f f i c u l t to u n d e rs ta n d . (Baver

po in ted out th a t th e H io n is u s u a lly co n sid ered n o t

hy d rated , on th e b a s i s o f t r a n s f e r e n c e m ea su re m e n ts,)

H e a t E f f e c t s When C l a y s a r e I m m e r s e d i n E l e c t r o l y t e s

V ery l i t t l e w o rk h a s b e e n d o n e on t h e h e a t e f f e c t s

o b t a i n e d when c l a y s are im m ersed i n e le ctro ly te s.

Bouyoucos (68) m easured th e d i f f e r e n c e s in h e a t of

r e a c t i o n betw een a r t i f i c i a l and s o i l g e l s o f s i l i c a ,

a lu m in a and i r o n w i t h h y d r o x id e s .' He f o u n d n o m e a s u r a b l e

h e a t o f r e a c t i o n betw een s o i l s and s a l t s b u t t h e r e was a

r e a c tio n w ith hyd ro x id es, e s p e c i a l l y w i t h KOH a n d NaOH.

NaOI-I w a s r e p o r t e d to g iv e a hig h er heat of re a c tio n th an

KOH w i t h e v e r y m a t e r i a l stu d ied . The h e a t o f r e a c t i o n

was t h o u g h t t o be c a u s e d by:

(a) so lu tio n

(b) n e u t r a l i z a t i o n

(c) ad so rp tio n

S o l u t i o n seem ed t o be t h e m ain f a c t o r b e c a u s e th e m a te ria ls

w ere a c t u a l l y seen to d is so lv e and a l a r g e r heat of reac­

t i o n v.ra s f o u n a i n c a s e s w h e r e m o r e s o l u t i o n occurred. The

 50

m in eral c o n s titu tio n and c o n d i t i o n o f th e a d s o r b e d io n s

of th e s o ils s t u d i e d -were n o t s p e c i f i e d .

S tr& tlin g (69) (70) stu d ied th e a ctiv ity of k a o lin

calcin ed a t v ario u s t e m p e r a t u r e s by m e a s u rin g its heat of

w ettin g i n w a t e r a n d i n CaO s o l u t i o n . T he h i g h e r v a l u e s

w h ic h were fo u n d f o r t h e CaO s o l u t i o n w e r e i n t e r p r e t e d as

being c a u s e d by t h e h e a t o f a b s o r p t i o n o f CaO b y t h e k a o l i n .

The g r e a t e s t a b s o r p t i o n o c c u r r e d i n th e ra n g e o f 500~700°C.

GENERAL METHODS OF CALORIMETRY

Many t y p e s of calo rim eters have been used to s tu d y

the h eat of w ettin g o f p o w d e rs by l i q u i d s . T h e m o s t common

ty p es a re th e vacuum -w alled, th e a d ia b a t i c , and th e ice

c alo rim e te r. The a d i a b a t i c c alo rim e te r is d iffic u lt to

o p erate. T he i c e calo rim eter has th e a d v a n ta g e o f b e in g

ab le t o m e a s u re v e r y s lo w r e a c t i o n s w i t h t h e same a c c u r a c y

as t h a t o b tain ed i n o t h e r m ethods o f c a l o r i m e t r y and w i t h o u t

s o m an y e l a b o r a t e a c c e s s o r i e s . Its m ost s e r i o u s lim ita ­

tio n is th at i t c a n be u s e d o n ly a t 0°C. V acuum -w alled

c a l o r i m e t e r s a r e m o st u s e d I n work n o t i n v o l v i n g h igh

p recisio n , T hey a r e more s i m p l e to o p erate.

T he p r i n c i p l e s of calo rim etry are d iscu ssed in d e ta il

by W h it e (80)

The I m p o r t a n t f a c t o r s in th e d e sig n of any c a lo rim e te r

are in clu d ed in the fo llo w in g :

(l) T em p eratu re m easurem ent. The s i m p l e s t m e th o d

em ploy s a Beckmann t h e r m o m e t e r . The l i m i t of

 51
*
accuracy of m erc u ry -in -g lass therm om eters (75)

is p ro b a b ly a b o u t 0 .0 0 0 5 °C . F o r m ore r e f i ^ d c f ^ ’' .

work e i t h e r a resistan ce therm om eter o r a

m u ltip le j u n c t i o n th erm o co u p le m ust be u s e d .

(2) S tirrin g of th e l iq u i d . The w hole m ass o f t h e

l i q u i d m ust be c i r c u l a t e d by th e s t i r r e r .

D ick in so n (81) found a sc re w s t i r r e r to be

more e f f i c i e n t than a rin g stirrer in regard to

th e r a t e a t w hich th e te m p e ra tu re e q u ilib riu m

was a t t a i n e d . The e n e r g y d i s s i p a t e d by th e

s c r e w was a l s o less th a n t h a t from th e r i n g

stirre r. The s p e e d o f s t i r r i n g m ust re m a in

uniform , as th e r a t e of heat pro d u ctio n v a rie s

as the cube o f th e speed (73).

(5) T herm al le a k a g e . Two m e t h o d s a r e g e n e r a l l y

em ployed t o c o n tro l therm al leak ag e. In th e

first m ethod, the te m p e ra tu re in th e o u te r jack et

is kept co n stan t. In th e seco n d m ethod, th e

ad ia b atic, the e n v i r o n m e n t i s k e p t a t t h e same

tem p eratu re as th e c a lo r im e te r . The h e a t i n t e r ­

change b etw een th e c a l o r i m e t e r and i t s surround­

in g s is p ro p o rtio n a l to th e tem p eratu re d i f f e r ­

ence, except fo r effects due to ev ap o ratio n ,

co n v ectio n , and r a d i a t i o n .
 52

S p e c ia l C o n sid eratio n s i n Heat o f

W etting D e te rm in a tio n s

In a d d itio n to th e g e n e ra l p rin c ip le s of calo rim etry ,

th efo llo w in g f a c t o r s sh o u ld he c o n sid e re d in d eterm in in g

th e heat of w ettin g of cla y ,

(1) B efore te s tin g the c la y , th e a d so rb e d w a te r m ust

be rem oved by d r y i n g a t so m e e l e v a t e d t e m p e r a t u r e .

The c l a y m u s t n o t b e a l l o w e d t o r e - a b s o r b m o i s ­

tu r e during c o o lin g .

(2) The c l a y s a m p l e m u s t be a t t h e same t e m p e r a t u r e

as th e l i q u i d w i t h w hich i t is to be w e tte d .

(3) The c l a y m u s t b e c o m p l e t e l y w e t t e d b y t h e l i q u i d .

T his im p lies th a t adsorbed, or e n trap p ed a i r

m ust n o t be p r e s e n t . Some e n e r g y - w o u l d b e r e ­

q u ired to d isp la c e th e adsorbed a i r , in ad d i­

tio n to t h a t f a c t t h a t th e a i r m ig h t n o t be

d isp laced .

In th e s tu d ie s of th e heat o f w e ttin g o f c la y s w hich

have b e e n m ade p r e v i o u s l y , th ese fa c to rs have n o t r e c e i v e d

f u l l co n sid eratio n .

A b rief summary o f t y p i c a l m e th o d s w h i c h h av e b e e n

used in s tu d ie s of h eats o f w ettin g fo llo w s.

R eview o f M eth ods u s e d i n D e t e r m i n a t i o n s

o f Heat of W ettin g

Janert (53) u s e d a Beckmann t h e r m o m e t e r , Dewar f l a s k ,

b u t no c lo s e tem p e ra tu re c o n tr o l of th e su rro u n d in g s.
 53

T h e c l a y s a m p l e Yta.s d r i e d a t 1 1 0 ° C . , c o o l e d f a s t i n a

d e s s i c a t o r o v e r f r e s h C a C l^ , p l a c e d i n a b o t t l e , sto p p e re d ,

and se a le d w ith p a ra ffin * A t t h e tim e o f t h e m easurem ent

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

th e c a lo rim e te r. T he c h i e f o b j e c t i o n s t o t h i s m eth o d

in c lu d e th e d i f f i c u l t y o f h a v in g th e c la y and w a te r a t

th e sam e t e m p e r a t u r e b e f o r e m i x i n g , th e p o s s ib i l i ty of re ­

a d s o r p tio n o f w a te r v ap o r by th e c la y d u rin g c o o lin g

(e v e n o v e r C a C l2 ) , an d t h e p o s s i b l e e f f e c t o f ad so rb ed

a ir.

H arm an a n d F r a u l i n i (57) and P a rm e le e and F r e c h e t t e

(6 5 ) u s e d t h e m eth o d o f J a n e r t . A n d erso n (8 2 ) used a s im i­

l a r m eth o d . In o rd er to h a v e t h e s a m p l e a t t h e sam e t e m p ­

e ra tu re as th e liq u id b e fo re w e ttin g , it is d e sira b le to

have t h e sa m p le c o m p le te ly s u r r o u n d e d by t h e l i q u i d .

P a t r i c k a n d G r im (2 6 ) u s e d t h i s m e t h o d i n a stu d y o f th e

h e a t o f w e ttin g s ilic a g e l. T he v e s s e l w h i c h c o n t a i n e d

t h e g e l was p r o v id e d w i t h a g ro u n d g l a s s sto p p e r. A g la ss

r o d w as s e a l e d to th e b o tto m o f th e v e s s e l . U pon t u r n i n g

and l i f t i n g th is ro d , t h e g e l w as th ro w n i n t o th e l iq u i d .

A g la ss hook a t t a c h e d to th e s to p p e r e n a b le d th e g e l to

b e c o m p l e t e ly rem oved fro m t h e b o t t l e . I t w as n o t n e c e s ­

s a r y f o r P a t r i c k a n d G rim t o e v a c u a te th e g e l.

M itsc h e rlic h (3 9 ) e v a c u a te d c la y b e fo re w e ttin g it,

and opened th e c o n ta in e r u n d er w a te r (in an ic e c a lo r im e te r ) .

No s t i r r i n g was u s e d .
 £4

B eh ren s (2 3 ) u s e d a m eth o d s i m i l a r t o t h a t o f M it­

sc h e rlic h . The s a m p le w as p l a c e d i n a s p e c i a l c o n t a i n e r

h a v in g a g ro u n d g l a s s to p w ith a v a lv e . T he c o n t a i n e r w as

e v a c u a te d "before p l a c i n g in th e c a lo rim e te r. The s a m p l e

w as w e t t e d b y o p e n i n g t h e v a l v e u n d e r t h e su rface o f th e

liq u id in th e c a lo rim e te r. T he t e m p e r a t u r e r i s e w a s m e a ­

s u r e d by t h e e x p a n s io n o f to lu e n e p la c e d b e tw e e n t h e w a l l s

o f th e c a lo r im e te r . Ho s t i r r i n g w as u s e d . The h e a t

lib e ra te d had to p a s s t h r o u g h th e w a l l s of th e g la s s

c o n ta in e r.

H oseh (62) a ls o re c o g n iz e d th e im p o rta n c e o f ev ac u ­

a tin g th e c la y b efo re w e ttin g . A s p e c i a l c a l o r i m e t e r w as

used, c o n sistin g o f a D ew ar f l a s k w i t h a g r o u n d g l a s s jo in t.

T he c l a y w a s p l a c e d i n s i d e o f t h e Dew ar f l a s k , and th e

w h o le c a l o r i m e t e r w as e v a c u a t e d . The w e t t i n g l i q u i d w as

th e n added to th e c la y in th e f la s k . A lth o u g h c o m p le te

w e ttin g to o k p la c e b e c a u s e o f th e e v a c u a t io n , no p r o v i s i o n

w a s m ade f o r s t i r r i n g . T he t e m p e r a t u r e r i s e was m e a su re d

by m eans o f a m u l t i p l e j u n c tio n th e rm o c o u p le .

H a r k i n s a n d E w in g ( 8 3 ) -used a m e t h o d i n w h i c h t h e

p o w d er t o b e w e t t e d w as p l a c e d i n a g l a s s b u l b , w h ic h w as

th en " o u t-g a s s e d ." The t i p of th e b u l b was b r o k e n o f f

in sid e o f th e c a lo r im e te r , a llo w in g th e w e ttin g liq u id to

e n te r. A c o m p le te s h a t t e r i n g o f t h e b u l b w o u ld seem

p re fe ra b le .

B a r t e l l and Fu (58) e n c lo se d th e pow der t o b e w e tte d

in a th in -w a lle d g la s s t u b e , w h i c h w as s e a l e d in a g la s s
 55

h o ld e r. The b u l b w as b r o k e n b y p u s h in g it a g a in s t th e w a ll

o f th e c a lo rim e te r (a Dewar f l a s k ) .

C l a r k a n d T hom as ( 8 4 ) stu d ie d th e h e a t o f w e ttin g

o f q u a rtz , u sin g a c a lo rim e te r v e ry s im ila r in d e sig n to

th e one u se d i n th is in v e s tig a tio n . The q u a r t z w as c o n ­

ta in e d i n a g l a s s b u l b , w h ic h w as d r i e d , e v a c u a te d and

s e a le d . T he b u l b w a s p l a c e d o n a b r a s s p l a t e w h i c h f i t t e d

i n t h e b o tto m o f th e c a l o r i m e t e r . T he s h a f t o f t h e s t i r r e r

w as h o llo w , and a llo w e d th e i n t r o d u c t i o n o f a ro d to b re a k

th e b u lb by im p a c t, th e re b y w e ttin g th e p o w der.

APPROACH TO THE PROBLEM

M any m e t h o d s h a v e b e e n u s e d t o s t u d y t h e r e l a t i o n ­

s h ip s o f c la y and w a te r. As s h o w n a b o v e , m e a s u r e m e n t s

m ad e b y s i m i l a r m e t h o d s f r e q u e n t l y f a i l to a g r e e , and th e

i n f o r m a t i o n g a i n e d by one m eth o d i s o fte n d i f f i c u l t to

c o r r e l a t e w i t h t h a t fo u n d by o t h e r m e th o d s. M u ch o f t h e

d i s a g r e e m e n t m ay b e a t t r i b u t e d to f a i l u r e s to d e fin e th e

ty p e o f c la y m in e ra ls in v o lv e d , and to la c k o f s ta n d ­

a r d iz a tio n in th e tre a tm e n t o f th e c la j^ s. I n t h i s w ork,

a n e f f o r t w a s m ad e t o d e f i n e th e c la y and i t s p re p a ra tio n .

T he p r i n c i p a l m e t h o d o f s t u d y e m p l o y e d h e r e w a s t h a t

o f th e h eat of w e ttin g , in o rd er to g a in in fo rm a tio n in

reg ard to th e e n e rg y w i t h w h ic h w a te r i s a ttra c te d by c l a y s .

T h is m eth o d a l s o p re se n te d th e o p p o rtu n ity of i n v e s ti ­

g a tin g th e h e a t e f f e c t s w h ic h t a k e p l a c e w hen c l a y s a r e

im m ersed i n e le c tro ly te s.
 56

The c a p a c i t y o f c l a y s t o a t t r a c t w a te r w as m easu red

by d e te rm in in g th e w e ig h t o f w a te r so rb e d u n d e r v a rio u s

c o n d itio n s.

The i n t e n s i t y w i t h w h ic h w a t e r i s b o u n d t o c l a y s w as

s tu d ie d a ls o by a d i f f e r e n t i a l t h e r m a l m eth o d w h ic h m e a s u r e s

th e en erg y r e q u ir e d t o rem o v e w a t e r fro m t h e c la y .

 67

EXPERIMENTAL PROCEDURE

IDENTIFICATION AND PREPARATION OF CLAYS

C la y s U sed i n T h is I n v e s t i g a t i o n

K a o lin

S e v e r a l c l a y s w e re e x a m in e d i n a n e f f o r t t o o b ta in

th e p u rest k a o lin ite a v a ila b le . I t w as c o n s i d e r e d d e s i r ­

a b le t o u s e a k a o l i n w h ic h c o u ld be o b t a i n e d a s m in e d ,

th a t is, w ith o u t any f u r th e r tr e a tm e n t by th e p ro d u c e r.

The k a o l i n y /h ic h w as f i n a l l y s e l e c t e d w as o n e fro m

t h e McNamee m i n e , n e a r L a n g l e y , S o u t h C a r o l i n a , a n d w as

o b t a i n e d f r o m W a r d Ts N a t u r a l S c i e n c e E s t a b l i s h m e n t , In c .,

R o c h e s t e r , New Y o r k .

T h i s k a o l i n w a s a l s o u s e d by H arm an a n d F r a u l i n i (5 7 ),

w ho s t a t e d th a t X -ray d i f f r a c t i o n p a tte rn s f a ile d t o show

e v id e n c e o f a p p r e c ia b le am o u n ts o f a n y m i n e r a l o t h e r t h a n

k a o lin ite . T h e i r p a t t e r n s w e r e e x a m i n e d b y W. F„ B r a d l e y ,

Illin o is S t a t e G e o l o g i c a l S u r v e y , who r e p o r t e d w e a k l i n e s

c o rre sp o n d in g to th o se o f d ic k ite in th e f r a c tio n s one

m ic ro n and f i n e r . As d i c k i t e b e lo n g s to th e k a o l i n g ro u p

and re s e m b le s k a o l i n i n m ost r e s p e c t s , it is b e lie v e d th a t

s u c h m a t e r i a l p r e s e n t i n s m a l l a m o u n ts i s n o t a v e ry ob­

je c tio n a b le c o n ta m in a tio n .

Wy o m in g B e n t o n i t e

T h i s m a t e r i a l w a s a t y p i c a l s w e l l i n g Wyoming b e n t o n i t e ,

o f c o m m erc ial g r a d e . Its e x a c t s o u r c e i s n o t k n o y /n , b u t o n

th e rm a l a n a ly s is it gave a c u rv e v e ry s im ila r to th a t of
 58

s t a n d a r d 11V o l e l a y " , o b t a i n e d fro m t h e A m e ric an C o l l o i d

C om pany, 363 W est S u p e r i o r S t r e e t , C h ic a g o , Illin o is .

It is Im p o ssib le to o b ta in la r g e q u a n titie s o f c la y s

c o n ta in in g 100$ m o n tm o r i l l o n i t e . A c c o rd in g to t h e A m e ric a n

C o l l o i d C o m p an y , ’' V o l c l a y ” c o n t a i n s 8 8 - 9 0 $ m o n t m o r i l l o n i t e .

A riz o n a B e n to n ite

T h i s m a t e r i a l w a s re c o m m e n d e d b y W a rd * s N a t u r a l

S c ie n c e E sta b lish m e n t as th e p u re s t m o n tm o rillo n ite th ey

had a v a i l a b l e , a l t h o u g h i t w as a d m i t t e d t o c o n ta in o th e r

unknow n m i n e r a l s . T h is c l a y w as m in e d i n Y a v a p a i C o u n ty ,

A riz o n a *

S e v e r a l ty p e s o f m e a su re m e n ts m u st be u s e d I n i d e n t i ­

fy in g c la y m in e ra ls c o m p le te ly . In c lu d e d in th e se a re

c h e m ic a l a n a l y s i s , p e tro g ra p h ic e x a m in a tio n , X -ra y a n a l y s i s ,

th e rm a l a n a ly s is , and a s tu d y o f th e c o l l o i d a l b e h a v io r

of th e c la y .

C h e m ic a l a n a l y s i s by i t s e l f m eans v e r y l i t t l e .

P e tro g ra p h ic e x a m in a tio n s a re u s e f u l o n ly i n th e c a s e o f

c o a rse -g ra in e d c la y s , and even th e n e x p e r t i n t e r p r e t a t i o n

is needed. X -ra y w ork l i k e w i s e r e q u i r e s a sk ill in th is

ty p e o f w ork, and even th e n i s c a p a b le o f r e v e a lin g th e

p re s e n c e o f o n ly r e l a t i v e l y la rg e a m o u n ts o f i m p u r i t i e s .

It is b e lie v e d t h a t among t h e s im p le s t and m ost con­

c l u s i v e m e th o d s a v a i l a b l e fo r th e id e n tific a tio n o f c la y

m in e ra ls a re th o se o f th e rm a l a n a ly s is c o m b in ed w i t h a

s tu d y o f th e c o l l o i d a l b e h a v io r o f th e c la y s . It is tru e

t h a t b o t h o f t h e s e m e th o d s a r e r e l a t i v e l y cru d e. Com-
 59

p a r a t i v e l y l a r g e a m o u n t s o f i m p u r i t i e s m ay b e p r e s e n t

b efo re th e y can be d e t e c t e d by t h e d i f f e r e n t i a l th e r m a l

m e th o d , a c c o rd in g to N o rto n (7 4 ). H ow ever, c o m b in e d w i t h

an a n a ly sis of th e c o llo id a l b e h a v io r, th e rm a l a n a ly s is

can p ro v id e r a th e r c o n c lu s iv e in fo rm a tio n . F o r e x a m p le ,

th e p r e s e n c e o f o n ly a s m a ll am ount o f m o n tm o r illo n ite in

a s a m p le o f k a o l i n i t e w o u ld c a u s e a m a rk e d i n c r e a s e in th e

base exchange c a p a c i ty o f th e sa m p le .

D i f f e r e n t i a l T h erm al A n a ly se s

T he d e h y d r a t i o n b e h a v i o r o f c l a y m i n e r a l s has been

fo u n d to be c h a r a c t e r i s t i c o f th e m in e ra ls in v o lv e d , and

can th e re fo re be u se d a s a m eans o f t h e i r id e n tific a tio n .

T he m e t h o d u s e d w a s s i m i l a r t o t h a t o f N o rto n (7 4 ), H arm an

and F ra u lin i (5 7 ), and M itc h e ll (7 5 ).

T he a p p a r a t u s u s e d w a s t h a t w h i c h M i t c h e l l d e s c r i b e d

a n d u s e d , w i t h so m e m o d i f i c a t i o n s . A ste a d y h e a tin g r a te

o f a p p r o x i m a t e l y 6®C. p e r m i n u t e w a s m a i n t a i n e d . (M itc h e ll

a n d N o r t o n u s e d 14®C. p e r m i n u t e ; H arm an a n d F r a u l i n i u s e d

6 °C . p e r m i n u t e . ) D iffe re n tia l te m p e r a tu re s w ere m easured

w ith a g a lv a n o m e te r a tta c h e d to a Type K L e e d s a n d N o r th r u p

p o te n tio m e te r. T h e r e a d i n g s w e r e m ade i n g a l v a n o m e t e r

sc a le d iv is io n s .

T he a t t a c h e d p o t e n t i o m e t e r p e rm itte d c o u n te rb a la n c in g

th e d e f le c tio n o f t h e g a l v a n o m e t e r w hen h e a t e f f e c t s

c a u s e d l a r g e d e f l e c t i o n s w h i c h w o u l d h a v e m o v ed t h e g a l v a n ­
 60

o m e te r r e f l e c t i o n o ff th e s c a le . H e a d in g s o f tim e e l a p s e d ,

te m p e r a tu r e and d e f l e c t i o n w ere m ade. A fte r th e te m p e ra tu re ­

tim e c u rv e had b een e s t a b l i s h e d b y m any r u n s , i t w as p o s ­

sib le t o m ake r a p i d r e a d i n g s o f tim e and d e f l e c t i o n w ith

le s s f r e q u e n t c h e c k s on t h e t e m p e r a tu r e , th u s p e rm ittin g

a c o n tin u o u s r e c o r d o f d e f l e c t i o n s (o r h eat e f f e c t s ) .

M i t c h e l l * s m eth o d r e q u i r e d tw o o p e r a t o r s . The a p p a r a ­

t u s w as m o d i f i e d b y P o o l e * t o p e r m i t o n e o p e r a t o r t o m ak e

a ll o f th e r e a d in g s . The e l e c t r i c a l c i r c u i t is show n i n

F ig u re 1.

I n t e r p r e t a t i o n o f th e Therm al A n a ly ses

K ao lin

The k a o l i n show ed a s t r o n g e n d o th e rm ic p e a k a t 6 1 0 -

S15°C . and a s t r o n g e x o th e rm ic p eak i n t h e r e g i o n o f 980® C.

( F i g u r e 2) No o t h e r e f f e c t s w e r e a p p a r e n t . As m e n t i o n e d

b efo re, th is c l a y w a s a l s o u s e d b y H arm an a n d F r a u l i n i ,

who a l s o r e p o r t e d p e a k s a t 607-617® C . N o rto n r e p o r te d

a n e n d o th e rm ic p e a k i n k a o l i n i t e a t 6 1 0 ° C ., and an ex o ­

th e rm ic e f f e c t a t 980°C . T h erefo re, th e s e v a lu e s a g re e

w ith th o se p u b lis h e d f o r k a o l i n i t e .

W yom ing B e n t o n i t e

A la rg e e n d o th e rm ic e f f e c t w as fo u n d a t lo w t e m p e r a ­

tu re s , in d ic a tin g t h e re m o v a l o f a r a t h e r l a r g e am ount

o f a d so rb ed w a te r (F ig u re 3 ) . N o rto n r e p o r te d a d o u b le

e n d o t h e r m i c p e a k a t lo w t e m p e r a t u r e s . H e n d ric k s , N e lso n

and A le x a n d e r (5) a lso sh o w e d t h i s e ffe c t, and r e p o r t e d

* J, P . P o o le , R e s e a r c h A s s i s t a n t i n C e ra m ic s
 To p o t e n t i o m e t e r
( T e m p e r a t u r e i n A120 3 )

To
galvano m eter
(D if f e r e n t i a l
tem p eratu re)

A12 0 3 C lay

C = c.irouiel
A = alum el

DIFFER Sri TIAL THERMOCOUPLE CIRCUIT

F igure 1
 ]•" " ) i' " .:r : : i : : n | —It r:: r | r q t t - t r r ; r T J

le r n ia l e s [ o f . K a o l i n : wi t h V a r i o u s ' A d s o r b e d

K a d i i n j:( 99.42$ r e l a t i v e ! humid i t y j :

K a q lin •( a i r d ried )-! ' ' ; :

: num

ure 2

60b
T e m p e ra tu re ■
! 100 9 ( ^ 1 . 1 i.M Od
'v is'; ’‘ b '\ls ;*Ad. is ’*1 ’7 "’t''*'i :h ’:’t^'"!! ’:..i
!es: a i r d r i e d

! a s re c e iv e d

J_

rT s t a n d a r d ^ V o lelav ^

4 00 j ! 500
THermaj.1 A ija ly s e s o f A r i z o &a IM^n t f f l ^ r i l i o n l f e e

rece-i-ved :

and -mleronJjCr.adt.loii

P09
50.0.: . ,80Q:i '..'.'idpti
 61

th a t i t d e p e n d s u p o n t h e t y p e o f a d s o r b e d |c » B n a n d t h e r e l a ­

tiv e h u m id ity o f t h e a tm o s p h e re t o w h ic h t h e c l a y w as e x ­

posed p r i o r to th e te s t. An e n d o t h e r m i c p e a k w a s f o u n d a t

7 0 0 -7 1 5 ° C ., and a s m a ll e r e n d o th e r m ic p e a k w as v i s i b l e at

a b o u t 875°C . N o rto n r e p o r t e d t h e s e p e a k s a t 690°C . and

870°C . r e s p e c t i v e l y , i n so m e s a m p l e s o f m o n t m o r i l l o n i t e

a n d i n W yoming b e n t o n i t e . In a d d itio n to th e s e p e a k s,

w h ic h a g re e w e l l w i t h t h o s e p r e v i o u s l y r e p o r t e d , an exo­

t h e r m i c p e a k w a s f o u n d a t a b o u t 925® C. T h i s p e a k lia s n o t

been re p o rte d in th e lite ra tu re .

A riz o n a B e n to n ite

T h is c l a y show ed a v e r y l a r g e e n d o th e rm ic e f f e c t a t

lo w t e m p e r a t u r e s , In d ic a tin g th e rem o v al o f a la r g e am ount

o f a d so rb e d w a te r (F ig u re 4 ) . A b ro a d e n d o th e rm ic effect

w as f o u n d i n th e r e g i o n o f 650°C . an d a s h a r p e r e n d o th e rm ic

peak a t 835°C . T h e se p e a k s do n o t a g r e e w i t h t h o s e o f a n y

m in e ra l o f th e c la y ty p e r e p o r te d by N o rto n . An e x o t h e r m i c

p e a k i n t h e r e g i o n o f 9 3 5 °C . was a p p a r e n t . T h is p e a k was

a ls o n o te d in t h e W yoming b e n t o n i t e . The p e a k a t 6 5 0 °C .

m ay i n d i c a t e th e p resen ce of i l l i t e . B ased on th e i n t e r ­

p re ta tio n o f th e rm a l a n a ly s is a lo n e , th e re fo re , t h is m a te r­

i a l w o u ld n o t seem t o be com posed l a r g e l y o f m o n tm o rillo ­

n ite . H ow ever, th e r e s u l t s o f t h e m e a su re m e n ts o f t h e

base exchange c a p a c ity o f t h is m a te r ia l, a s w i l l b e show n

la te r, In d ic a te a r a t h e r la rg e base exchange c a p a c ity , su ch

as h as b e e n p r e v i o u s l y show n t o e x i s t o n ly i n c la y m in e ra ls

of th e m o n tm o rillo n ite ty p e .
 62

S e d im e n ta tio n T e s ts w ith K a o lin

S e d im e n ta tio n t e s t s w e r e m ade w i t h t h e k a o l i n a c c o r d -

in g t o t h e m eth o d o f B o u y o u c o s (76) u sin g th e C asag ran d e

n o m o g rap h (77) i n o rd e r to d e te rm in e th e a p p a re n t ch an g es

in p a rtic le siz e d is tr ib u tio n o f th e c la y w ith v a rio u s

a m o u n t s o f NaOH a n d t h u s fin d t h e o p tim u m c o n d i t i o n f o r

d e f lo c c u la tio n of th e s u s p e n s io n in o rd e r t h a t p a r t i c l e

siz e se p a ra tio n s c o u ld l a t e r b e m ad e u n d e r t h e sa m e c o n ­

d itio n s o f c o n c e n t r a t i o n an d pH. The r e s u l t s a re p re se n te d

in F ig u re 5.

It c a n b e s e e n t h a t o p tim u m d e f l o c c u l a t i o n o c c u r r e d

w h en 8 - 1 6 m . e . o f NaOH p e r 1 0 0 gm. c l a y had b e e n a d d e d .

M e a s u r e m e n t s o f t h e pH o f a l l t h e s e s u s p e n s i o n s w e r e m ade

w ith a n a n tim o n y e l e c t r o d e . (T h w in g -A lb e rt I n s tr u m e n t C o .,

P h ila d e lp h ia , P a » , T y p e PH N o . 8 4 6 8 )

The a n tim o n y e l e c t r o d e h as th e a d v a n ta g e o f b e in g

v e ry sim p le to o p e ra te ; it c a n b e u s e d a t v e r y h i g h pH

(w h ile m ost g l a s s e le c tro d e s c a n n o t), an d w as s u f f i c i e n t l y

re lia b le fo r th is ty p e o f d e te r m in a tio n . T he pH r e a d i n g s

o b t a in e d w i t h t h e a n tim o n y e l e c t r o d e w e re com pared w i t h

r e a d i n g s o b t a i n e d o n t h e sa m e s a m p l e s w i t h t h e hydrogen

e l e c t r o d e u s e d by H enry a n d T a y l o r (3 5 ). The r e a d i n g s

o b t a i n e d w i t h t h e a n t i m o n y e l e c t r o d e a t pH l e s s th a n 10

w ere s l i g h t l y h ig h e r th a n th o se o b ta in e d w ith th e hy d ro ­

gen e le c tr o d e , b u t a t pH g r e a t e r t h a n 1 0 t h e r e w as l i t t l e

d iffe re n c e . T he o p tim u m c o n d i t i o n s f o r maximum d i s p e r s i o n

in th is c o n c e n t r a ti o n o f c l a y to w a te r w ere t h e r e f o r e fo u n d

t o b e f r o m pH 1 1 . 0 - 1 1 . 5 .
 PjOO&CLE --S1ZS- -DXStcilBUXiiD^ -O E-LA iiiiLH E-iJU & H i

WITH 1/IFFSHEMT iuiOUWTS OF• FL3CTR0LYTE

maOH .
* ;1 00; gia.- pH- :

4>. - 7 . 0 I - - - - : ....................................

-50
1 1 . 3 Optimum;;
11.$ d e f l o c c u l a t i o n
; ______
12.2

.10

101 0.2

62a
N Q »£ IAICJ O jL X K 3 •.*i •
i 3 d ? e HdVSD N 3 □ Z J. 3 1G
 63

The p e r c e n t a g e o f c l a y f i n e r t h a n a n y g i v e n d i a m e t e r

c a n be r e a d f r o m t h e f i g u r e . S l i g h t l y l e s s t h a n 40% o f

t h e k a o l i n a s r e c e i v e d was f o u n d t o h a v e a p a r t i c l e s i z e

s m a l l e r t h a n one m i c r o n .

P a r t i c l e S i z e S e p a r a t i o n o f The K a o l i n

K a o lin s a r e r e l a t i v e l y i n a c t i v e from t h e c o l l o i d a l

v i e w p o i n t . , c o m p a r e d w i t h m i n e r a l s h a v i n g a much l a r g e r

base exchange c a p a c i t y . I t i s obvious t h a t a g r e a t e r

r e a c t i v i t y would p e r m i t a s t u d y o f t h e e f f e c t o f v a r i o u s

c a t i o n s on t h e p r o p e r t i e s o f t h e c l a y t o be made more

easily . Since th e c o ll o i d a l a c t i v i t y in c re a s e s w ith

an i n c r e a s e i n s p e c i f i c s u r f a c e , t h e r e a p p e a r e d t o be an

ad v an tag e i n u s in g t h e s m a l l e r p a r t i c l e s i z e s f o r t h i s work.

Two m e t h o d s a r e a v a i l a b l e f o r t h e f r a c t i o n a t i o n o f

clay s: (l) s e d im e n ta tio n , or s e t t l i n g , m ethods, (.2) c e n t r i ­

f u g a l m ethods. S edim entation procedures a re s u i t a b l e fo r

t h e s e p a r a t i o n o f f r a c t i o n s l a r g e r t h a n one m i c r o n . The

s u p e r c e n t r i f u g e m u s t be u s e d t o o b t a i n f r a c t i o n s o f a s i z e

s m a l l e r t h a n one m i c r o n .

F r a c t i o n s s m a l l e r t h a n o ne m i c r o n w e r e o b t a i n e d by

th e use of th e S h a rp ie s s u p e r c e n tr i f u g e . T his procedure

r e q u i r e d much t i m e i n o r d e r t o o b t a i n a v e r y s m a l l y i e l d

o f c l a y from a m a t e r i a l as c o a r s e g r a i n e d a s t h e k a o l i n .

I t was c a l c u l a t e d , a f t e r f i n d i n g how s m a l l t h e y i e l d w a s ,

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

req u ire d to f r a c t i o n a t e a p p re c ia b le q u a n titie s of t h i s c la y .

F o r t h i s r e a s o n , no s e p a r a t i o n s w e r e made by t n i s m e t h o d on

a large sc a le .
 64

Sed im e n ta tio n P ro c ed u re

P a rtic le s o f t h e k a o l i n lea v in g a d i a m e t e r o f l e s s than

one m ic r o n w e re o b t a i n e d by d i s p e r s i n g t h e c l a y and a l l o w ­

ing i t to s e t t l e . A l a r g e volume ( a b o u t 30 g a l l o n s ) of the

s u s p e n s i o n was p r e p a r e d , c o n t a i n i n g 35 gm. o f t h e c l a y a s

r e c e i v e d p e r 100 m l. of d istille d w ater. D eflo ccu latio n

was a c c o m p l i s h e d b y a d d i n g e n o u g h NaOH t o b r i n g t h e pH

u p t o 1 1 . 0 - 1 1 . 5 , w h i c h h a d b e e n s h o w n t o b e t h e o p t im u m

pH r a n g e f o r d i s p e r s i o n . The s u s p e n s i o n was p a s s e d t h r o u g h

a 32 5 m e s h s c r e e n , and e q u a l p o r t i o n s o f i t w ere p la c e d

in crocks of 5 g a llo n s c a p a c ity .

E a c h s u s p e n s i o n was a l l o w e d t o s t a n d a b o u t 2 4 h o u r s ,

a f t e r w h i c h t h e u p p e r p o r t i o n o f t h e s u s p e n s i o n was rem oved

by s ip h o n in g . S p e c i a l g l a s s s ip h o n s w ere c o n s t r u c t e d to

p e rm it a m easurem ent o f th e d e p th to w h ich th e o r i f i c e of

t h e s i p h o n was im m ersed b e lo w t h e s u r f a c e o f t h e s u s p e n ­

sio n . The o r i f i c e o f t h e s i p h o n was d i r e c t e d u p w a rd ,

p rev en tin g th e rem oval o f p a r t i c l e s having a s i z e g r e a t e r

than th a t d e s ir e d .

The d e p t h t o w h i c h t h e s i p h o n was im m ersed d e p e n d e d

on t h e tim e o f s e t t l i n g and t h e t e m p e r a t u r e . T h is d is ta n c e

was c a l c u l a t e d b y m e a n s o f t h e C a s a g r a n d e n o m o g r a p h ( 7 7 ) ,

A p p r o x i m a t e l y 8 cm. w e r e r e m o v e d e v e r y 2 4 h o u r s . One s i ­

phoning o p e r a t i o n , of course, c o u l d n o t rem ove a l l the

p a rtic le s less t h a n one m i c r o n , b e c a u s e t h e s e 7/ere o r i g i n a l ­

ly d istrib u te d t h r o u g h o u t th e volume o f t h e l i q u i d . A fter

 65

th e f i r s t siphoning o p e r a t i o n t h e s u s p e n s i o n was d i l u t e d to

its o r i g i n a l volum e. The pH o f t h e r e s u l t i n g su sp en sio n

was t h e n m e a s u r e d w i t h a n a n t i m o n y e l e c t r o d e . In v ariab ly

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

w ater. E n o u g h NaOH s o l u t i o n w a s t h e n a d d e d t o b r i n g t h e

pH b a c k t o i t s o rig in a l v alu e. I n t h i s m aim er c o m p le te

d e f l o c c u l a t i o n was m a i n t a i n e d a t a l l tim es. The s u s p e n s i o n

was t h e n a l l o w e d t o s e t t l e a n d t h e p r o c e d u r e was r e p e a t e d .

I t was n e c e s s a r y t o go t h r o u g h t h i s o p eratio n fiv e tim es

for each c o n ta in e r , a f t e r w hich p r a c t i c a l l y a ll o f the

p articles less t h a n one m ic r o n had b e e n r e m o v e d . S ix

e a r t h e n w a r e c r o c k s w ere u s e d a t one t i m e , and t h e whole

c y c l e was r e p e a t e d tw ice w ith each of the six co n tain ers.

I n t h i s manner a b o u t 2 ,0 0 0 gm s. o f c l a y w ere o b ta in e d

V i s c o s i t y M easurem ents W ith K a o lin

The a p p a r e n t v i s c o s i t y o f t h e c l a y a s r e c e i v e d sh o w e d

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

a decrease a s m o r e NaOH w a s a d d e d , Henry and T a y lo r (35)

b eliev ed th a t s u c h b e h a v i o r was c a u s e d by t h e p r e s e n c e o f

a sw ellin g m in e ra l, and J o h n s o n and N o r to n (73) and B a v er

(79) showed t h a t sw ellin g c o u l d be c a u s e d by t h e p r e s e n c e

of o rganic m a tte r.
The c l a y w a s t h e n p a s s e d t h r o u g h a 3 2 5 - m e s h s c r e e n a n d

electro d ialy sed . A ro u g h m easurem ent o f th e v i s c o s i t y b e ­

h a v i o r w a s m ade by a d d i n g su c ce ssiv e p o rtio n s o f NaOH t o

t h e sa m e s a m p l e o f c l a y . The v i s c o s i t y c u r v e showed a
 66

minimum a t 4 m . e . o f NaOH p e r 1 0 0 gm. o f c l a y . . Increas­

i n g a m o u n t s o f NaOH c a u s e d a s l i g h t i n c r e a s e In v i s c o s ity

b u t n o hump o c c u r r e d i n t h e c u r v e .

It is th erefo re s e e n t h a t s c r e e n i n g and e l e c t r o -

d i a l y s i s rem oved t h e c a u s e o f t h e hump. The hump was

p r o b a b ly c a u se d by th e p re s e n c e o f o rg a n ic m a t t e r . These

b rie f v isc o sity te sts showed t h e p r e s e n c e o f no m i n e r a l

other than k a o l i n i t e in the c la y .

P r e p a r a tio n o f H -k ao lin

The f r a c t i o n o f t h e k a o l i n w h i c h was l e s s t h a n one

m ic ro n i n d i a m e t e r a s o b t a i n e d by t h e s e d im e n ta t io n m ethods

c o n t a i n e d NaOH w h i c h h a d b e e n a d d e d a s a d e f l o c c u l a n t „

Any o r g a n i c m a t t e r w h i c h w a s p r e s e n t i n t h e c l a y was

also p re s e n t In th e su sp en sio n . Stexis w ere t h e n t a k e n t o

fo rm a n H - k a o l i n a n d t o rem ove o r g a n i c m a t t e r . The k a o l i n

was w a s h e d w i t h HC1, e l e c t r o d i a l y z e d , t r e a t e d w i t h Hs 0 a ,

and e l e c t r o d i a l y z e d a g a i n . These o p e r a t io n s are d escrib ed

i n more d e t a i l b e lo w .

T r e a t m e n t wi t h HC1
HC1 w a s a d d e d t o t h e d e f l o c c u l a t e d su sp en sio n in

a m o u n t s s u f f i c i e n t t o r e a c h pH 7 . At t h i s pH t h e k a o l i n

was f l o c c u l a t e d and s e t t l e d to th e bottom o f th e c o n t a i n e r s .

D i s t i l l e d w a t e r was a d d e d , the f lo c c u la te d clay s lip was

blu n g ed , a n d t h e c l a y was a g a i n a l l o w e d t o s e t t l e . T h is

o p e r a t i o n o f w ashing and s e t t l i n g was r e p e a t e d a b o u t s i x

tim e s t o rem ove a s much o f t h e e x c e s s e le ctro ly te as p o ss ib le .

 67

E lectro d ialy sis

E l e c t r o d i a l y s i s was c a r r i e d out in la rg e , th ree -

cham bered M a tts o n ty p e c e l l s , d escrib ed by Henry and

T aylor (35)«

A sm all c e l l of th e t y p e u s e d by H e n ry was f i t t e d

w ith a d e v ic e fo r c o n tin u o u s flow o f d i s t i l l e d w ater th ro u g h

th e o u te r co m p artm en ts, A s t i r r e r w a s a l s o made w h i c h

ag itated th e c la y s lip b y m o v i n g u p a n d down i n t h e c e n t r a l

com partm ent. T h i s c e l l was u s e d a t a v o l t a g e o f a b o u t 180

v o l t s D.C* f u r n i s h e d b y t h e r e c t i f i e r d e s c r i b e d by Henry (35),

I t was fo u n d t h a t t h i s sm all c e l l , w ith co ntinuous

change o f d i s t i l l e d w ater in t h e o u t e r c o m p a r tm e n ts , and

w ith co n tin u o u s stirrin g produced an H -clay w hich d id

not d iffe r a p p r e c i a b l y from t h a t p ro d u c e d by t h e l a r g e r

c e l l s n o t so e q u ip p e d . As t h e c a p a c i t y o f t h e l a r g e r c e l l s

was m o r e t h a n t e n t i m e s t h a t of th e sm all c e l l , i t was

decided to u se o n ly th e l a r g e r c e lls.

E l e c t r o d i a l y s i s w a s c o n t i n u e d a t 1 1 0 D.C-. w i t h f r e ­

quent changes of d i s t i l l e d w a te r u n t i l t h e amount o f c u r r e n t

p assing th ro u g h each c e l l , w ith th e clay s l i p in the c e n t r a l

com partm ent, a p p r o a c h e d t h a t w h i c h was p a s s e d w h e n t h e

c e n t r a l c o m p a r t m e n t was f i l l e d w ith d i s t i l l e d w ater a lo n e .

About f o u r d a y s were r e q u i r e d f o r th e e le ctro d ialy sis of

each b a tc h o f kao lin ..

Removal o f O r g a n ic M a t t e r

A fter the p relim in ary e le c tr o d ia ly s is th e clay s l i p

was t r e a t e d w i t h a n a m o u n t o f . H2 0 a e q u a l t o 1% o f t h e
 68

w eight o f th e c la y (78) . Some a u t h o r s have s a i d t h a t

t r e a t m e n t w i t h H2 0 2 s h o u l d b e c o n t i n u e d u n t i l n o b u b b l i n g

c an be d e t e c t e d , supposedly in d ic a tin g t h a t n o C02 i s

b e in g evolved,. I t was f o u n d t h a t b u b b l i n g p e r s i s t e d f o r

many d a y s , p r o b a b ly long a f t e r th e o r g a n i c m a t t e r had b e e n

decomposed* T h is bub b lin g is a ttrib u te d to th e decom posi­

t i o n o f H2.02 b y t h e c o l l o i d a l m a t e r i a l , n o t t o the form a­

t i o n o f C02 *

A more r e l i a b l e te st for com pletion o f th e o x id a tio n

of th e o rganic m a tte r Is a t e s t f o r t h e e v o l u t i o n o f C02 .

An a l k a l i n e b a r i u m c h l o r i d e s o l u t i o n was u s e d i n t h i s

te st. When n o m o r e C02 w a s e v o l v e d n o p r e c i p i t a t e o f BaCOs

was d e t e c t e d .

R e -electro d ialy sis

A fter th e o x id a tio n of th e organic m a tte r , th e c lay

s l i p was e l e c t r o d i a l y z e d again* The c l a y was t h e n d r i e d

on P y r e x p l a t e s a t a b o u t 60°C.

P r e p a r a tio n of H -b en to n ites

Ho p a r t i c l e size s e p a r a t i o n s w e r e made i n the case of

t h e Wyoming b e n t o n i t e a n d t h e A r i z o n a b e n t o n i t e * The

m a jo rity of the p a r t i c l e s In th e se c la y s a re so sm all th a t

i t was b e l i e v e d th at th e rem oval of p a r t i c l e s g reater than

one m ic r o n i n d i a m e t e r by s e t t l i n g m ethods w ould be w i t h ­

out v alu e.

Removal of O rg a n ic M a tte r

The b e n t o n i t e s w e r e t r e a t e d w i t h H-jOg a s d e s c r i b e d i n

th e tre a tm e n t of th e k ao lin *
 69

E le c tro d ia ly sis

T he b e n t o n i t e s w e r e e l e c t r o d i a l y z e d in th e m anner d e­

sc rib e d in th e tr e a tm e n t o f th e k a o l i n , ex cep t t h a t lo n g e r

t r e a t m e n t w as r e q u i r e d .

T h e Wyoming b e n t o n i t e w as e l e c t r o d i a l y z e d f o r s i x d a y s

w ith fre q u e n t changes o f d i s t i l l e d w a t e r i n t h e o u t e r com­

p a rtm e n ts* I t w a s p r o b a b l e t h a t i r o n . w a s re m o v e d f r o m t h e

c la y , b e c a u s e a r e d d i s h - b r o w n , f l o c c u l a n t p r e c i p i t a t e w as

a p p a r e n t i n t h e c a t h o d e c o m p a rtm e n t* In o rd er to sh o w

w h e th e r o r n o t r a d i c a l ch an g es i n th e s t r u c t u r e o f th e

b e n t o n i t e w ere c a u s e d by e l e c t r o d i a l y s i s , d i f f e r e n t i a l

t h e r m a l a n a l y s e s w e r e m ade b e f o r e a n d a f t e r e le c tro d ia ly s is .

Wo g r e a t d i f f e r e n c e w as f o u n d i n t h e t y p e o f c u r v e o b t a i n e d .

(S ee F i g u r e 3 ) . I t m ay, t h e r e f o r e , be c o n c lu d e d t h a t th e

e le c tijja ia ly s is t r e a t m e n t d i d n o t a p p r e c i a b l y b r e a k down t h e

stru c tu re o f th e m o n tm o rillo n ite .

The A r i z o n a b e n t o n i t e p r e s e n t e d a p r o b l e m i n r e g a r d

to fo rm a tio n o f an H - b e n to n ite . G r e a t a m o u n ts o f a d s o r b e d

io n s o r s a l t s w e re rem oved fro m t h i s c la y by e l e c t r o d i a l y s i s .

The d i a l y s a t e w a s c o n c e n t r a t e d b y e v a p o r a t i o n a n d t h e s a l t s

w ere rem o v ed an d c o l l e c t e d fo r a n a ly sis. At p resen t te s ts

f o r t h e i o n s rem o v ed h av e n o t b e e n m ade, b u t i t ap p ears

t h a t e i t h e r Ca o r Mg, o r b o t h , w e r e r e m o v e d i n l a r g e a m o u n t s

b e c a u s e a w h i t e p r e c i p i t a t e was fo rm e d i n t h e d i a l y s a t e

liq u id on i t s sta n d in g in a ir . The c o m p o s i t i o n o f p r e c i ­

p ita te is t h o u g h t t o b e e i t h e r CaC03 o r MgC03 . T h is s u p -

 70

p o s i t i o n i s m ad e m o re p r o b a b l e b e c a u s e t h i s b e n to n ite is

of th e n o n -sw e llin g ty p e, i n w h ic h C a * is u s u a l l y p r e s e n t

a s th e a d s o r b e d io n *

D i a l y s i s w as c o n tin u e d f o r s e v e r a l w eeks w i t h f r e ­

q u en t changes o f th e w a te r i n th e e le c tr o d e c o m p a rtm e n ts.

Even a f t e r t h i s le n g th of tim e , c o n s i d e r a b l e am o u n ts o f

i o n s w ere s t i l l b e in g rem oved. H ow ever, t h e d i a l y s i s w as

d i s c o n t i n u e d a n d t h e c l a y a s u s e d w as p r o b a b l y l a r g e l y ,

b u t n o t c o m p le te ly , s a t u r a t e d w i t h hydrogen i o n s .

A fte r e le c tr o d ia ly s is , b o t h t h e Wyoming a n d A r i z o n a

b e n t o n i t e s w ere d r i e d a t 60°C .

M easu rem en t o f B ase E xchange C a p a c i t i e s

Of t h e C l a y s U s e d .

T he b a s e e x c h a n g e c a p a c i t y o f e a c h c l a y w as d e t e r m i n e d

by t i t r a t i n g t h e H - c l a y w i t h NaOH a n d m e a s u r i n g t h e pH

of th e su s p e n s io n . A B e ck m an pH m e t e r , I n d u s t r i a l M o d e l ,

was u s e d f o r t h e pH d e t e r m i n a t i o n .

K a o lin

T h e r e l a t i o n o f pH t o a m o u n t o f NaOH a d d e d i s s h o w n

in F ig u re 6. An i n f l e c t i o n in th e t i t r a t i o n c u r v e w as

f o u n d a t pH 8 , c o rre sp o n d in g t o a b a s e e x c lia n g e c a p a c i t y

o f 3 m . e . p e r 1 0 0 gm . o f c l a y . T h is r e s u l t com pares w e l l
i
w i t h t h a t o f H arm an a n d F r a u l i n i ( 5 7 ) , who m e a s u r e d t h e

b a s e e x c lia n g e c a p a c i t y o f t h i s c l a y b y t h e ammonium a c e t a t e

d i s t i l l a t i o n m eth o d . They fo u n d t h e b a s e e x c lia n g e c a p a c i t y

o f th e f r a c t i o n fro m 1 m ic ro n to 0 .5 m ic ro n i n d ia m e te r
HO^M
 71

t o be a p p r o x im a te ly 3 .7 m .e . p e r 100 gm . They d i d n o t

tre a t t h e c l a y t o r e m o v e o r g a n i c m a t t e r , w h i c h may a c c o u n t

fo r th e s lig h tly h ig h e r v a lu e w h ic h th e y o b t a i n e d .

The d r y H - c la y w as a l s o titra te d w i t h C a(0H )2 a f t e r

it had b e e n s t a n d i n g a b o u t one m o n th . I t m ay b e n o t e d

( i n F ig u r e 6) th a t a lth o u g h th e in f le c ti o n p o in t is o b ta in e d

a g a in a t 3 m .e . o f C a ( 0 H ) 2 p e r 1 0 0 gm . o f c l a y , t h e pH

o f th e H -c la y su sp en d ed i n d i s t i l l e d w a te r i s som ew hat

h ig h e r. T h i s i n d i c a t e s t h e v a r i a b i l i t y w h i c h may b e e x p e c t e d

in th is ty p e o f w o rk . A p p a r e n t l y som e s u r f a c e c h a n g e s

o c cu r on s t a n d i n g .

Wyom ing b e n t o n i t e

The r e l a t i o n o f pH t o a m o u n t o f NaOH a d d e d i s show n

in F ig u re 7. An i n f l e c t i o n p o i n t i n t h e c u r v e i s ap p aren t

a t pH 9 c o r r e s p o n d i n g t o a n a d d i t i o n o f 75 m . e . o f NaOH

p e r 1 0 0 gm. A pH o f 8 w as a t t a i n e d w i t h t h e a d d i t i o n o f

70 m. e . p e r 1 0 0 gm.

A riz o n a b e n to n i t e

The r e l a t i o n o f pH t o t h e a m o u n t o f NaOH a d d e d i s

sh o w n i n F i g u r e 7. T he s h a p e o f t h e c u r v e o b t a i n e d i s

ra th e r p e c u lia r. T h e pH i s ra th e r h ig h o v e r a lo n g r a n g e ,

b u t w ith an a d d it i o n o f up to 7 0 m . e . p e r 1 0 0 gm. t h e pH

o b t a i n e d vm s o n l y 7 . 2 . T h erefo re, t h i s m a t e r i a l has an

im p o rta n t c h a r a c t e r i s t i c of m o n tm o rillo n ite , i.e ., a h ig h

b a s e e x c lia n g e c a p a c i t y .
 72

C o n c lu s io n s r e g a r d in g M in e ra l

C o m p o sitio n o f th e C la y s

Ka o l i n

T he k a o l i n u s e d w as s h o w n t o c o n s i s t o f k a o l i n i t e ,

w ith v ery l i t t l e c o n ta m in a tio n , if any. T herm al a n a ly s e s

c u rv es a g re e d v e ry w e ll w ith e x is tin g d a ta . T he b a s e

e x c l ia n g e c a p a c i t y o f t h e k a o l i n w a s f o u n d t o be 3 m .e . o f

NaOH p e r 1 0 0 gm . o f c l a y , w h ic h a l s o c o in c id e s w ith a v a i l ­

a b le in fo rm a tio n . T he v i s c o s i t y b e h a v i o r o f t h e k a o l i n

w i t h NaOH a d d i t i o n s a l s o i n d i c a t e d t h a t no s w e llin g m in e r­

a ls , s u c h a s m o n t m o r i l l o n i t e , w ere p r e s e n t .

Wy o m in g b e n t o n i t e

T h e r m a l a n a l y s e s sh o w e d t h i s c la y to be t y p i c a l o f

th o se c o n ta in in g la rg e q u a n titie s o f m o n tm o rillo n ite .

The s w e l l i n g w a s l i k e w i s e c h a ra c te ristic of m o n tm o rillo n ite .

The b a s e e x c l i a n g e c a p a c i t y w a s f o u n d t o be 6 0 -7 5 m .e . o f

NaOH p e r 1 0 0 gm. M o n tm o rillo n ite i s th e o n ly c la y m in e ra l

know n t o have a b a se exchange c a p a c ity i n t h i s ran g e*

A riz o n a b e n to n ite

T h is c la y a l s o had a v e ry l a r g e b a s e ex ch a n g e c a p a c i t y

( a b o u t 70 m . e . p e r 1 0 0 g m . ) , a n d w a s t h e r e f o r e in d ic a te d

t o be com posed o f a m i n e r a l o f t h e m o n t m o r i l l o n i t e t y p e .

H o w e v e r, t h e r m a l a n a l y s e s i n d i c a t e d th e p resen ce o f o th e r

m in e r a ls w h ic h c o u ld n o t be i d e n t i f i e d . For th is reaso n ,

Wyoming b e n t o n i t e w as u s e d i n t h e w o r k o n h e a t o f w e t t i n g .

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

re m a in d e r o f th e e x p e r i m e n t a l w ork f o r p u r p o s e s o f c o m p a ris o n .
 73

P r e p a r a t i o n o f N a - , K - , C a - C la y s

P r e p a r a t io n o f N a-. K - » C a -K ao lin s

N a - , K - , a n d C a - k a o l i n s w e re p r e p a r e d by t h e a d d i t i o n

o f 3 m . e . o f NaOH, KOH a n d Ca(OH)2 , r e s p e c t i v e l y t o 100 gm.

o f th e H -k a o lin . S u f f i c i e n t d i s t i l l e d w a t e r was a d d e d t o

p e rm it a g i t a t i o n o f th e s u s p e n s io n s . The p r e p a r a t i o n s

w e re a g e d a b o u t 24 h o u r s , when m e a s u r e m e n ts o f pH w e r e made

to check th e p ro p e r a d d it i o n o f th e h y d ro x id e s. The s l i p s

w e re p o u r e d i n t o P y r e x t r a y s , d r i e d a t a b o u t 6 0 °C . a n d t h e

c l a y g r o u n d t o p a s s a 30 m e s h s c r e e n .

P r e p a r a t i o n o f N a - . K - . Ca-Wvoming b e n t o n i t e s

N a - , K~, Ca-Wyoming b e n t o n i t e s w e re p r e p a r e d by t h e

a d d i t i o n o f 70 m . e . o f NaOH, KOH, a n d C a (0 H )2 , r e s p e c t i v e l y

t o 100 gm. o f t h e H - b e n t o n i t e . The r e m a i n d e r o f t h e p r o c e ­

d u r e was t h e sam e a s f o r t h e k a o l i n , e x c e p t t h a t t h e d r y

b e n t o n i t e was p a s s e d t h r o u g h a 2 3 0 m esh s c r e e n .

P r e p a r a t i o n o f N a -. K -. C a -A riz o n a b e n t o n i t e s

N a - , K - , C a - A r i z o n a b e n t o n i t e s w e re p r e p a r e d by a d d i n g

70 m .e . o f NaOH, KOH, a n d C a ( 0 H )2 r e s p e c t i v e l y t o 100 gif-,

o f th e b e n to n ite . The r e m a i n d e r o f t h e p r o c e d u r e was t h e

same a s f o r t h e Wyoming b e n t o n i t e . I t w as n o t e d t h a t t h e

pH o f t h e r e s u l t i n g s u s p e n s i o n s , u n f o r t u n a t e l y , d i d n o t

c h e c k w e l l w i t h t h a t f o u n d i n t h e t i t r a t i o n c u r v e , b u t was

c o n s id e ra b ly h ig h e r ( a b o u t pH l l ) . T h is i s , p e r h a p s , a

r e s u l t o f t h e f a c t t h a t i t was v e r y d i f f i c u l t t o o b t a i n

H - b e n t o n i t e , i n t h i s c l a y , by e l e c t r o d i a l y s i s . P erhaps
 74

som e a d d i t i o n a l i o n s w h i c h s h o u l d h a v e b e e n r e m o v e d b y

e l e c t r o d i a l y s i s m ay h a v e f o u n d t h e i r w ay t o th e su rfa c e

o f th e m a te r ia l upon a g in g .

CALORIMETRY

G en eral P ro ced u re f o r H eat of

W e ttin g D e te rm in a tio n s

In s e le c tin g th e p ro ced u re to be used in th is in v e s ti­

g a tio n , a n e f f o r t w a s m ad e t o k e e p i n m in d t h e l i m i t a t i o n s

in v o lv e d i n th is ty p e o f m e a su re m e n t.

T he m e t h o d , b r i e f l y , c o n siste d o f d ry in g th e c la y

in a g la s s b u lb a t a c o n s ta n t te m p e ra tu re (1 1 5 °C .) in a

vacuum . T he b u l b w a s s e a l e d w h i l e b e i n g d r i e d a n d e v a c u ­

a te d . The b u l b was t h e n p l a c e d i n t h e c a l o r i m e t e r , b ro k en

by im p a c t , an d t h e te m p e ra tu re r i s e w as m e a s u r e d . T he

am ount o f h e a t e v o lv e d w as d e te r m i n e d b y i n t r o d u c i n g a

known q u a n t i t y o f e l e c t r i c a l e n e r g y i n t o th e c a lo rim e te r,

w ith i t s c o n te n ts , and d e te r m in in g th e te m p e ra tu re r i s e .

An e l e c t r i c a l c a l i b r a t i o n m e th o d w as u s e d i n p r e f e r e n c e to

th e a l t e r n a t i v e of c a lc u la tin g th e q u a n t i t y o f h e a t e v o lv e d

fro m c o n s i d e r a t i o n s o f t h e w a te r e q u i v a l e n t o f t h e c a l o r i ­

m e ter and th e s p e c i f i c h e a t and w e ig h ts o f t h e c l a y and

g la ss.

P r o c e d u r e f o r D ry in g and

E v a c u a tin g C lay

T he c l a y w a s p L aced i n a th in g la s s b u lb , h a v in g a

d i a m e t e r o f 1—? / 8 n + 1 / 8 " , made b y F . M a l l o y , d l a s s b l o w e r ,

 '•rrtrrr:~

e : Exc h a nge. C

-Try ora irtg~ xjsrrcxm±r,e

i^ n to n ita

- V i ' :' V ••
1_J

: . 9

74a
[■; [

e . MQH p e r 100 gm* ■ clay.,.::

 75

S c h o o l o f C h e m is try a n d P h y s i c s , T h e 'P e n n s y lv a n i a S t a t e

C o lle g e . P y rex tu b in g , 10 mm. i n d i a m e t e r , w a s f o u n d t o

be m ost s a t i s f a c t o r y in th e ir p re p a ra tio n . The b u l b s

had t o b e m ade w i t h a w a l l t h i c k enough to w ith s ta n d

a tm o s p h e ric p r e s s u r e a f t e r b e in g e v a c u a te d , y e t t h i n

enough to be e a s i l y s h a t t e r e d by t h e b r e a k e r r o d i n t h e

c a lo rim e te r.

The b u l b w as w e ig h e d and f i l l e d w ith c la y , and th e n

t h e t u b e w as c o n s t r i c t e d , b u t n o t c lo s e d , im m e d ia te ly

above th e b u lb . The b u l b , w i t h t h e c l a y i n i t , w as p l a c e d

i n a sm a ll d ry in g o v e n a t 1 1 5 ° C . , sh o w n i n F i g u r e 8 .

A f t e r b e in g i n t h e o v e n a b o u t one h o u r , a vacuum was g r a d u ­

a lly c re a te d in th e b u lb by s lo w ly c lo s in g t h e v a lv e w h ic h

p e rm itte d a i r to le a k i n t o th e sy ste m . I t w as n e c e s s a r y

to e v a c u a te s lo w ly i n o r d e r t o p r e v e n t th e c l a y fro m b e in g

s w e p t o u t o f t h e b u l b a s t h e a i r w as re m o v e d . A Cenco

I-Iyvac pump ( C e n t r a l S c i e n t i f i c C o ., C h ic a g o , Illin o is ),

c a p a b l e o f p r o d u c i n g a v a c u u m o f 0 . 0 0 0 4 mm. o f m e r c u r y was

used. E v a c u a t i o n w as c o n ti n u e d f o r a p e r i o d o f t h r e e hours

a fte r c lo s in g th e v a lv e .

T he b u l b w a s t h e n s e a l e d w i t h a g a s - a i r f l a m e a p p l i e d

a t th e c o n s tr ic tio n above th e b u lb . T h is c a u se d th e tu b e

t o be c l o s e d , a n d a t t h e sa m e t i m e p e r m i t t e d th e b u lb to

d ro p i n t o a c o p p e r sp o n g e bed i n t h e b o tto m o f th e o v e n .

T he p u r p o s e o f t h e s p o n g e w as t o c u s h i o n t h e f a l l o f th e

b u lb and p re v e n t i t fro m b r e a k i n g .
 To v a c u u m <—

V alve

A sb esto s s h e e t N ichrom e w in d ing

in su latio n

B ulb
w ith
clay

A sbestos
Oil- b a t h — sheet
in su latio n

APPARATUS USED IN DRYING AND EVACUATING CLAY

F igure 8
 76

The b u l b was t h e n t r a n s f e r r e d f r o m t h e o v e n i n t o a

c o n t a i n e r p r e h e a t e d t o 1 1 0 ° C . a n d was a l l o w e d t o r e a c h room

tem p eratu re as t h i s c o n ta in e r co o le d .

The b u l b a nd c l a y , a l o n g w i t h t h e p i e c e o f t u b i n g f r o m

w h i c h i t was s e p a r a t e d i n s e a l i n g w e r e w e i g h e d t o d e t e r m i n e

the d ry w eight o f c l a y .

C o n stru c tio n of th e C alorim eter

F i g u r e 9 shows t h e i n n e r m e c h a n i s m o f t h e c a l o r i m e t e r

The i n n e r m e c h a n i s m was f i t t e d i n t o a s i l v e r e d vacuum t u b e

(Dewar) o f P y r e x g l a s s h a v i n g a c a p a c i t y o f 665 m l . , a

d e p t h o f 190 mm. an d a n i n s i d e d i a m e t e r o f 70 mm.

The g l a s s b u l b was h e l d by a b r a s s r i n g , 2 - 1 / 2 ” O.D.

and 1 - 5 / 4 ” I . D . The h o l d e r f o r t h e b u l b c o u l d be r e m o v e d

i n o r d e r t o i n s e r t t h e b u l b , an d t h e h e i g h t a t w h i c h t h e

sc re w s on t h e h o l d e r w ere p l a c e d c o u ld be a d j u s t e d t o p e r m i t

th e u se o f b u lb s w hich v a r i e d s l i g h t l y i n d ia m e te r . A

p i e c e o f b r a s s t u b i n g , 1 / 4 ” O.D, a n d 3 / 1 6 ” I . D . , s u p p o r t e d

t h e b u l b h o l d e r a n d had a h o l l o w i n s e r t o f b a k e l i t e , 5 / 8 ” O.D.

and 1 / 4 ” I . D . , t o r e d u c e t h e t h e r m a l l e a k a g e w h i c h w o u ld

have o c c u r r e d more r e a d i l y w i t h t h e b r a s s t u b e a l o n e .

(The b a k e l i t e was o b t a i n e d f r o m t h e S y t h a n e C o r p o r a t i o n ,

Oaks, P e n n s y l v a n i a ) The b r a s s s u p p o r t f o r t h e b u l b was a t ­

t a c h e d t o t h e b r a s s c o v e r w h i c h was 1 / 2 ” i n t h i c k n e s s an d

5” i n d ia m e te r . A ll p a rts of brass in sid e the c alo rim e te r

w ere g o l d p l a t e d .
 7U

F ig u re 9

INNER MECHANISM
Copper le a d OF CALORIMETER
w ires to
h e atin g c o il
Beckmann T h erm o m e ter

B rass tu b e i n to
w hich b r e a k e r ro d
is in tro d u ced

P ulley
C o n n ectio n f o r
le a d w ires

B ak elite

B rass
cover

Hollow B a k e l i t e
in sert

B rass s t i r r e r
4 - hole p o r c e la in shaft
tu b in g , coated
w ith p a ra ffin
B rass tube
support fo r
b u lb holder

B ra ss screw
H eating c o i l o f stirrer
m anganin w i r e ,
coated w ith
p a ra ffin
G lass b u lb
B rass holder (A ll b ra s s
f o r bulb p arts ■I
gold p la te d )I
 77

M ethod o f W e ttin g C la y

The c l a y i n t h e e v a c u a t e d b u l b was w e t t e d b y d r o p p i n g

a gold p la te d b ra ss ro d , 1 /8 ” in d iam eter ( n o t shown i n

illu stra tio n ) t h r o u g h t h e b r a s s tu b e and b r e a k in g t h e b u lb

by i m p a c t . The r o d had a s t o p w h i c h p r e v e n t e d i t s strik ­

ing th e b o t t o m o f t h e Dewar f l a s k , b u t p e rm itte d it to

break b o th th e to p and bottom o f the. g l a s s b u lb . Because

th e r o d was i n t h e c a l o r i m e t e r o n l y d u r i n g t h e t im e o f b r e a k ­

ingth e b u lb , it had no e f f e c t on t h e t e m p e r a t u r e . At a l l

o th e r tim es the h o l e i n t h e t u b e was s t o p p e r e d .

T em p era tu re M easurem ent

The t e m p e r a t u r e c h a n g e s w ere m ea su re d b y means o f a

Beckmann t h e r m o m e t e r , g ra d u a te d to 0.0 1 °C . and r e a d to

0 .0 0 1 °C .

St i r r i n g

A s t i r r e r was m a d e o f l / 4 n b r a s s tu b in g , f i t t e d w ith

a s c re w p r o p e l l e r 1” i n d ia m e te r and w i t h a b a k e l i t e in se rt,

1/4" in d ia m e te r, to red u c e th erm al le a k a g e . A b ak elite

b earin g , lu b ric a te d w ith o il, was u s e d . A p u lley , d riv en

by a m o to r w i t h a s m a l l b e l t , ro tated th e s t i r r e r a t ap p ro x i­

m a te ly 200 r . p . m . The t e m p e r a t u r e r i s e due to th e s t i r r i n g

a lo n e was 0 .0 0 0 1 ° p e r m in u te f o r a p e r i o d o f a s lo n g a s

one h o u r . •

P r e p a r a t io n o f H eating C o il

T h e h e a t i n g c o i l was m ade o f 1 3 . 3 " o f 2 6 g a u g e , c o t t o n

in su lated , m anganin w ir e h av in g a r e s i s t a n c e o f 1 . 1 7 ohms

per fo o t ( D r i v e r —H a r r i s C o . , H arriso n , N . J . ) . Two s h o r t

l e a d s o f 26 gau g e co p p er w ir e w ere s o l d e r e d t o e a c h end o f

 78

t h e m anganin w i r e . Of t h e s e f o u r l e a d s , two. w e r e u s e d t o

in tro d u ce th e e l e c t r i c c u r r e n t a n d tw o w e r e u s e d t o d e t e r ­

m ine t h e v o l t a g e d r o p a c r o s s th e c o il . The m a n g a n in w i r e

was wound i n a c o i l a r o u n d a c y l i n d e r made o f c o p p e r f o i l ,

3 / 8 ” h ig h and 2 -1 /2 " i n d ia m e te r . C ontact w ith th e copper

f o i l was p r e v e n t e d by m eans o f a d h e s i v e t a p e . T he w h o l e

c o i l was t h e n c o a t e d w i t h s o f t p a r a f f i n t o p r e v e n t a r e a c ­

t io n w ith th e c o n te n ts o f the c a lo r im e te r . The c o p p e r f o i l

served to k eep t h e m anganin w ire i n a f i x e d p o s i t i o n , and

was o f s u c h a d i a m e t e r t h a t t h e g l a s s bulb in i t s holder

c o u ld be s l i p p e d i n t o it. In t h i s way, th e h e a t ev o lved

in th e e l e c t r i c a l c a l i b r a t i o n vra.s l i b e r a t e d u n i f o r m l y a r o u n d

the b u lb . The c o p p e r f o i l was u s e d t o f a s t e n t h e h eatin g

c o il to th e fo u r-h o le p o rc e la in tu b in g th ro u g h w hich th e

c o p p e r w ir e s from t h e c o i l w ere l e a d . The c o p p e r l e a d s

w ere s o l d e r e d on t h e o u t s i d e o f t h e c a l o r i m e t e r t o a 5-way

plug from an o ld r a d i o tu b e. T h is p l u g was a c o n v e n i e n t

m ethod o f a t t a c h i n g and rem oving t h e 18-g au g e i n s u l a t e d

copper w ire lead s to th e rem ainder o f th e e l e c t r i c a l c i r c u i t .

D eterm in atio n of th e R e sistan c e of th e H eating C o il

The e l e c t r i c a l c i r c u i t u s e d i n t h e c a l i b r a t i o n o f t h e

h e a t ev o lv ed i n w e ttin g th e c la y is shown i n F i g u r e 1 0 .

T he r e s i s t a n c e o f t h e m anganin h e a t in g c o i l was f o u n d by

in tro d u cin g a known c u r r e n t an d m e a s u r i n g t h e p o t e n t i a l d r o p

across the h e a tin g c o i l . A R u b ic o n H igh P r e c i s i o n , t y p e B,

p o t e n t i o m e t e r was u s e d w i t h a R u b i c o n No. 5 4 0 1 -H s p o t l i g h t
 A u x iliary o lm
standard To p o t e n t i o m e t e r
resistan ce

n
D ouble-pole}
d o u b l e t h r o w s w i t c h (D)

Ideating c o i l
in c a lo rim e te r (il)

To
p o ten tio m eter

CIRCUIT FOR ELECTRICAL CALIBRATION

F i g u r e 10
 73

galv an o m eter to d e term in e the p o t e n t i a l d ro p . The r e s i s ­

t a n c e o f t h e m a n g a n in c o i l was f o u n d t o b e 1 . 2 7 0 3 ohm s.

I n s u l a t i on o f C a l o r i m e t e r and T e m p e r a tu r e C o n t r o l

T h e Dewar f l a s k w a s s u r r o u n d e d b y a 3 / 4 " a i r jack et.

The a i r j a c k e t w a s e s s e n t i a l l y m ade u p o f o n e c a n i n s i d e

o f a n o t h e r w i t h a s p a c e o f 3 / 4 ” b e tw ee n them . The j a c k e t

w a s m ade o f 2 4 g a u g e g a l v a n i z e d s h e e t . The b r a s s c o v e r

was f i t t e d tig h tly to th is a ir j a c k e t by means o f e i g h t

1 /4 ” b o l t s w hich w ere screw ed i n t o the 1 /2 ” b ra s s top of

the a i r jack et. The Dewar f l a s k was p r e s s e d f i r m l y a g a i n s t

the b ra s s c o v e r by means o f a r u b b e r s p o n g e a t t h e b o tto m

o f t h e c a n i n t o w h i c h t h e De wa r f i t t e d snu g ly . The o u t e r

edges of th e a i r j a c k e t w ere e x te n d e d 1 ” above t h e b r a s s

cover. In to th is space, a sheet of in su la tin g board,

c o v e r e d b y a s h e e t o f c o r k was f i t t e d . T i n f o i l was u s e d

to cover th e cork in o rd e r to red u ce changes of tem p eratu re

cau sed by r a d i a t i o n .

The a i r j a c k e t was s u r r o u n d e d by a 4 g a l l o n w a t e r

b a th . T h e t e m p e r a t u r e o f t h e b a t h was c o n t r o l l e d b y a

m ercury th e r m o - r e g u la to r . The t e m p e r a t u r e c o n t r o l c i r c u i t

i s show n i n F i g u r e 1 1 .

T h i s t y p e o f c o n t r o l was f o u n d t o r e g u l a t e th e tem pera­

tu re of th e b a th to i 0 .0 l°C . As i t was n e c e s s a r y t o c o n t r o l

only th e r a t e o f c h a n g e o f t e m p e r a t u r e w i t h i n t h e Dewar

flask , t l i i s p r e c i s i o n o f c o n t r o l o f t h e s u r r o u n d i n g s was

sa tisfac to ry . The t e m p e r a t u r e w i t h i n t h e Dewar f l a s k a t

 79a

110V A . C .

R ectifie r-
transforraer

3V D.C

2 ufd. H eater
condenser in b ath

M ercury t.ie n a o -
reg u la to r
in w ater b a th 110V A . C .

CIRCUIT FOR TEMPERATURE CONTROL IN WATER bATH

F i g u r e 11
 80

e q u i l i b r i u m was f o u n d t o c h a n g e a b o u t 0 . 0 0 1 ° p e r h o u r , o r

less. Most o f t h e o b s e r v a t i o n s w e r e made a t a b o u t 2 8 ° C .

D u r i n g v e r y warm w e a t h e r i t was n e c e s s a r y t o r a i s e t h e b a t h

te m p e ra tu re to a b o u t 29°C. The c a l o r i m e t e r was s e t u p i n

a room h a v i n g n e a r l y c o n s t a n t t e m p e r a t u r e . T h i s r oo m ( a

d a r k room) ha d h o l l o w t i l e 7 / a l l s , n o windows a n d n o r a d i a t o r s ,

and a d o u b le d o o r .

Procedure f o r the D eterm ination of

Heat o f W e ttin g

Ty/o m a i n s t e p s w e r e i n v o l v e d in the d e te rm in a tio n o f

h e at of w e ttin g : (l) th e m easurement o f th e te m p e ra tu re

r i s e p r o d u c e d b y w e t t i n g t h e c l a y s , and (2) t h e measurement

o f t h e t e m p e r a t u r e r i s e r e s u l t i n g from t h e i n t r o d u c t i o n o f

a knov/n am o u n t o f e l e c t r i c a l e n e r g y i n t o t h e c a l o r i m e t e r

w i t h t h e same c o n t e n t s .

The Dewar f l a s k was f i l l e d v / i t h 300 m l . o f s o l u t i o n

and was t h e n p l a c e d i n t o i t s jac k et described p rev io u sly .

The b u l b c o n t a i n i n g t h e e v a c u a t e d c l a y was p l a c e d i n t h e

i n n e r m e c h a n i s m , w h i c h was t h e n l o w e r e d i n t o t h e Dewar and

s e t up a s d e s c r i b e d . The t e m p e r a t u r e o f t h e w a t e r i n t h e

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

d e g r e e o f t h e e q u i l i b r i u m t e m p e r a t u r e , f o u n d by e x p e r i e n c e .

A b o u t twTe l v e h o u r s w e r e t h e n r e q u i r e d f o r f i n a l t n e r m a l

e q u i l i b r i u m t o be a t t a i n e d .

De t e r m i n a t i o n o f T e m p e r a t u r e I n c r e a s e on. We t t i n g _ . C l a -y

The s t i r r e r was o p e r a t e d f o r a b o u t 500 s e c o n d s i n

o r d e r t o c h ec k t h e r a t e o f t e m p e r a t u r e r i s e due t o s t i r r i n g
 SI

alo n e. The " b r e a k e r r o d was t h e n b r i e f l y i n s e r t e d a nd d r o p p e d ,

s h a t t e r i n g t h e b u l b , and w e t t i n g c l a y . R eadings o f tim e

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

o f t e m p e r a t u r e was v e r y s m a l l . The t e m p e r a t u r e r i s e was

f o u n d a s shown i n t h e t y p i c a l c u r v e , F i g u r e 1 2 .

Procedure f o r E l e c t r i c a l

C alib ratio n

The e l e c t r i c a l c i r c u i t i s shown i n F i g u r e 1 0 . S w itch D

was t h r o w n t o i n c l u d e t h e a u x i l i a r y c o i l (A) w h i c h was u s e d

to d i s c h a r g e t h e s t o r a g e b a t t e r y t o a p o i n t where t h e amper­

age m a in ta in e d a s t e a d y v a lu e . I t was f o u n d t h a t i f t h i s

s te p were n o t ta k e n , t h e amperage would d ro p c o n s i d e r a b l y

during th e p e rio d of th e e l e c t r i c a l c a l i b r a t i o n . By e x ­

p e r i e n c e , i t was f o u n d t h a t a b o u t 20 m i n u t e s w e r e r e q u i r e d

to re a c h t h is ste a d y s t a t e . The s w i t c h (D) was t h e n

o p e r a t e d t o th ro w o u t t h e a u x i l i a r y c o i l and i n s e r t th e

heating c o i l (H) i n t h e c a l o r i m e t e r . The amount o f t i m e

e l a p s e d d u r i n g t h e p a s s a g e o f t h e c u r r e n t was n o t e d i n

seconds. The l e n g t h o f t h i s p e r i o d d e p e n d e d u p o n t h e d e ­

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

to the valu e o b tain ed in th e w etting of th e c la y . D uring

the passage of the c u rr e n t, t h e a m p e r a g e i n t h e c i r c u i t was

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

standard r e s is ta n c e . ( R e s i s t a n c e S t a n d a r d S e r i a l No. 2 8 8 2 9 3
t e m p e r a t u r e c o e f f i c i e n t b e t w e e n 20 a n d 2 7 °C . + 0 . 0 0 0 0 0 5 / ° C . ,

b e t w e e n 27 a n d S 5 ° C . i n . 0 0 0 0 0 2 / ° C . : l i m i t o f e r r o r up t o

1 w a t t = 0 . 0 2%, up t o t e n w a t t s = 0 . 0 5 $ )
 w i t h ieli e c t ' 3 i c ah c a i l S r d t I o n ' o v e r : s a m e i
i .

i£ou

:: J G i i i i r i e M :

o Hi
0

t
rrss*'
c l a y - = 0 . 1J4Y°e-;

e n -;

PIS
Tune ftiundredii--dr. .se condsJj
 ecfetoaiiiii therm oiqetea

-(X .

c+ c+
O trf
I—
1
OS'
H1

H' H*

H-> (ti
•6
-K^-p
f :t-

'TP
 The t e m p e r a t u r e r e a d i n g s w e r e a g a i n r e c o r d e d u n t i l

the r a t e o f c h a n g e o f t e m p e r a t u r e was s m a l l .

The e l e c t r i c a l c a l i b r a t i o n w a s made e i t h e r a t t h e end

of th e m easurem ent o f th e tem p eratu re in c re a s e in w ettin g

th e cla y , i.e ., at a slig h tly ele v ated tem p eratu re w ith a

som ewhat h i g h e r te n d e n cy tow ard th e rm a l le a k a g e , or over

t h e same t e m p e r a t u r e r a n g e . The l a t t e r p r o c e d u r e was a d o p te d

in th e early p a rt o f t h i s w ork, i.e ., in th e d e te rm in a tio n

of th e h eat o f w e ttin g of th e k a o lin s , because i t was c o n ­

s i d e r e d m ore s o u n d fro m t h e t h e o r e t i c a l s t a n d p o i n t . How­

ever, the tim e r e q u i r e d t o make a c o m p l e t e d e t e r m i n a t i o n

was t h e r e b y d o u b l e d , as tw elv e h o u rs w ere a g a i n r e q u i r e d to

atta in th erm al e q u ilib riu m a f t e r th e w ettin g of th e c la y .

In th e l a t t e r p a r t o f th e w ork, i.e ., w i t h Wyoming b e n t o ­

n ite , th e e le c tric a l c a l i b r a t i o n w a s m ad e i m m e d i a t e l y a f t e r

determ in in g the tem p eratu re r i s e p r o d u c e d by w e t t i n g th e c la y .

C a l c u l a t i o n o f H eat E volved i n W e ttin g

The h e a t i n c a l o r i e s d ev elo p ed i n a c i r c u i t by an

e le c tric c u r r e n t o f i am peres flow ing th ro u g h a r e s i s t a n c e

of r ohms, w i t h a d i f f e r e n c e of p o te n tia l of E v o lts for a

tim e o f t seconds i s :
H = r lg _t = (i)
4 .1 8 1 4.1 8 1

( l gram c a l o r i e (2 0 °C .) = 4 .1 8 1 jo u le s )

The h e a t o f w e t t i n g of th e c l a y co u ld th e n be found by

u sin g the e q u atio n : Hw = He , i n w h i c h

dTw dT c
 33

Hw = H e a t i n c a l o r i e s d e v e l o p e d o n w e t t i n g c l a y .

dTw = T e m p e r a t u r e r i s e (°C .) on w e t ti n g clay .

He = H e a t i n c a l o r i e s d e v e l o p e d i n e l e c t r i c a l c a l i ­

b ratio n , c a l c u l a t e d from e q u a t i o n (l).

dT c = T e m p e r a t u r e r i s e (°C .) in e le c tric a l c alib ra tio n .

SORPTION OF WATER FROM THE VAPOR PHASE

The a m o u n ts o f w a t e r s o r b e d b y c l a y s exposed f o r

vario u s len g th s o f tim e to a tm o sp h e res o f g iv e n r e l a t i v e

h u m id i t ie s w ere d e te r m in e d a s f o l l o w s . T hree d u p l i c a t e

sam p les o f e a c h ty p e o f c la y , a p p r o x im a te ly 2 gram s f o r

t h e k a o l i n and 1 gram f o r t h e b e n t o n i t e s , w ere p l a c e d i n

w eig h in g b o t t l e s 5 0 x 3 0 mm. The d r y w e i g h t o f t h e c l a y

was o b t a i n e d by d r y i n g it a t 110°C. and c o o lin g it rap id ly

w i t h t h e c o v e r on th e w e ig h in g b o t t l e , o v e r ’’D r i e r i t e ”

in a d e ssic a to r.

The s a m p le s w e r e e x p o s e d t o a t m o s p h e r e s o f c o n t r o l l e d

h u m id ity , over s u lp h u ric acid s o lu tio n s (86), f o r from

5 t o 14 d a y s , and re -w e ig h e d . The r e l a t i v e h u m id ite s w ere

10$, 8 1 .5 # , and 9 9 . 9 $ , o b tain ed w ith s o lu tio n s co n ta in ­

ing 6 4 .8 $ , 2 6 .4 $ , and 1$ s u l p h u r i c a c i d by w e i g h t , resp ect­

iv ely .

The g l a s s surface o f a w eig h in g b o ttle adsorbs

m o is tu re from th e a tm o s p h e r e , d e p e n d in g on t h e r e l a t i v e

hu m id ity o f th e a i r at th e tim e. W eighings f o r th is study

w e r e m ad e w i t h a . t a r e , i.e ., an em pty w eig h in g b o ttle

placed on t h e Y feighing p a n o f t h e b a l a n c e . Thus, if th e

 84

b o ttle c o n tain in g the c la y adsorbed w ater w h ile s ta n d in g ,

the tare d id lik e w ise , and t h i s f a c t o r was c a n c e l l e d .

Empty w e i g h i n g b o t t l e s w e r e t h e r e f o r e exposed a t e ac h

re la tiv e h u m id ity , in o rd er to check th e a d so rp tio n of

v a p o r by t h e b o t t l e s alo n e. The r e s u l t s , in p ercentage of

w a te r s o rb e d by th e c l a y s on th e b a s i s of t h e i r dry

w e i g h t, a r e shown i n T a b le s VI t o IX.

INVESTIGATION OF WATER SORPTION PHENOMENA

BY DIFFERENTIAL THERMAL METHODS

The c a p a c i t y o f c l a y s to b i n d w a t e r was i n v e s t i g a t e d

by w e ig h in g th e clay s before and a f t e r exposure to certain

rela tiv e h u m id itie s. The i n t e n s i t y w i t h w h ic h t h e w a t e r '

was h e l d w a s t h e n s t u d i e d by d i f f e r e n t i a l t h e r m a l m e th o d s ,

in w hich th e r e l a t i v e amount of h e a t and the tem perature

req u ired t o rem ove t h e w a t e r fro m t h e c l a y was m e a s u r e d .

The p r o c e d u r e u s e d w a s s i m i l a r to th a t d escrib ed

p r e v i o u s l y i n th e s e c t i o n on d i f f e r e n t i a l th e rm a l a n a ly s e s

in th e id en tific atio n of clay m in erals. The c l a y s w e r e

teste d o n l y i n t h e low t e m p e r a t u r e endotherm ic r e g io n .

T h e r m a l t e s t s w e r e m ade o n 2 « o gm. s a m p l e s o f H - ,

C a - , N a - , K-Wyoming b e n t o n i t e s w h i c h h a d b e e n e x p o s e d a t

1 0$ a n d 9 9 . 9 $ r e l a t i v e h u m id itie s. The c u r v e s o b t a i n e d

on s a m p l e s e x p o s e d t o 10$ r e l a t i v e h u m id ity showed g r e a t e r

d ifferen ces a n d more s t r u c t u r e than th o se o b tain ed a t

99.9$ r e l a t i v e h u m id ity , and a r e shown i n F i g u r e 1 4 .

 85

The k a o l i n s w ere n o t s t u d i e d i n a s much d e t a i l a s

the b e n to n ite s because th e k a o lin s sorbed co m p arativ ely

s m a l l a m o u n ts o f w a t e r a t low h u m i d i t i e s , and t h e r e f o r e

d ifferen ces i n t h e low t e m p e r a t u r e e n d o th e rm ic p e ak s w ere

d iffic u lt to d etect* The r e s u l t s o f a few t e s t s on a i r -

d ried k a o lin and k a o l i n s exposed a t 9 9 .2 $ r e l a t i v e hum id ity

a r e show n i n F i g u r e 2 .
 86

EXPERIMENTAL RESULTS AMD DISCUSSION OF RESULTS

HEAT OF WETTING

K a o l i n i t e was s e l e c t e d as th e m ost s u i t a b l e m in e r a l

for th is stu d y because of i t s p u rity , its Im p o rtan ce i n

ceram ics, and b ecau se I t d o e s n o t show s w e l l i n g , w h i c h

m ight c o m p li c a te t h e i n t e r p r e t a t i o n o f r e s u l t s by i n t r o ­

d u cing o t h e r heat e ffe c ts. However, a b e n t o n i t e was a l s o

stu d ied fo r p u rp o se s o f co m p ariso n and b e ca u se o f i t s

g reater r e a c tiv ity .

Heat o f W ettin g o f K a o lin s

I n W ater

As s h o w n i n T a b l e I I , more h e a t was e v o l v e d i n w e t t i n g

Ca- and H - k a o lin s t h a n i n w e t ti n g N a- and K - k a o li n s :

Ca \ H > Na > K

1 .4 5 1 .4 0 1 .3 0 1 .8 2 (average v a lu e s ,

in calo rie s p e r gram

of clay )

The f i g u r e s g i v e n a r e n o t p r e c i s e to 0 .0 1 c a l o r i e per

gram , but th e o rd e r o f the s e r ie s is d e fin ite .

H eat of W ettin g K a o lin s in

A lk alin e S o lu tio n s
i
H -K aolin i n A l k a lin e S o lu tio n s.

When H - k a o l i n w a s I m m e r s e d I n 0 . 1 N NaOH s o l u t i o n ,

o r i n 0 .0 1 5 N C a(0H )2 s o l u t i o n , more h e a t was e v o l v e d t h a n

when t h e H - k a o l i n was w e t t e d by w a t e r . The i n c r e a s e a m o u n te d

to about 0 .2 c a l o r ie p e r gram o f c l a y .
 To face 0 6 b

TABLE I I
Heat o f w ettin g
K aolin, not d ilu te d w ith quartz

Ho, A.dsorbed W etting Weight Temp.

Sample ion e le c t r o ly t e sample r is e on
(gm.) w etting
(°C)

21 H H30 3 5 .8 9 4 .147

28 H II20 35.036 .344

27 II h2o 23.751 .127

31 H h2o 2 6 .8 3 2 .117

32 H KaOH 2 8 ,9 8 5 .144

35 H HaOI-I 29.657 .147

39 H HaOH 2 7 .8 2 2 .137
1
67 H Ca(0H ) 2 3 3 .1 8 4 .163

68 H Ca(0H)s 2 6 .8 3 6 .134

38 Ha H20 34-778 .135

36 Ha h2o 33.029 .128

60 Ha h 2o 24.323 .099

58 Ha HaOH 21.930 .098

I4JU- K H20 24.749 .089

54 K h2 o 2 4 .8 9 2 .095

55 K KOH 21.349 .093

kl Ca h2o 25.953 .116

45 Ca h2 o 2 2 .2 8 4 .099
 86b

E l e c t r i c a l C a lib r a tio n Heat C a lo rie s

Amps. V o lts Time Temp, Heat evolved. p er
( s e c .) r is e in p u t on gm.
. (°c) ( c a l .) w e ttin g c la y
( c a l .)

.I+07U .5171+ 1000 J .51 5 0 . 1+2 1+9.09 1.37

. 1+161+ .5288 1000 .1 6 0 52.88 1+7.59 1 .3 6

.1+11+7 .5267 1000 .1 6 2 52.38 1+1.07 1.1+3

♦i+173 .5300 1000 .1 6 1 52.91 33.1+5 ' 1.1+3

. 1+096 .5202 900 . 11+1 1+5.37 1+6.78 1 .6 1

.1)095 .5201 900 . 11+1 1+5.85 1+7.73 1 .6 1

. 1+066 . 5161+ 900 .139 1+5 .2 0 1)1+. 55 1 .6 0

. 1)058 .515U 1000 .11+9 5 0.02 51+.72 1 .6 5

. 1+023 .5109 1000 . 11+8 1+9 .1 6 I+I+.51 1 .6 6

. 1+072 .5171 900 1.37 1+5*33 I+I+.67 1.28

.1+059 .5155 900 .135 1+5 .0 2 1+2.69 1.29

. 1+025 • 5113 700 .1 0 5 31+.1+9 3 2 .5 2 1.31+

.1+028 .5116 700 .1 0 6 31+.50 3 1 .9 0 1.1+5

.1+01+9 .511+1 700 .1 0 6 31+.85 2 9 .2 6 1.13

-U0II.3 .5135 700 .1 0 6 31+.73 31.13 1 .2 5

.1+01+3 .5135 700 .1 0 6 31+.72 3 2 .1 0 1.50

. 70 .5169 800 . 121+ I+0 .2 5 37.65 1.1+5

. 1)051 .511+5 700 .108 31+.90 31.99 1 . 1)1+

 To face 8 6 d

TABLE I I I
Heat of W etting
K aolin, d ilu te d w ith quartz

No. Adsorbed W etting Weight Weight Weight Temp.

Sample ion e le c t r o ly t e cla y & c la y quartz r ise
quartz on
Wetting
clay &
quartz

91 H H20 61.965 11.711 5 0 . 251+ .058

93 H h2 o 63.309 1 2 .0 6 0 51.71+9 .057

90 H NaOH 5 6 .0 1 1 1 0 .5 8 6 1+5.14+3 .062

86 H NaOH 55.377 IO ./466 /4+.911 .061

96 H Ca(0H) 2 6 3 .6 6 9 12.033 5 1 .6 3 6 . 06 I+

9k H Ca(0H)a 59.070 1 1 . 161+ 1+7.906 .062

Na H20 55-536 [+5.080

O•
1 0 .5 0 6

O
79
83 Na II20 61+. 081 1 2 .1 1 1 51 .9 7 0 .056

85 Na NaOH 5k-363 1 0 .2 7 6 1+L+.092 .050

8k Na NaOH 59.60k 1 1 .2 6 5 1+8 .3 3 9 .057

92 Na NaOH 6 2 . 5L+5 11.821 5 0 . 721+ .060

101 K h2 o 6 1 . 05/4 11.539 1+9 .5 1 5 . 0I+6

100 K h2 o 6 0 .0 7 5 11.351+ 1+3.721 .01+1+

105 K KOII 72.57U 13.716 58.358 .063

99 K KOH 6 2 . 2/42 11.76k 50.1+73 .055

 86cl

E l e c t r i c a l C a lib r a tio n V----------

Heat Heat ■'Heat Calor:
Amps. V o lts Time Temp. Heat evolved evolved evolved per
( s e c .) r i s e in p u t in in in gram
(°C) ( c a l .) w e ttin g w e ttin g v rettin g c la y
q u a rtz & c la y q u a rt z c la y
( c a l .) ( c a l .) ( c a l.)

.1+063 .5160 1+50 .065 2 2.5 6 20.13 1 .1 6 18.97 1 .6 2

.1+071 .5170 1+50 .0 6 9 22.6 5 18.71 1.19 17.52 1.1+5

.i +061 .5157 1+50 .069 22 . 5I+ 2 0 .2 5 1.05 19.20 1.91
.14063 .5160 1+50 .066 2 2 .5 6 2 0.85 1.03 19.32 1.89
.1+079 .5179 U50 .069 22.73 21.08 1.19 19.39 1 .6 5

. 1+070 .5169 1+55 .070 2 2 .8 9 2 0.27 1 .10 19.17 1.72

.1+077 .5178 1+50 .070 22.73 16 . 21+ 1 . 01+ 15.20 1.1+5

CO
CO
CO

.I +005 .5086 1+50 .065 2 1.9 2 1 .20 17.6 cj 1 . 1+6

ft

.I +052 . 511+6 I+50 .070 2 2 . 1+1+ 16.03 1 .0 1 15.02 1 . 1+6

. 1+025 .5112 I+50 .070 2 2.1 5 1 8 .0l+ 1 .11 16.93 1.50

. 1+080 .5182 I+50 .070 22.52 19.30 1.17 18.13 1.53
.1+081 • 5183 I+50 .072 22.77 H+.55 1 . 11+ 13.1+1 1 .1 6

. 1+01+2 .5133 1+50 .071 22.33 13 . 81+ 1.1 2 12.72 1 .12

. 1+060 .5156 1+50 .072 22.53 19.71 1.35 18.36 1.3 h

.I +079 .5180 1+50 .071 22.71+ 17.63 1 .1 6 16.1+7 l.l+o
 To face: 3 6fr

TABLE IV
H eat o f w e ttin g o f q u a rtz
Ho. N e ttin g W eight Temp. Rise
Sample e le c tro ly te q u a rtz on w etting
quart z

81 Hs 0 75.315 .006

106 NaOII 7 2 .0 0 1 .006

TABLE V
H eat o f w e ttin g
Wyoming b e n to n ite , d i l u t e d w ith q u a rtz
Ho. A dsorbed N e ttin g W eight W eight W eight Temp.rise
Sample io n e le c tro ly te c la y & c la y q u a rtz on w etting
q u a rtz c la y &
q u artz

57 H H30 6 7 .8 8 8 2 .3 5 5 6 5 .5 5 2 .Ikk

78 H NaOH 6I|.2i.7 2 .2 1 0 62.037 .166

97 Ha h2 o 70.611 2.L.30 68.181 .096

98 Na h 2o 58.397 2.026 56.371 .080

lOij. Na NaOH 6 0 .2 3 8 2 .0 7 2 58.166 .100

102 Na NaOH 69.2Lj9 2.3 8 2 66.867 .110

110 K H20 5 6 .6 9 5 1.950 5U.7U5 .0 5 6

108 K Hs 0 51.119 1.758 U9-361 .05U

109 K KOH 57.ii.71 1.977 55.ii 3k .072

112 K KOH 58.121 1.999 56.122 .070

103 Ca h 2o 73,559 2,668 70.871 .180

 E l e c t r i c a l C a lib r a tio n Heat C a lo r ie s
Amps. V o lts Time Temp. Heat ev o lv ed per
( s e c . ) r i s e in p u t in gram
(°C) ( c a l . ) w e ttin g
quartz
__________ (cal.)

.1.077 .517S 60 .0 1 1 3 .O3 I .6 5 3 .0 2 2

. 1(012 .5 0 9 5 60 .0 1 0 2 .9 3 I .7 5 8 . 02 U

E l e c t r i c a l C a lib r a tio n Iieat Heat Heat C a lo r ie s

Amps. V o lts Time Temp. Heat ev o lv ed ev o lv ed ev o lv ed per
( s e c . ) r i s e in p u t in in in gram
(°C) ( c a l . ) w e ttin g w e ttin g w e ttin g c la y
q uartz & c la y qu artz c la y
(cal.) (cal.) (cal.)

.I. 03 I. .5 123 1100 .1 6 2 5U.37 U8.33 I .5 1 I4.6 .S 2 2 0 .1

.L 076 .5 1 7 7 1100 . 161). 5 3 .1 0 53.75 1.U3 5 1 .6 7 23.h

.I. 07 U . 517 U 600 .0 9 4 3 0 . 2k 3 0 .8 8 1 .5 7 2 9 .3 1 1 2 .1

0L050 . 511^ 600 .0 9 4 2 9 .9 0 25.U5 1 .3 0 21+.15 1 1.9

, 1)0614. .5 1 6 1 600 .0 9 0 3 0 .1 0 33.1-5 . 1.3U 3 2 .1 1 15 .5

1—

.L082 . 5181). 600 .0 9 0 3 0 .3 7 3 7 .1 2 3 5 .5 8 H i-9

•
1

.L 075 .5 1 7 5 600 .09U 3 0 .2 6 18.03 1 .2 6 16.77 8 .6

. 1(021 .5 1 0 7 600 .0 9 0 2 9 .ii7 1 7 .6 8 1 . 11+ 1 6 . 5I4. 9 .6

.1)075 .5175 600 .0 9 6 3 0 .2 6 2 2 .7 0 1 .2 8 2 1 . 1-2 1 0 .8

-1<077 .5178 600 .0 9 6 3 0 .3 0 2 2 .0 9 1 .2 9 2 0 .8 0 1 0 . 1|.

./+O64 .5161 1100 .163 5 5 .1 8 6 0 .9 3 1 .6 3 59.3 0 22.2

 87

If th is i n c r e a s e were t o be i n t e r p r e t e d as th e r e s u l t

of th e h e at of fo rm atio n o f w ater in th e exchange r e a c t i o n ,

the fo llo w in g c o n s i d e r a t i o n s m u st be made.

When NaOH i s added to H -k ao lin , an a c id -b a s e r e a c tio n

occurs:

H - k a o l i n + NaOH = N a - k a o l i n + H2 0 .

The n e u t r a l i z a t i o n o f a s t r o n g a c i d by a s t r o n g b a s e

in d ilu te s o lu tio n c o n s is ts s o le ly in the com bination of

hydrogen and h y d ro x y l io n s to form u n d i s s o c i a t e d w a te r .

T he h e a t o f t h i s io n ic r e a c t i o n i s ab o u t 1 3 .8 k ilo g ra m -

c alo ries p e r mol o f w a te r fo rm ed . When w e a k a c i d s a r e

n e u tra liz ed by b a s e s , the h e a t o f n e u t r a l i z a t i o n may b e

e ith er g re a te r or less th a n 1 3 .8 k i lo g r a m - c a l o r i e s . T he

d ifferen ces a r e due to th e h eat of d i s s o c i a t i o n of th e

w e a k a c i d s , w h i c h may b e e i t h e r p o s i t i v e or n eg ativ e.

Thus, fro m a know ledge o f th e h e a t o f n e u t r a l i z a t i o n , th e

approxim ate v a lu e of the h e a t o f d i s s o c i a t i o n o f a weak

a c i d may b e e s t i m a t e d .

H -k ao lin i s a weak a c i d ; th at is , the hydrogen does

not d isso ciate rea d ily . Thus, i t m igh t be ex p ected t h a t

t h e h e a t o f n e u t r a l i z a t i o n o f H - k a o l i n b y NaOH w o u l d n o t

be e q u i v a l e n t t o the h e a t of f o r m a tio n o f w a te r from i t s

io n s. T h e h e a t o f t h e r e a c t i o n may b e d e t e r m i n e d i n tw o

w ays:
(l) T h e d r y c l a y m ay b e i m m e r s e d i n NaOH s o l u t i o n ,

i n w hich ev en t th e fo llo w in g e f f e c t s w ould have

t o be c o n s id e r e d :
 88

(a) heat of w ettin g of H -k ao lin

(b) h eat of d i s s o c i a t i o n of H -k ao lin

(c) h eat of fo rm a tio n of w ater

If t h e s e w ere th e o n ly e f f e c t s ta k in g place., th e a c id

stre n g th of k a o lin itic acid , i.e ., H -k a o lin , co uld be

calcu lated .

(2) NaOH s o l u t i o n may b e a d d e d t o a s u s p e n s i o n o f

H -k ao lin , w ith th e fo llo w in g heat effects:

(a) heat o f d i l u t i o n o f NaOH

(b) heat of d i s s o c i a t i o n of H -k ao lin

(c) heat of fo rm a tio n of w ater

T he c a l o r i m e t e r w a s d e s i g n e d p r i m a r i l y t o s t u d y t h e

heat of w ettin g of clay s, a n d was n o t w e l l a d a p t e d t o t h e

secon d ty p e o f m easu rem en t. As m e n t i o n e d b e f o r e , it is

d iffic u lt to nw o r k 1’ a d e f l o c c u l a t i n g agent in to a flo ccu ­

lated clay , such as H -clay , a n d more a g i t a t i o n i s r e q u i r e d

t h a n was o b t a i n a b l e i n th is calo rim eter. Hence, o n ly

th e f i r s t t y p e o f m ethod was u s e d i n t h e study of th e h e at

effects o c c u r r i n g when e l e c t r o l y t e s a r e a d d e d t o c l a y s .

The b a s e e x c h a n g e c a p a c i t y o f H - k a o l i n was 3 m . e . per

1 0 0 gm. o f c l a y , o r 0 . 0 3 m . e . p e r gm . o f c l a y . The 0 . 1

N NaOH s o l u t i o n r e p r e s e n t e d about a 3 0 -fo ld excess over th a t

req u ired to s a tu ra te th e c l a y t o pH 8 . T his c o n c e n tr a tio n

was u s e d t o a s s u re com plete io n ic exchange.

I n th e n e u t r a l i z a t i o n o f 1 m .e. of fre e H i o n s b y OH

ions, th e fo r m a tio n o f w a te r e v o lv es a p p ro x im a te ly 1 3 .8
 89

c alo rie s. T he n e u t r a l i z a t i o n o f 0 . 0 5 m . e . o f H i o n s t h e r e ­

fore e v o lv e s 0 .4 1 4 c a l o r i e s . Thus, i f no h e a t were r e q u i r e d

to d i s s o c i a t e th e H io n s from th e H -k a o lin , th e heat

evolved i n t h e n e u t r a l i z a t i o n o f t h e c l a y a c i d would be

equal to 0 . 4 1 4 c a l o r i e s p e r gm. o f c l a y .

S i n c e a n i n c r e a s e o f 0 . 2 c a l o r i e p e r g r a m was o b t a i n e d ,

th e rem ain d er of th e h eat ( a b o u t 5 0 % ) , m ig h t, b e c o n s i d e r e d

to have b e e n expended i n th e d i s s o c i a t i o n o f th e H - k a o lin .

As w i l l b e s h o w n i n t h e f o l l o w i n g d i s c u s s i o n , the r e a c t i o n

was n o t t h i s s im p le , and o th e r heat e ffe c ts occurred.

When H - k a o l i n w a s i m m e r s e d i n 0 . 0 1 5 N C a ( 0 H ) s t h e

in creased h e a t was a b o u t 0 . 2 c a l o r i e p e r gram was more t h a n

when t h e c l a y was w e t t e d by w a t e r . (T able I I ) The C a ( 0 H ) 2

s o lu tio n re p re s e n te d ap p ro x im ately a 2 -fo ld ex cess over

th a t req u ired to s a tu ra te th e c l a y t o pH 8 .

N a-. and K -K a o lin s i n A lk a lin e S o l u t i o n s

When N a - k a o l i n w a s i m m e r s e d i n 0 . 1 N NaOH s o l u t i o n ,

m o r e h e a t w a s e v o l v e d t h a n w h e n t h e s a m e c l a y was w e t t e d

in w ater (T able I I ) . A s im ila r e f f e c t occurred in the

i m m e r s i o n o f K - k a o l i n i n KOH. O bviously, th is increased

h e a t e f f e c t c a n n o t be a t t r i b u t e d e n tir e ly to a heat of

n e u tra liz atio n . A lth o u g h i t is p o s s ib le t h a t a sm all

f r a c t i o n o f H i o n s may n o t h a v e b e e n r e p l a c e d by N a - o r

K—i o n s i n t h e p re p a ra tio n of th e c la y s a l t s by t i t r a t i o n

t o pH 8 , a s man y H i o n s c o u ld n o t be r e p l a c e d as i n th e

H—c l a y . However, t h e h e a t i n c r e a s e i n e a c h c a s e was o f t h e

sa m e o r d e r o f m a g n i t u d e .
 90

th e process o f d ry in g and ag in g t h e H—c l a y may h a v e p e r m i t ­

ted ions o th e r th an H ions t o become a v a i l a b l e f o r e x c h a n g e .

I t was u n d e r s t o o d t h a t t h e p r e s e n c e o f e x c e s s NaOH o r KOH

m ight r e p r e s s t h e d i s s o c i a t i o n o f th e N a- o r K - c la y and

c a u s e more h e a t t o be e v o l v e d . Howeveij a s t h e heat of

t h e d i s s o c i a t i o n o f a s m a l l number o f i o n s i s probably

n o t a s g r e a t a s t h e e f f e c t o b s e r v e d t h i s w o u ld n o t be t h e

en tire ex p lan atio n .

An a d d i t i o n a l f a c t o r to be c o n s i d e r e d was t h e presence

o f C02 w h i c h w ould bed i f f i c u l t to exclude in a l l of the

o p e ra tio n s w ith the c la y . In th e case of N a-k ao lin , for

exam ple, t h e a d s o r b e d c a t i o n may f o r m c a r b o n a t e s , or i t

is p o ssib le t h a t a n i o n e x c h a n g e may o c c u r w i t h t h e c a r ­

bonate io n , r e p la c in g adsorbed hydroxyl Io n s.

A nother p o s s ib l e v a r i a b l e was a p h y s i c a l o n e , due t o

th e d if f e r e n c e in s tr u c tu r e of th e clay s a f te r w ettin g .

I t was o b s e r v e d t h a t i n w e t t i n g a ll of th e k a o lin s (H-,

C a-, N a-, and K -k a o lin ) by w a t e r a l o n e , the c la y s had a

ten d en cy to rem ain i n a r a t h e r com pact m ass, in stead of

sla k in g . On t h e o t h e r hand, im m ersion o f th e s e c la y s i n

alk a3 .ine s o l u t i o n s c a u se d th e m ass to d i s i n t e g r a t e , for

th e c la y passed th ro u g h th e s ta g e s o f d e f l o c c u l a t i o n and

reflo ccu latio n , because of th e excess e le c t r o ly te . It

was f e l t t h a t a more r e l i a b l e co m parison o f r e s u l t s co u ld

be made i f the s tru c tu re o f t h e w e t t e d c l a y w e r e t h e sa m e

in a l l cases.
 91

A d d itio n o f Q u artz t o C lay

In order to perm it th e c la y to sla k e a f t e r w ettin g

and to lite ra te th e h e a t more r e a d i l y , q u artz, bein g

co m p arativ ely i n e r t , was m ix ed w i t h t h e c l a y . The q u a r t z

u s e d was a g l a s s sand, - 4 0 + 50 m e s h , w h i c h was b o i l e d i n

aqua r e g i a and i n d i s t i l l e d w a te r and th e n d r i e d . The

calo rim e tric e x p e r im e n ts w ere t h e n r e p e a t e d .

Heat o f W ettin g o f Q u a rtz i n W ater and i n A lk a lin e S o l u t i o n

The h e a t o f w e t t i n g of q u artz i n w a t e r a n d i n 0 , 1 N NaOH

was 0 . 0 2 2 and 0 . 0 2 4 c a l o r i e s p e r gram , r e s p e c t i v e l y (T able

III). The v a l u e s are n o t p re c ise to 0 ,0 0 2 c a l o r i e s , and

th ere fo re it was c o n c l u d e d t h a t t h e r e was no a p p r e c i a b l e

r e a c t i o n b e t w e e n t h e NaOH s o l u t i o n a n d q u a r t z o f t h i s

coarse p a rticle size.

In o rd er to fin d th e h e a t e v o lv e d by th e c l a y i n w e t­

tin g it in th e p resen ce of q u a rtz , i t was n e c e s s a r y t o

allo w f o r th e h e a t evo lv ed i n w e ttin g th e q u a rtz . The

q u a r t z was a ssu m ed t o e v o lv e 0 .0 2 3 c a l o r i e s p e r gram ;

th is f i g u r e m u l t i p l i e d by t h e w e i g h t o f q u a r t z gave th e

h e a t ev o lv ed in w e ttin g it. (T ables I I , IV)

Heat o f W etting K a o lin s , D ilu ted

W ith Q u a rtz , i n W ater

The f o l l o w i n g s e r i e s was fo u n d i n t h e order of de­

creased h eat of w e ttin g :

H > Na > K

1 ,5 4 1 ,4 6 1 .1 4 (average v alu es in c a lo rie s

p e r gram o f c l a y , from T able I I I )

%
 92

A lth o u g h t h e s e v a l u e s v a r y somewhat from t h o s e o b t a i n e d

in w ettin g t h e same k a o l i n s w i t h o u t d i l u t i o n w i t h q u a r t z ,

th e o rd er of th e s e r ie s is sim ilar.

H eat o f W etting K a o lin s , D ilu te d w ith Q u a rtz ,

In A lk alin e S olu tio n s

The h e a t l i b e r a t e d in w ettin g H - k a o l i n i n 0 . 1 N NaOH

was g r e a t e r th an th a t lib e r a te d in w ettin g t h e sa m e c l a y

in w ater, by a b o u t 0 .3 c a l o r i e s p e r gram o f c l a y (T able I I I ) .

S im ilarly , more h e a t ( a b o u t 0 . 1 5 c a l o r i e p e r g r a m ) was

lib e rate d in w ettin g th e c l a y i n 0.0 1 5 N C a(0H )2 .

It c an be s e e n t h a t even w ith th e a d d i t i o n o f q u a rtz

to th e c la y s , more h e a t was e v o l v e d when t h e c l a y s w e re

im m ersed i n a l k a l i n e so lu tio n s, t h a n when im m e rsed i n

w ater. I t may b e c o n c l u d e d , th erefo re, th at th e s tr u c tu r e

o f t h e c l a y m ass was n o t t h e p r i n c i p l e cause of th is in ­

crease. It is also ev id en t, t h a t the heat of n e u tra liz a ­

tio n o f H - c l a y b y NaOH s o l u t i o n w a s n o t t h e o n l y e f f e c t

m e a s u r e d by t h i s m e th o d .

Heat o f W e ttin g B e n t o n i t e s , D ilu te d

W ith Q u a rtz , i n W ater

The b e n t o n i t e s w e re d i l u t e d w i t h q u a r t z f o r th e heat

of w ettin g d e te rm in a tio n s, b e c a u s e i t v/as f o u n d t h a t i t h e

u n d i l u t e d b e n t o n i t e s were n o t w e t te d t h o r o u g h ly by th e

w ater.
 The f o l l o w i n g s e r i e s was f o u n d , in th e o rd er of de­
c re a s e d h e at evo lv ed :

Ca > H » Na > K

2 2 .2 2 0 .1 1 2 .0 9 .1 (average v alu es in c alo rie s

p e r gram o f b e n t o n i t e , from

T a b l e V)

Heat o f W ettin g B e n t o n i t e s , D i l u te d w i t h Q u a rtz ,

In A lk alin e S o lu tio n s

As s h o w n i n T a b l e Y , a c o m p a r i s o n o f t h e h e a t s evolved

in w ettin g th e b e n to n ite s in a lk alin e s o lu tio n s w ith th o se

o b ta in e d by w e ttin g i n w a t e r s h o w s t h a t m o r e h e a t was

evolved i n a l k a l i n e so lu tio n s. T h i s w a s t r u e f o r H-

b en to n ite i n 0 . 1 N HaOH, N a - b e n t o n i t e i n 0 . 1 N NaOH, a n d

K -b en to n itei n 0 , 1 N KOH.
i
Some o f t h e c a u s e s c o n t r i b u t i n g to th ese in cre ases

have b e e n d i s c u s s e d i n r e g a r d t o s i m i l a r e f f e c t s w h ic h were

found f o r th e k a o lin s . In ad d itio n to th ese p o ssib le

causes, b e n t o n i t e i s known t o s w e l l , and a d d i t i o n a l h e a t

e f f e c t s may b e i n t r o d u c e d .

C o n c lu s io n s I n Regard to Heat o f W etting

K a o lin s and B e n t o n i t e s i n W ater

The a v e r a g e v a l u e s , in c alo rie s p e r gram , obtained

for heat of w ettin g of c la y s w ith v a rio u s adsorbed io n s a re

shown b e lo w f o r p u rp o se s o f co m p ariso n .
 94

K ao lin s (not d ilu te d w ith quartz)

Ca > H > Na > K

1*45 >1*40 > 1 .3 0 > 1 .2 2

K ao lin s (d ilu ted in q u artz)

Ii > Na > IC

1..54 1*46 1*14

B en to n ites (d ilu ted in q u artz)

Ca > H » Na > K

2 2 .2 2 0 ,1 12*0 9.1

L e s s h e a t was e v o l v e d i n w e t t i n g N a - an d K - c l a y s

th an in w ettin g C a- and H - c l a y s , reg ard less o f w hether

t h e c l a y was o f t h e k a o l i n t y p e or th e m o n tm o rillo n ite

ty p e. The r e l a t i v e p o s i t i o n o f H- a n d C a - c l a y s w a s n o t

c o n c l u s i v e l y shown, b u t i t app ears t h a t C a-clays evolved

s l i g h t l y more h e a t t h a n H - c l a y s .

J a n e r t and o t h e r s (53)(56) have assumed t h a t the heat

evolved i n th e w e ttin g o f c l a y s was m e r e l y a r e p r e s e n t a ­

tio n of the h e a t o f h y d r a t i o n o f th e a d s o r b e d ion* The

fo llo w in g co m p ariso n of th e h e a t evolved i n w e ttin g k a o lin s

a n d b e n t o n i t e s w a s made o n t h e b a s i s o f t h e amount o f

adsorbed ions on e a c h c l a y , using th e fig u re s obtained

f o r t h e c l a y s d i l u t e d w i t h q u a r t z and assum ing 0 .0 3 m .e.

e x c h a n g e a b le c a t i o n p e r gram o f b e n t o n i t e , the h e a t evolved

in c a lo rie s per m .e. o f e x c h a n g e a b l e c a t i o n was c a l c u l a t e d

to be:
 95

K ao lin s

H > Na >. K

5 1 .4 4 8 .7 3 3 .0

B e n to n ites

Ca > H >> Na > K

3 1 .7 2 3 .7 1 7 .2 1 3.0

Thus l e s s h e a t Yvra s e v o l v e d p e r m . e . of exchang eable c a tio n

in b e n to n ite than in k a o lin .

T h is seem s to show t h a t th e adsorbed w ater se rv e s two

purposes: (l) to wet th e s u rfa c e of th e m in eral* and

(2) to p a rtly h y d rate th e adsorbed io n s. The g r e a t e r

h e a t e v o lv e d p er m .e. o f exch an g eab le c a t io n i n k a o l i n

may b e a t t r i b u t e d to a g reater amount o f w a te r h y d ratin g

th e m in e ra l s u rfa c e i n co m parison w i t h t h a t h y d ra tin g the

c a tio n s.

M o n tm o rillo n ite p ro b ab ly has a g r e a t e r p r o p o r tio n of

its surface c o v ered by e x c h a n g e a b le c a t i o n s th a n has

k ao lin ite* where a d s o rb e d io n s a r e p ro b a b ly c o n c e n tr a te d

a t th e broken edges of f l a k e s . T herefore* c a t i o n s w ould

be e x p e c t e d t o p l a y a p r o p o r t i o n a t e l y g reater ro le in

m o n tm o rillo n ite than in k a o l i n i t e . F o r exam ple* the

sa tu ratio n of b en to n ite by one c a t i o n in place of a n o th er

caused a g re a te r d if f e r e n c e in th e heat of w ettin g than

w ith k a o lin . The h e a t s of w ettin g o f H -b e n to n ite w ere i n

the r a t i o o f 2:1* w h e re a s i n k a o l i n th e y were o n ly 1 . 3 : 1 ,

These com parisons seem to d i s p r o v e the th e o ry of

J a n e r t and o th e r s th a t the heat of w ettin g of clay s is

 96

m erely a r e p r e s e n t a t i o n of th e heat of h y d ratio n of th e

adsorbed c a tio n s . T he m i n e r a l s u r f a c e itse lf plays a

part m th e hydratio n . O ther ev id e n ce to support th is

c o n c e p t w i l l be d i s c u s s e d in the g e n e ra l c o n c lu sio n .

H ow ever, i t s h o u ld be m en tio n ed a g a i n t h a t c o m p a ri­

sons of th e heat of w ettin g of k a o li n i te and m o n tm o r illo ­

n ite p r o b a b l y s h o u l d n o t b e made d i r e c t l y b e c a u s e o f t h e

p o ssib ility th at sw ellin g i n n o n t n o r i l l o n i t e may i n t r o ­

duce an a d d i t i o n a l h e a t e f f e c t . A ccording to L ew is,

S q u ir e s and B roughton ( 5 5 , p . 22 ),. 11t h e sw ellin g of d ry ,

g el-fo rm in g m a te ria ls i n s o lv e n t u s u a l l y ev olves h e a t and

is a cc o m p a n ie d by a s m a ll b u t im p o rtan t, s h r in k a g e in to ta l

v o l u m e . 11 As H a ~ b e n t o n . i t e s a r e h n o v n t o s w e l l more t h a n

H— a n d C a - b e n t o n i t e s , b u t nave a l o w e r hear of w e ttin g ,

sw ellin g probably is n o t an im p o rtan t c o n tr ib u tio n of the

heat e ff e c ts observed. A nother f a c t o r , a ls o noted p rev i­

o u sly , is t h a t c o m p le te p e n e t r a t i o n o f w a te r betw een th e

lay ers of th e l a t t i c e o f m o n t m o r i l l o n i t e may r e q u i r e m o r e

tin e th a n t h a t w hich e la p s e d i n th e m easurem ents of heat

of w e ttin g .

C o n clu sio n s in R egard t o W ettin g K a o lin s

And B e n t o n i t e s in A lk alin e S o lu tio n s

It h a s b e e n s h o w n t h a t m o r e h o s t was e v o l v e s , i n

im m ersing c la y s in a lk a lin e so lu tio n s then in w ater. T in s

e f f e c t was o b s e r v e d f o r k a o l i n s and b e n t o n i t e s , and o c c u r r e d

i n N a - an d K~cl& ys a s w e l l a s i n H - c l a y s . S everal f a c to r s
 97

have been s u g g e s te d as c o n t r i b u ti n g to th e observed e f f e c t s .

These i n c l u d e :

(l) The r e a c t i o n , I l - c l a y + HaOH = K a - c l a y + H2 0 ,

tak es p lace, and h eat i s ev o lv ed b ecau se of th e fo rm a tio n

o f vrater *

(f) The d i s s o c i a t i o n of the c lay s a l t s ( i . e . > Na-

c la y or K -clay ) may b e r e p r e s s e d b y t h e excess catio n s in

the so lu tio n *

(?) A d s o r b e d c a t i o n s may f o r m a s m a l l a m o u n t o f

carb o n ates on tIre s u r f a c e of th e c la y due to presence of

C0a . T h e c a r b o n a t e may t h e n c o n t r i b u t e to th e heat e f f e c t.

The c a r b o n a t e i o n map' p o s s i b l y be in v o lv e d i n a n io n ex ­

change r e a c t i o n s .

(i) Changes i n p h y s ic a l s t r u c t u r e , i.e ., flo cc u la tio n

and d e f l o c c u l a t i o n effects.

(5) S w ellin g phenomena.

In a l l cases, th e excess amount o f e l e c t r o l y t e over

th a t req u ired by t h e b a s e e x c h a n g e c a p a c i t y may h a v e h a d

some e f f e c t . A m o r e c o m p l e t e s t u d y s h o u l d b e made u s i n g

vario u s c o n cen tratio n s of e le c tro ly te per u n it of clay .

Bouyoucos (6 8 ) a lso showed a n i n c r e a s e d h e a t e f f e c t

’Mien c l a y s w e r e i m m e r s e d I n h y d r o x i d e s (of a g r e a te r con­

cen tratio n than th o se used • in t h is w ork).

 98

SORPTION OF WATER FROM VAPOR PHASE

The e f f e c t s o f t h e a d s o rb e d io n s a r e sum m arized i n

T a b l e s VI t o IX, in clu siv e. The K i o n c a u s e d a p r o n o u n c e d

decrease in w ater s o r p tio n a t a l l h u m id ities re g a rd le s s

o f w h e th e r t h e c l a y was a k a o l i n o r a b e n t o n i t e , except

perhaps in th e case o f t h e k a o l i n a t a v e r y low h u m id i t y ,

w h ere s m a l l d i f f e r e n c e s w e re m ore d i f f i c u l t to d is tin g u is h

because of th e low w a t e r s o r p t i o n . A nother i n t e r e s t i n g

featu re o b s e r v e d was t h e s h i f t i n p o s i t i o n o f Ca. At

a v e r y low r e l a t i v e hu m id ity (10% ), t h e C a - c l a y s showed

g reater so rp tio n th a n the H -c la y s. T h is e f f e c t was m o st

a p p a r e n t I n Wyoming b e n t o i t e . As t h e hum id ity in c r e a s e d ,

th e Ca- and H -k a o lin s so rb e d a p p ro x im a te ly e q u a l q u a n t i t i e s

o f w a te r and th e H -b en to n ites s o r b e d s l i g h t l y more w a t e r

t h a n t h e C a —b e n t o n i t e s „ In a ll the clay s s t u d i e d , Na+

m a i n t a i n e d a p o s i t i o n b e t w e e n H+ o r Ca++ a n d K> a t a l l

h u m id itie s.

The r e s u l t s o b t a i n e d show good a g re e m e n t w i t h t h o s e

of H en d rick s, N elso n , and A le x a n d e r ( 5 ) , who f o u n d t h a t

K -b en to n ite sorbed le s s w ater a t a l l h u m id itie s th a n Na-

b en to n ite, and t h a t N a-b en t.o n ite so rb e d l e s s t h a n H- o r

C a -b en to n ite. They showed t h a t C a - b e n t o n i t e s o r b e d more

w ater th a n H -b e n to n ite a t low h u m i d i t i e s , and t h a t a t high

h u m id ities the so rp tio n of H—b e n t o n i t e "was a l m o s t e q u a l t o

th a t of C a -b en to n ite. The a u t h o r fo u n d t h a t H -b en to n ites

slig h tly s u r p a s s e d C a —b e n t o n i t e s in so rp tio n a t higher

h u m id itie s th a n th o s e u sed by H e n d ric k s .

 , 93a

TABLE VI
SORPTIOK 0? ¥ATER FID.4 VAPOR PPIASS
K ao lin
ie la tiv e Time % wat e r s o r p t i o n , bast 'id on d r y %rt. o f c l a y a t 110*0
Humidity ex p o sed H Ca Na K
(£) .— f e y s L . .
_

10 6 0 .2 7 0 .3 6 0 .2 3 0 .2 3

0 .2 3 0 .3 5 0 .2 6 0 .2 7

0 .2 3 0 .3 3 0,23 0 .2 3

0 .2 3 civ. 0 .3 6 a v . 0 .2 6 av . 0 .2 3 a v .

3 1 .5 5 1 .4 0 1-36 1.2S 1 .0 9

1 .4 0 1 .3 6 1.2S 1 .0 3

1 .3 9 1 .3 9 1 .2 9 1 .1 0

1 .4 0 a v . 1 .3 7 a v . *JL
1 O O0
•
Q V
cv V * 1 .0 9 a v .

9 9 .9 3 3 .2 1 O
J
1 A
9 i . ’-J' 3-16 2 .6 8
O
^
O -!
* " «U 3 .1 1 3*16 2 .7 9

3 .1 3 0 T p
3 .1 3 2 .7 9

3 .2 0 a v . 1 3 .1 1 a v . 3 .1 5 a v . 2 ,7 5 a v .

99*9 14 4 .2 3 4 .2 5 3 .9 3
/
/+ •
o n
/ 4 .2 5 4 .2 3 3 .9 2

4 .2 4 4 .2 5 4 .2 1 3 .9 3

4 .2 6 a v , 4-2 5 a v . 4 .2 5 a v . 3-93 a v .

su: l.:ary

R e l a t i v e H um idity Time exp o sed O rder o f d e c r e a s i n g s o r p t i o n

/
f n /\
lays } V-

10 6 Ca > il !Ta - X

S I . 5 5 K e Ca > Na > > i:

9 9 ,9
r>
O H ^ Ca K a» K

9 9 .9 14 H - Ca - Ka>> K
 9Bb

TABLE VII
SORPTION 01 7JATEK ITCTI VAPOR PHASE
}Tyo~ilng Ban t o n i t e _________
R e la ti v e Time % v 'a t e r s o r p t .ion, b a s e d on d r y vrt. o f c l a y a t 1 1 0 'c ,
l u m i d it y exposed II Ca Na K

10 6 1*53 3*59 1 '.0 1 .0 4

1 .5 7 . 3*70 1 .4 2 1 .0 4
o n
1 .6 0 3 .3 4 -L• > / 1 .0 4

1 .5 3 a v . 3 .6 5 a v . 1 .4 0 av* 1 .0 4 av .

31 . 5 5 9 0 .3 2 0 .0 15*9 1 0 ,7

19*0 19*4 1 6 ,9 10-9

2 0 .0 19*2 1 6 .0 1 1 ,0

1 9 -2 a v . 19*5 a v. 16 *0 av * 1 0 .9 a v .

99*9 3 25. 9 2 7 .3 2<+. 7 1 7 .4

32*1 2 6 .6 2 4 .7 1 7 .7

2 7 .9 2 6 .4 2 5 .0 1 7 .6

29*6 a v . 26*3 a v . 24*3 a v . 17*6 a v .

9 9 .9 14 31*2 30*1 2 7 .7 1 9 .4

2 9 .3 29*4 oni © v. j-9, ^

3 1 .0 29*1 2 3 .0 19*5

30*5 av* ors

*_s * x ?.v« 2 7 .3 a v . 1 9 .6 a v .

SUI f,T3V

R e l a t i v e Hum idity Time Exposed O rder o f d e c r e a s i n g s o r p t i o n

K&J (days)

30 6 Ca>>H>Na >E

31*5 5 K « Ca > N a » K

99*9 S H ^Ca > N a » K

9 9 .9 14 H>Ca>Na» K
 93c

TABLE V III
SCR.FTIOR OF ’TITER 3R0H VAPOR PHASE
A rizo na B e n to n ite

R e la tiv e Time % w at e r s o rp tio n ,, b a s e d on d r y vrt. o f c l a y a t 110°C.

H um idity exposed H Ca Na K
(£) (d ays)

10 6 5.34 6 .3 3 3 .6 9 3 .2 4

5 . 34 6 . 6 3 3-73 3 .6 3

5.35 6 .8 4 3 .3 4 3*75

5.35 av « 6 «62 a v . 3 .7 7 a v . 3 .5 4 a v .

3 1 .5 5 o > ^
.'S - * 3 2 .9 2 3 .3 2 1 .9

3 4 .2 3 2 .9 2 3 .3 2 1 .9 .

3 4 .4 • 'O 2 3 .3 2 2.0

34-3 a v . 3 2 .9 a v . 2 3 .3 a v . 2 1 .9 av.

9 9 .9 S 4 1.2 3 5 .1 3 6 .9 2 7 .4

41.3 ^O O O
*• J 3 6 .6 2 7 .4

4 1 .3 0 A
J CJ e O 3 6 .5 2 7 .6

4 1.3 a v . 3 3 .3 av . 3 6 .7 a v . 2 7 .5 a v .

9 9 .9 14 ‘~t~ r * *4 */ 4IJto• */4 4 0 .3 2 9 .8

4 4 .3 4 1 .5 4 0 ,2 2 9 .7

l\i -r . 3 4 1 .5 4 0.2 2 9 .7

44 .3 a v . 4 1 .5 a v . 40.2 a v . 2 9 .7 av.

StriiARY'
R e l a t i v e H umidity Time Exposed O rder o f d e c r e a s i n g so rp tio n .
( of \ (days)

10 6 Ca > H >i:a » K

8 1 .5 e H >C a>N a» K

9 9 .9 c H > 03- >Na>> K

99 *9 3.4 H >Ca> R a » K
 TABLE IX

SOLFTIO'I OF WATER FROH VAFGR PHASE

R e la tiv e Time Grams o f vrater p er ra.e. o f exchangeable c a tio n

Humidity exposed c a lc u la te d from r e s u lt s in T ables VI, V II, V III
{%) (d a y s) H Ca Ea K
K aolin
10 A 9 .3 3 1 2 .0 0 8 .6 6 9 .3 3

3 1 .5 c
s
.: 4 6 .6 6 4 5 .6 6 4 2 .6 6 36.33
nn n
y J *y O
r>
1 06 .6 6 1 03 .6 6 1 0 5 .0 9 1 .6 6

CIO 0 1.4 141.99 141*65 141 .6 5 13 0.99

ryoming B en ton ite

10 6 i.C 'j
c 09 2 ,00 1 .4 9

3 1 .5 5 2 3 .3 2 7 .9 2 2 .9 1 5 .6

9 9 .9 3 4 2 ,3 3 3 .3 35*4 2 5 .2

1.4 4 3 ,6 /n 0 qo n
2 3 .0
9 9 .9 Jj s * t

A rizona B en ton ite

10 /
o 3 .3 6 5.39 5.0 6

3 1 .5 5 4 9 .2 ■/HO n i(-U»9 31*3

9 9 .9 8 59.1 54-7 52 .4 39*3

99*9 14 63.3 59.3 5 7 .4 4 2 .4

 99

C o m p a r i s o n s w i t h o t h e r w o r k s a r e more d i f f i c u l t to

make, m a in ly b e c a u se o f th e l a c k o f i n f o r m a tio n c o n c e rn in g

t h e ty p e o f c l a y and d i f f e r e n c e s i n i t s treatm en t* How­

e v e r , m an y s t u d i e s h a v e a g r e e d t h a t K+ d e c r e a s e s t h e a m o u n t

o f w ater s o r p tio n (78) (?)

T a b l e IX s h o w s t h e a m o u n t o f w a t e r s o r b e d b y t h e c l a y s

from t h e vapor p h ase p e r m .e. o f ex ch an g eab le c a t i o n .

It is a p p a r e n t t h a t more w a t e r was s o r b e d p e r m .e . of

e x c h a n g e a b l e c a t i o n i n k a o l i n t h a n i n Wyoming b e n t o n i t e

or A rizona b e n to n ite . I n m aking c o m p a r is o n s b e tw e e n t h e

th ree c la y s, it s h o u l d be rem em bered t h a t t h e A r i z o n a b e n t o ­

n ite co n tain ed m in e rals o th e r th a n m o n tm o rillo n ite . There­

fore, o n l y t h e r e l a t i o n b e t w e e n k a o l i n a n d Wyoming b e n t o ­

n ite are d iscu ssed here, i n o r d e r to c o n fin e th e com pari­

son to c la y s w h ic h w ere e s s e n t i a l l y sin g le m in erals.

It a p p e a r s t h a t p r o p o r t i o n a t e l y more w a t e r was h e l d

i n t h e k a o l i n t h a n i n b e n t o n i t e b y some m a n n e r o t h e r t h a n

by t h e a d s o r b e d c a t i o n s . As p o i n t e d o u t b e f o r e , probably

a g re a te r p ro p o rtio n of the su rfa c e of m o n tm o rillo n ite is

c o v e re d by ex ch a n g ea b le , c a t i o n s th an in k a o lin ite . There­

fore t h e c a t i o n s w o u ld p l a y a more i m p o r t a n t r o l e i n

m o n tm o rillo n ite th an in k a o l i n i t e . A fu rth er in d ic atio n

of th e g re a te r e f f e c t of th e c a tio n in the h y d ratio n of

m o n tm o rillo n ite is th at, in g en eral, H -k aolins sorbed

o n l y s l i g h t l y more w a t e r t h a n K - k a o l i n s p e r m .e . o f ex­

ch angeable c a tio n , w h i l e H—b e n t o n i t e s s o r b e d a l m o s t t w i c e

 100

a s m u c h w a t e r a s K—b e n t o n i t e s on t h e same b a s i s . T his i s

c o n s iste n t w ith th e r e s u lts r e p o r t e d by B a v e r ("iz.), who

sta te d th at a lth o u g h a d s o rp tio n of w ater vapor in c re a s e d

w ith in c re a sin g exchange c a p a c ity (using v a rio u s c la y s ) ,

t h e r e l a t i o n s h i p was n o t a s i m p l e one* He r e p o r t e d th at

the a m o u n t o f w a t e r s o r b e d p e r m .e* of ex ch an g eab le H

ions in cre ased w ith decreasin g exchange c a p a c ity .

H ow ever, it sh o u ld be n o ted t h a t th e m in e r a lo g ic a l

stru c tu re of m o n tm o rillo n ite is such th a t a larg e propor­

tio n o f th e exchangeable c a t i o n s , and o f t h e w a te r , is

h eld b etw een th e l a y e r s of th e l a t t i c e . In k a o lin ite , on

the o th er hand, th e c a tio n s and w a te r a re h e ld o n ly on t h e

ex tern al su rface. T herefore, h y d r a t i o n w o u ld o c c u r more

c o m p le te ly i n a s h o r t tim e In k a o l i n th a n i n m o n tm o rillo ­

n ite * Thus, the i n f l u e n c e o f t i m e may b e a n i m p o r t a n t

facto r i n t h e amount o f w a te r s o r b e d . U n fo rtu n ate ly , not

e n o u g h tim e was a v a i l a b l e to p e rm it an e x te n siv e stu d y

of th is e ffe ct. I t -was i n d i c a t e d t h a t 8 days were n o t

su fficie n t t o p e r m i t t h e a t t a i n m e n t o f e q u i l i b r i u m when

th e h u m i d i t y was v e r y h i g h , as sam ples sh o w e d s l i g h t l y

m ore s o r p t i o n a t t h e end o f 14 d a y s w i t h r e s p e c t t o t h e

amount o f w a te r s o rb e d i n 8 d a y s. In th is b r ie f survey

at a h i g h h u m id ity no s h i f t in p o s itio n of the i o n s was

observed w ith in c re a se d tim e. A more c o m p le te s t u d y o f t h e

effect of tim e, covering a p erio d o f s e v e r a l m onths o r m o re,

m ay c o n t r i b u t e a d d i t i o n a l p e r t i n e n t d a t a .
 101

INVESTIGATION OF WATER SORPTION PHENOMENA BY

DIFFERENTIAL THERMAL METHODS

The r e s u l t s of th e d i f f e r e n t i a l therm al s tu d ie s of

W yoming b e n t o n i t e s tre a te d w ith vario u s ions and exposed

to a low r e l a t i v e h u m id ity (10$) a r e shown i n F i g u r e 1 4 .

The a r e a u n d e r a c u r v e r e p r e s e n t s th e amount o f w a te r

a s so c ia te d w ith th e c la y . It c a n be s e e n t h a t the a re a

under th e c u rv e s fo llo w ed t h e sam e o r d e r a s t h e am ount

o f s o r b e d w a t e r d e t e r m i n e d more a c c u r a t e l y by w e i g h i n g .

Of m o r e i n t e r e s t here is th e i n f o r m a t i o n w h ic h was

o b tain ed in regard to the in te n sity of b in d in g of w ater.

The m o st a p p a r e n t d i f f e r e n c e in th e curves is th a t a double

p e a k 7/as f o u n d f o r C a - m o n t m o r l l l o n i t e , w h i l e H -, N a -, and

K -m o n tm o rillo n it.es showed o n l y a s i n g l e p e a k . The lo w

tem p eratu re peak of th e C a-clay o ccu rred a t 175°, th e

h ig h tem p eratu re peak a t 250°. The s i n g l e peak o f th e

H - m o n t m o r i l l o n i t e v/as f o u n d a t 1 7 5 ° , t h a t o f t h e N a-m ontm or-

illo n ite a t 155°, and t h a t of th e K -m o n tm o rillo n ite at

150°. It appears, th ere fo re , th at t h e w a t e r was r e m o v e d

som ew hat m ore e a s i l y fro m t h e K - m o n t m o r l l l o n l t e t h a n fro m

N a - m o n t m o r i l l o n i t e a n d t h a t c o n s i d e r a b l y m ore e n e r g y was

req u ired t o rem ove t h i s w a t e r f r o m H- a n d C a —m o n t m o r i l l o n i t e s .

It a l s o was a p p a r e n t th at t h e C a - m o n t m o r i l l o n i t e was h y d r a t e d

w ith a d d itio n a l w ater, as is shown by t h e se c o n d p e ak

w hich o c c u rre d a t th e h ig h er te m p era tu re . T h i s w a t e r was

a p p a r e n t l y m ore t i g h t l y h eld , a n d more e n e r g y was r e q u i r e d

to rem ove i t .
 101a
7r*7~
r ■1.J'',
:;:L: =

I:: '
•r :.ll:
-P i e r < - T i ^ m 4 l ; ; 4 i a k y s e s ,•
...x;
..: V.
rfrr- .YtyoiBing. B e n t o n l c e ^ w i t h V a r i m s : ' ;; C a t i o n s 1
;:i:L •- j r i; ’: T T T

. 1 0 /3 f l e l a t i r e t H i m l a Lt y :j

: . 100: :.: £ . 0 .0 .:. .....500. .400 :

T em perature (°.C«) . ,

... .; .. Fjigur.e 1 4
 102

These r e s u l t s agree very w e ll w ith th o se o f H en d rick s,

N elson, and A le x a n d e r ( 5) , who s t u d i e d t h e c h a n g e s t a k i n g

place in the s tr u c tu r e of the p e a k s when r a o n t r n o r i l l o n i t e s

w ere exposed to a w ide ra n g e o f r e l a t i v e h u m id ities.

H e n d r i c k s showed t h a t t h e c u r v e s o b t a i n e d at. l o w e r h u m i d i ­

tie s w ere c a p a b le o f more a c c u r a t e an aly sis, because of

th eir stru c tu re , th an th o se reco rd ed a t higher h u m id itie s.

H endricks u se d a r a t e of h eatin g o f 12° p e r m in u te w h i l e

a rate o f 6° p e r m i n u t e was u s e d h e r e . He o b t a i n e d c u r v e s

very sim ila r to th o s e found i n t h i s w ork. A t 10% r e l a t i v e

h u m i d i t y he f o u n d s i n g l e peaks f o r H-, N a - , and K-

m o n tm o rillo n it.es and a do u b le peak f o r C a -m o n tm o rillo n ite .

H is p e a k s o c c u r r e d a t s l i g h t l y higher tem p eratu res th an th o se

of th e a u th o r because o f h is f a s t e r r a t e of h eatin g . A

c lo se in s p e c tio n of h is curves r e v e a l s 't h a t th e s in g le

p e a k s o f K -, N a- and H - m o n tm o r il lo n it e s w ere fo u n d a t

ap p ro x im ately 165°, 170° and 182° r e s p e c t i v e l y , and t h a t

t h e low t e m p e r a t u r e p e a k o f t h e C a - m o n t m o r i l l o n i t e o c c u r r e d

a t ap p ro x im ately 185°. H e n d r i c k s may h a v e b e l i e v e d t'h a t

t h e s e d i f f e r e n c e s w ere n o t w o rth y o f em p h asis, but i t is

sig n ific a n t th at th e same t r e n d was f o u n d i n t h i s w ork.

H endricks c o r r e l a t e d the }iigher t e m p e r a t u r e peak found

in the C a -s a lt w ith the h y d ra tio n of the exchangeable c a t ­

ion. The r e m a i n i n g w a t e r , i.e ., t h a t r e p r e s e n te d by th e

low t e m p e r a t u r e p e a k , he b e l i e v e d was t h a t r e q u i r e d to

h y d rate th e su rfa c e ad jacen t to , b u t n o t c o v e r e d by t h e

ex ch an g eab le c a tio n . T herefore, he c o n c l u d e s t . i a t t h e

 103

Ca++ i o n -was n y d r a t e d , w h i l e Na+3 E+, a n d H+ w e r e n o t *

H en d rick s a ls o found t h a t the h ig h er tem p eratu re peak d id

n o i- c h a n g e i n s i z e w n e n t h e c l a y s w e r e e x p o s e d t o higher

h u m id ities, hut th at t h e lo w e r t e m p e r a t u r e p e ak became

larg er* . From t n i s it was d e d u c e d t h a t th e f i r s t p o rtio n

of w ater is used to h y d rate th e c a tio n (where th e c a t i o n

is h y d r a t e d ) , and t h a t a d d itio n a l w ater h ydrates th e r e ­

m aining surface* T h ir d p eak s were in tr o d u c e d a t h ig h e r

.h u m id ities i n th e L i- and a l k a l i n e earth -salts, and

H en d rick s a t t r i b u t e d th ese to th e in tro d u c tio n of s t i l l

a n o th e r la y e r of w ater m o le cu le s. H endricks p o in te d o u t

t.’i a t t h e in tro d u c tio n of su ccessiv e lay ers of w ater is

not a sim p le p ro ce ss because th e p rev io u s la y e r i s probably

reo rg an ised . S ince a therm al a n a ly s is i s made by r e m o v i n g

th e w a te r, it d o e s n o t show7 t h e b i n d i n g co n d itio n s present

before any w ater i s removed*

A fu rth er c o r r e la tio n w ith re s p e c t to th e in te n s ity

w i t h w hich w a te r i s a t t r a c t e d may b e n o t e d w i t h t h e w o r k

of R u ssell (37) who f o u n d t h a t the re d u c tio n of s p e c ific

volum e o f c l a y s im m ersed i n liq u id s, in d ecreasin g order

of e f f e c t i v e n e s s w as: Mg, C a , H, N a , K . He r e p o r t e d t h a t

Mg i o n s o n t h e c la y h a d a b o u t s e v e n m o r e m o l e c u l e s a n d Ca

io n s a b o u t t h r e e m ore m o l e c u l e s o f w a t e r o f h y d r a t i o n t h a n

Na a n d K i o n s . He a t t r i b u t e d t h e d e c r e a s e i n volum e t o

t h e n u m b e r a n d mean d e n s i t y of th e e x ch a n g e c a t i o n on t h e

surface.
 104

CONCLUSIONS

The h y d r a t i o n c h a r a c t e r i s t i c s o f k a o l i n and b e n t o n i t e ,

s a tu ra te d w ith v ario u s ions (H+, C a + + , N a + , a n d K+) have

b e e n s t u d i e d , by means o f t h e f o l l o w i n g ty p es of m easure­

m ents: (l) heat of w e ttin g , (2) s o r p t i o n o f w ater from

the vapor p hase, and (o) d ifferen tial th erm al m ethods.

An e f f o r t w a s m ade t o d i s t i n g u i s h b e t w e e n c a p a c i t y

of th e c la y t o b in d w a t e r and t h e i n t e n s i t y w i t h w h ic h t h e

w ater is bound. The h e a t o f w e t t i n g is a re p re se n ta tio n

of th e lo ss of k in e tic energy o f w ater m olecu les r e s u l t ­

in g from t h e i r o r i e n t a t i o n by t h e c l a y p a r t i c l e s , and i s

p r o b a b l y i n f l u e n c e d m ore by t h e i n t e n s i t y w ith w hich

w ater i s a ttrac ted th a n by th e c a p a c ity of th e c la y to

sorb w ater. In o th e r w ords, th e f i r s t la y e r of w ater tak e n

up by d r y c l a y e v o lv e s th e m ost h e a t.

M e a s u r e m e n t s .o f t h e amount o f w a t e r s o r b e d fro m t h e

v a p o r p h a se com bine t h e f a c t o r s of in te n s ity an d 'c ap a city .

At low h u m i d i t i e s the in te n s ity of a ttra c tio n i s more

a p p a re n t, w hile at iiigh h u m id i t ie s th e c a p a c ity of the c la y

t o t a k e up w a t e r becomes t h e im p o rtan t f a c to r .

D iffe re n tia l th e r m a l m ethods r e v e a l b o t h th e cap acity

and i n t e n s i t y fac to r. A m easurem ent of th e te m p e ra tu re

req u ired t o rem ove t h e w a te r i s o b tain ed , as w e l l as an

in d ic atio n of th e to ta l amount o f h e a t r e q u i r e d . Thus,

if tw o c l a y s s o r b e q u a l am ounts o f w a t e r , the one w h ic h

lo ses it a t a h ig h er tem p eratu re a t t r a c t s the w ater w ith

the g re a te r in te n sity .
 105

A somewhat o v e r - s i m p l i f i e d r e v ie w o f t h e r e s u l t s of

th ese te sts, w h i c h h a v e "been d i s c u s s e d p rev io u sly , fo llo w s.

■K-- c l a y s showed t h e l o w e s t h e a t o f w e t t i n g , t h e low ­

e s t w ater so rp tio n , and s o r b e d w a t e r was rem oved a t t h e

lo w est tem p eratu re.

N a-clay s, com pared t o K - c la y s , had a somewhat h i g h e r

heat of w ettin g , a g r e a t e r w ater so rp tio n , and so rb e d

w a t e r was rem oved a t a slig h tly higher tem p eratu re.

H -clay s had s t i l l h ig h e r h e a t o f w e ttin g th a n Na-

or K -clay s, sorbed, g r e a t e r am ounts o f w a t e r , and t h e

tem p eratu re o f r e m o v a l o f s o r b e d w a t e r was M g h e r .

The p o s i t i o n of C a-clays w ith re s p e c t to H - c l a y s was

not th e sa m e i n a l l te sts. T he C a - c l a y s ev o lv ed a g r e a t e r

amount, o f h e a t on w e t t i n g . They show ed a g r e a t e r so rp tio n

of w ater a t a low h u m i d i t y b u t a som ew hat s m a l l e r so rp tio n

at h ig h er h u m id itie s, and r e q u ir e d th e m ost en erg y to r e ­

move t h e w a t e r .

T herefore, it appears th a t, in g en eral, clay s satu rated

w ith v a rio u s adsorbed c a tio n s sh o w t h e f o l l o w i n g order of

decreasin g h y d ratio n : Ca, H, H a , K .

A s t u d y was a l s o made o f trie h e a t effects o ccu rrin g

when c l a y s a re w etted in a lk a lin e so lu tio n s. I t was o b ­

s e r v e d t h a t more h e a t was e v o lv e d when the c la y s w ere

im m ersed i n a l k a l i n e so lu tio n s tlian i n w a te r a lo n e . T his

e f f e c t was f o u n d i n b o t h k a o l i n s and b e n t o n i t e s , and

o c c u r r e d i n Na— a n d K—c l a y s a s w e l l a s i n t h e H—c l a y s .

 106

The f a c t o r s co n trib u tin g to t h i s e f f e c t have b e e n d i s c u s s e d ,

b u t n o t enough d a ta a re a v a ila b le t o draw d e f i n i t e conclu­

sio n s .

Many o f t h e ex p la n atio n s p resen ted here are based

on th e a s s u m p tio n t h a t th e a d s o rb e d c a t i o n s are h eld a t

th e c la y m in eral su rfa c e , rath er t h a n a t so m e d i s t a n c e

from i t , as p o stu la te d in th e double la y e r theory. Much

ev id en ce i n the lite ra tu re s u p p o rts th e double la y e r th e o r y ,

i n w hich t h e c atio n s are c o n c e iv e d as s e p a r a t e d from t h e

cla y surface by an in n e r l a y e r o f OH i o n s .

Jo h n so n and H orton (15), for ex am ple, p o s t u l a t e t h e

a d s o r p t i o n o f OH i o n s 011 p o s i t i v e a re a s of th e broken

edges of k a o lin ite flak es, on th e a s s u m p t i o n t h a t A1+++

is the o nly p o s itiv e io n w hich co u ld f i t w e ll in to the

k a o lin ite la ttic e and i s p ro b ab ly n o t p r e s e n t in the form a­

tio n of k a o lin ite . The c a t i o n s are then v is u a lis e d as

c o u n t e r c barg e s .

H ow ever, much o f t h e r e c e n t evid en ce (5) (17) seem s t o

show t h a t th e c a tio n s are h eld a t th e c la y m in eral s u r f a c e .

Grim ( l ) sta te s th a t th e c o n c e p t o f a n i n n e r l a y e r o f OH

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

sin ce th e c h a r g e s on t h e la ttic e a re m ainly such t h a t

p o sitiv e charges are re q u ire d to sa tisfy them .

The r e s u l t s of th is i n v e s t i g a t i o n may b e e x p l a i n e d

b y t h e c o n c e p t o f c a t i o n a d s o r p t i o n a t trie s u r f a c e o f t h e

clay m in eral, b u t do n o t d i s p r o v e t h e d o u b le l a y e r t h e o r y .
 107

The w r i t e r b eliev es th a t th e h y d ratio n of clay s is

i n f l u e n c e d n o t o n l y by t h e (l) h y d ra tio n of th e adsorbed

io n s, but also by (2) tn e h y d ra tio n of th e c la y m in eral

surface i t s e l f , and by b o t h (o) the e f f e c t of th e adsorbed

io n s w ith re s p e c t to the h y d ra tio n of th e c la y m in eral

surface, and (4) th e e f f e c t of th e clay m in e ral su rface

on t h e h y d ratio n of the io n s.

(1) H y d ratio n o f adso rb ed ions

The h y d r a t i o n o f t h e i o n s d e p e n d s , a s has b e e n d i s c u s s e d

before, on t h e i r size, v a le n c e , a n d perhaps p o l a r i z a b i l i t y .

F o r exam ple, it is g e n e r a l l y a s s u m e d t h a t K+ s h o u l d a t t r a c t

less w a t e r t h a n Na+ b y v i r t u e of i t s g reater size.

How ever, i t is re c o g n iz e d th a t th e h y d ra tio n o f adsorbed

ions is p ro bably n o t th e same a s th a t of the io n s in so lu ­

tio n .

(2) H y d ratio n o f the m in eral su rfa c e

The h y d r a t i o n o f t h e surface o f th e m in e ra l depends

on t h e ch aracter of t h a t surface, in c lu d in g w hether or n o t

it c o n ta in s adsorbed c a tio n s .

( 5 ) E f f e c t o f a d s o r b e d i o n s on t h e h y d ratio n of th e clay
surface

E f f e c t o f a d s o r b e d i o n s on t h e h y d ra tio n of th e clay

surface.

I t w a s s h o w n t h a t w h e n k a o l i n a n d b e n t o n i t e w e r e com­

p a r e d 011 t h e b a s i s o f e q u i v a l e n t am ounts o f a d s o rb e d c a t i o n s ,

less h e a t was e v o l v e d , a nd l e s s w a t e r was s o r b e d , p er m .e.

o f ex ch an g eab le c a t io n in b e n to n ite. These r e s u l t s m ight

 108

be a t t r i b u t e d to a s m a ll e r amount o f w a te r h y d r a tin g th e

m in eral su rfa ce of b en to n ite in p ro p o rtio n to th at h y d rat­

ing th e c a tio n s , th an is th e case in k a o lin . M ontm orillo—

n ite p r o b a b l y l ia s a g r e a t e r f r a c t i o n o f i t s s u rfa c e covered

by c a t i o n s th an nas k a o l i n i t e . T herefore, th e c a tio n s

w o u ld be e x p e c t e d t o p l a y a more i m p o r t a n t r o l e i n m ont­

m o rillo n ite th an in k a o l i n i t e .

The a s s u m p t i o n t h a t m o n t m o r i l l o n i t e h a s a g r e a t e r f r a c ­

tio n of i t s s u r f a c e c o v e re d by c a t i o n s t h a n has k a o l i n i t e

is made on t h e b a s i s of th e fo llo w in g c o n s id e r a tio n s .

T h e c a t i o n s may b e h e l d a t t h e b r o k e n e d g e s o f f l a k e s

i n b o th m o n tm o r illo n ite and k a o l i n i t e , and a r e a ls o h eld

on t h e b a s a l oxygen p l a n e s of m o n tm o rillo n ite, b u t n o t on

th e b a s a l oxygen p la n e s of k a o lin ite . A p ro b ab le ex p lan a­

tio n for th is phenom enon h a s b e e n d i s c u s s e d by Grim ( l ) ,

who p o i n t e d o u t t h a t th e stru c tu re of m o n tm o rillo n ite

p r o p o s e d by Edelm ann and F a v e j e e (F ig u re $(3) shows t h a t

t h e b a s a l p l a n e s i n m o n t m o r i l l o n i t e c o n t a i n OH i o n s w h i c h

p r o v i d e h y d r o g e n s f o r r e p l a c e m e n t by c a t i o n s . F u rth erm o re,

the m o n tm o rillo n ite s tr u c tu r e c o n t a i n s two s u c h b a s a l

oxygen p la n e s com pared to o n ly one i n k a o l i n i t e . There i s

no r e a s o n to b e l i e v e th a t th e fra c tu re of a flak e of k a o lin ­

ite w o u ld l e a d t o more a c t i v e sp o ts per u n it a re a th an th e

fractu re of a flak e of m o n tm o rillo n ite. In a d d itio n ,

su b stitu tio n s o f i o n s may o c c u r i n m o n t m o r i l l o n i t e , but

not in k a o lin ite . T h e s e s u b s t i t u t i o n s may l e a d t o a n

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

of c atio n s.
 109

For th ese reasons i t s e e m s t h a t m o n t m o r i l l o n i t e may

h o l d m ore c a t i o n s per u n it of su rface than k a o lin ite .

The g r e a t e r r o l e w h ic h t h e c a t i o n s p la y i n m o n tm o ril­

lo n ite is fu rth er e v i d e n c e d by t h e f a c t t h a t t h e sa tu ratio n

o f b e n t o n i t e by one c a t i o n i n p l a c e of an o th er caused a

g r e a te r p ercen tag e d iffe re n c e in th e heat of w ettin g and

in w ater s o rp tio n th an a s im ila r replacem ent in k a o lin .

.(4 ) E f f e c t o f c l a y s u r f a c e on t h e h v d r a t i o n o f a d s o rb e d i o n s

It sh o u ld be m entioned t h a t p erh ap s th e a d so rb ed io n s

are h eld w ith d i f f e r e n t i n t e n s i t i e s by k a o l i n i t e and by

m o n tm o rillo n ite. It i s known t h a t a d s o r b e d i o n s a r e n o t

h y d rate d as co m p letely as f r e e io n s in s o lu tio n , and t h e r e ­

fore io n s w hich a r e l e s s tig h tly h e l d may b e m o r e c o m p l e t e l y

h y d rated . In o rd e r to e x p la in th e o b serv ed e f f e c t by t h i s

m eans, it w ould be n e c e s s a r y t o assum e t h a t t h e a d so rb e d

io n s are h eld l e s s tig h tly in k a o lin ite th a n i n m o ntm oril­

lo n ite . T h e r e d o e s n o t seem t o b e much e v i d e n c e i n f a v o r

o f su ch an a ssu m p tio n , and t h e r e f o r e i t w ould be n e c e s s a r y

to b eliev e th at th e e f f e c t of the surface of the k a o lin ite

is im p o rtan t.
It is a lso p o ssib le th a t th e p h y sic al s tru c tu re of th e

c la y ag g reg ates is i n f l u e n c e d by t h e a d so rp tio n of ions

in s u c h a way t h a t i t may b e a n I m p o r t a n t f a c t o r i n t h e

a p p a re n t d if f e r e n c e s found in th e a t t r a c t i o n of w ater fo r

c la y s. F o r exam ple, it i s w e l l known t h a t d r y N a - c l a y

co n tain s sm all p o re s , w h i l e C a — a n d H—c l a y s c o n t a i n l a r g e r

 110

pores. T h u s , w a t e r may p e n e t r a t e m o r e s l o w l y i n t o t h e

p o r e s o f Na a n d K - c l a y s a n d c a u s e t h e m t o b e w e t t e d l e s s

co m p letely . T h is f a c t o r p ro b a b ly ca n n o t be e lim in a te d

e n tire ly in stu d ie s of the a t t r a c t i o n of dry c lay s fo r

w ater. It is su g g ested , how ever, th a t fu rth er stu d ies

of th is tim e e f f e c t be made. How ever, i t is b eliev ed th a t

the ev id en ce of th e d i f f e r e n t i a l th e rm a l s t u d i e s , i n w hich

w ater i s rem oved fro m t h e c l a y r a t h e r th a n added to it,

in d ic ate s th at th is effect is of secondary im p o rtan ce.

It seem s, th erefo re, t h a t th e r e s u l t s of the heat of

w ettin g , w ater so rp tio n , and d i f f e r e n t i a l therm al t e s ts

are i n a g re em e n t w ith e ac h o t h e r and w ith th e theory,

and p re s e n t a u n if ie d p ictu re of th e h y d ratio n of c la y s.

 ACKNOWLEDGEMMTS

The w r i t e r w i s h e s t o e x p r e s s his th an k s and a p p r e c i ­

a t i o n f o r t h e a s s i s t a n c e o f D r . E . C. H en ry i n t h e p l a n ­

n in g and e x e c u tio n o f t h i s w ork. He i s a lso d eeply g r a te f u l

for th e c o o p e r a t i o n o f D r . N . W. T a y l o r . He a p p r e c i a t e s th e

sin cere in te re st shown by D r . H. M. D a v i s a n d D r . W. W e y l .

A l l o t h e r m embers o f t h e f a c u l t y and g r a d u a te s t u d e n ts of

th e D ep artm en t o f C eram ics a re thanked f o r t h e i r co o p eratio n .

D r. A. C l a r k , o f The B a t t e l l e M e m o r ia l I n s t i t u t e , and

D r. S . C. Schum an, o f th e School of C hem istry, gave v a lu a b le

ad v ice in re g a rd to th e c o n s tru c tio n of th e c a lo rim e te r.

M r. E . F . S h e e d e r , o f th e M ineral I n d u s tr ie s Instrum ent

Shop, is thanked f o r h is e x c e l l e n t work i n b u i l d i n g the

c alo rim e te r. M r . F . M a l l o y , who p r e p a r e d t h e g l a s s b u lb s,

was a l s o v e r y h e l p f u l . T h e a i d o f D r . F . C. T od d m u s t a l s o

be m en tioned, a n d D r . W. H . Ham o f t h e S c h o o l o f P h y s i c s i s

thanked f o r th e lo a n o f a sta n d a rd r e s is ta n c e . The w r i t e r

is m ost g r a t e f u l f o r th e a ssista n c e o f h is w ife , B ern ice

S ie fert, th ro u g h o u t th e c o u rs e o f t h i s work.
 BIBLIOGRAPHY

1 . R. E . G rim , "M odern C o n c e p ts o f C la v M a t e r i a l s , "

J o u r . G e o l o g y , 50 ,. ( 5 ) 2 2 5 - 7 5 ( 1 9 4 2 )
n«
U« H o f m a n n , K . E n d e l 3. a n d D* W i l m , " E r I s t a i l s t r u k t u r
u n d On b i l l i n g v o n M o n t m o r i l l o n i t , " Z e i t s c h r . E r i s t .
3 6 , 5 4 0 -4 8 (1955)
rz
C* H. E d e l m a n n a n d J . C h . L . F a v e j e e , "O n t h e Cr- ' b i , a l
S t r u c t u r e o f M o n tm o r illo n ite and H a l l o y s i t e , " .•e itsc n r.
K r i s t . 1 0 2 , 4 1 7 -5 1 (1940)

4 . G r u n e r , "The C r y s t a l S t r u c t u r e of K a o lin ite ," Z e itsc h r .

K r i s t . 3 5 , 7 5 -3 3 (1952)

5 . S . B . H e n d r i c l c s , R . A . N e l s o n , L„ T . A l e x a n d e r ,
" H y d r a t i o n m echanism o f th e C la y M in e r a l M o n t m o r i l l o n i t e
S a t u r a t e d w i t h V a r i o u s C a t i o n s , " J o u r . A m e r , Ch em.
S o c . 6 2 , 1457 (1940)

S. E . A, H au ser, " C o llo id C hem istry In C e ra m ic s," J o u r.

Amer. C e r a m . S o c . 2 4 , 1 7 9 - 3 9 (194V)

7* G. W i e g n e r , " S o m e P h y s i c a l - C h e m i c a l P r o p e r t i e s o f
C1 a y s I . B a s e Exc ■la n g e o r I o n i c Ex c h a n g e , " J o u r . S o c .
Chem. I n d . 5 0 , 6 5 ( 1 9 5 1 )

8 . R. B r a d f i e l d , "The C o n c e n t r a t i o n o f C a t i o n s i n C lay
S o l s , " J o u r . P h y s . C h e m . 3 6 , 3 4 0 ( .1 952)

9 * R . B r a d f i e l d , " T l ie B e a r i n g o f R e c e n t I n v e s t i g a t i o n s
i n S o i l C o l l o i d s on S o i l G l a s s i f i c a t i o n , " T r a n s . 3 rd
I n t e r n . C o n g r. S o i l . S c i . O x fo rd 2 , 1 3 4 -1 3 (1935)

10. S» M a t t s o n , " L a w s o f S o i l C o l l o i d a l B e h a v i o r . V I I I
Form s and F u n c t i o n s o f W a t e r , " S o i l S c i e n c e 5 5 , 301
(1932)

11 . W. W. M e y e r , " C o l l o i d a l N a t u r e a n d R e l a t e d P r o p e r t i e s
of C la y s," J o u r. R esearch N at. B ur. S tan d . 15, 245-58
( 1 9 5 4 ): R. P . 706

12 . L . B. B a v e r , "T h e E f f e c t o f t h e Amount a n d N a t u r e o f
E x c Vicing e a b l e C a t i o n s o n t h e S t r u c t u r e o f C o l l o i d a l
C l a y , " Mo. E x p . S t a . R e s . B u l l . 1 2 9 ( 1 9 2 9 )

15. H. J e n n y , " S t u d i e s o f t h e M e c h a n i s m o f I o n i c E x c h a n g e
i n C o l l o i d a l A l u m i n u m S i l i c a t e s , " J o u r . P h y s . C he m .
3 6 , 2 2 1 7 - 5 8 ( 1 9 5 2 ) Chem, A b s t . 2 6 , 5 2 4 2 .
14. H. J e n n y , " S i m p l e T h e o r y o f I o n i c iiixc . r a n g s . I Ions
o f E q u a l V a l e n c y , " J o u r . P h y s . Chem. 4 0 , 5 0 1 - 1 7 ( 1 9 5 6 )
Chem. A b s t . 5 0 , 47-39

15. A. L« J o I'ms o n a n d F . H. N o r t o n , " F u n d a m e n t a l S t u d y

o f C lay: I I , M echanism o f D e f l o c c u l a t i o n i n th e C l a y -
1 7 a t e r S y s t e m , " J o u r . A m e r. Ceram.. S o c . 9 4 , 1 3 9 - 2 0 3
(1941)

16. A* L» S» D a r a n d H, J . C. T e n d e l o o , " U b e r d i e D o p -
p e l s c . h i c h t d e r T o n k o l l o i d e , " K o l l o i d 3 e i h . 4 4 , 97
(lo ss) -

17. J . B. P ag o , "The r e l a t i o n o f I o n i c S i z e to t h e F i x a ­
t i o n o f P o ta s s iu m and o t h e r C a ti o n s by C o l l o i d a l
C l a y , " P h .D . t h e s i s , Ohio S t a t e U n i v e r s i t y (1 9 4 0 )

18. E . B la n c k , "H an d b u ch d e r B o d e n l e l i r e , " E r s t e r Erg&n-

zu n g sb an d . J u l i u s S p r i n g e r . B e r l i n , 1939. (C h a p te r
by F . A i t e n and B. K u rm ie s )

19. It. J . P a g e , " T h e I n v e s t i g a t i o n s o f K. K c G e d r o i z o n

Base Exchange and A b s o r p tio n ," a resu m e. I n t . S oc.
S o i l S c i . 2 n d Comm. 2 0 7 - 2 5 1 ( 1 9 2 6 - 1 9 2 7 )

20. P . V a g e l e r a n d F» A l t e n , "Bflden d e s N i l m id G a s h I I , "

Z . P f l a n c e r n a h r , Dflngung B o d e n k . A 2 1 , 5 3 5 ( l 9 3 l )

21. A. Pc V a n s e lo Y J , " E q u i l i b r i a o f t h e B a s e E x c h a n g e
R eactio n s o f B e n to n ite s ,P e rm u tite s , S o il C o llo id s
and Z e o l i t e s , " S o i l S c i . 3 3 , 9 5 -1 1 3 (1932) Chem.
A b s t. 26, 2542

22. P . S c h a c h t s c h a b e l , " A d s o r p t i o n by C la y M i n e r a l s and

O rganic S o i l C o llo id s," K o llo id B e it 51, (5 -7 ) 199-
2 7 6 ( 1 9 4 0 ) Chem. A b s t . . 5 4 ; 4 6 5 4

23. W. U. B e h r e n s , " B e s i e h u n g e n z v i s c h e n d e r O b e r f l S c h e ,
d e r H y g r o s k o p i z i t . s t und d e r B e n etzu n g s w S rm e d e s
B o d e n s ," Z . P f la n z * e rn a h r * D iingung. Bodenk. A 4 0 , 2 5 7 -
509 (1935)
24. M, 17. C h a p e k . " D i e D i c h t e d e s d u r c h d e n B o d e n a d s o r p -
t e n W a s s e r s , " Z . P f l a n z e n e r n a h r . Diingung B o d e n k .
A 3 4 , 2 6 5 ( 1 9 3 4 ) Che m. A b s t . 2 9 , 8 6 7

25. H. J a n e r t , " T h e A p p l i c a t i o n o f H e a t o f W e t t i n g M e a s u r
rnents t o S o i l R e s e a r c h P r o b l e m s ," J o u r , A g r . S c i . 24
1 3 6 -5 0 (1934)

26. W. A . P a t r i c k a n d F . V. G r i m , " H e a t o f W e t t i n g o f
S i l i c a G e l," 43, 2144-50 (l9 2 l)
27. R. Hour/ink, " E l a s t i c i t y , P l a s t i c i t y , and S t r u c t u r e of
M a t t e r , " C am b rid g e, U n i v e r s i t y P r e s s (1957)

28. YJ. N i t s s c h , "On t h e S t r u c t u r e o f t h e H y d r a t i o n H u l l

o f In o rg a n ic S o il C o llo id s ," K o llo id Z e i ts c h r . 95,
110-15 (1 9 4 0 ), c i t e d i n ( l )

29. S . B . H e n d r i c k s a n d M. E . J e f f e r s o n , " S t r u c t u r e s o f
K a o lin and T a l c - P y r o p h y l l i t e H y d ra te s and t h e i r
B e a r i n g on W a t e r S o r p t i o n o f t h e C l a y s , " A m er. M i n e r a l .
2 3 , 8 6 2 -7 5 (1938)

50. W. P . K e l l e y , Hans J e n n y , a n d S . M. B r o w n , " H y d r a t i o n

o f M in e ra ls and S o i l C o l lo i d s i n R e l a t i o n to C r y s t a l
S t r u c t u r e , " S o i l S c i . 4 1 , 2 5 9 -7 4 (1936)

31. L . D. B a v e r a n d G* M. H o r n e r , " W a t e r C o n t e n t o f S o i l
C o l lo i d s a s R e la te d to t h e i r C hem ical C o m n o sitio n ,"
S o i l S c i . 3 6 , 329 (1933)

32. L . D. B a v e r , "S o il P h y sic s," Jo h n Y /iley and Sons (1940)

33. A. M, B u s w e l l a n d B. F . D u d e n b o s t e l , " S p e c t o s c o p i c
S t u d i e s o f B a s e E x c h a n g e M a t e r i a l s , " J o u r . Am er. Chem.
S o c . 6 3 , 2554 (1941)

34. S . M a t t s o n , " T h e Laws o f S o i l C o l l o i d a l B e h a v i o r I , "

S o i l S c i . 2 g , 179-220

55. E . C. H e n r y a n d N. V/. T a y l o r , " A c i d a n d b a s e b i n d i n g

C a p a c i t i e s and V i s c o s i t y R e l a t i o n s i n C e r t a i n W h ite -
w a r e C l a y s , " J o u r . A m e r . C e r a m . S o c . 21* ( 5 ) 1 6 5 - 1 7 5
(1938)

36, G. J . B o u y o u c o s , " T h e P h e n o m e n a o f C o n t r a c t i o n a n d
e x p a n s i o n o f s o i l s when W e t t e d w i t h W a t e r , " S o i l S c i ,
2 3 , 1 1 9 - 2 6 ( 1 9 2 7 ) Chem. A b s t . 2 1 , 4 0 0 2 .

57. E . W. R u s s e l l , " T h e I n t e r a c t i o n o f C l a y w i t h Y J a te r
a n d O r g a n i c L i q u i d s a s M e a s u r e d , b y S p e c i f i c Volume
C h a n g e s a n d i t s R e l a t i o n t o t h e P h e n o m e n a o f Crumb
F o r m a t i o n i n S o i l s , " T r a n s , R oy. S o c . (London) A
2 5 3 , 3 6 1 - 8 9 ( 1 9 3 4 ) , Chem. A b s t . 2 9 , 2 6 6 .

380 D. R . B r i g g s , "YJater R e l a t i o n s h i p s i n C o l l o i d s . I
Vax^or P r e s s u r e M e a s u r e m e n t s o n E l a s t i c G e l s , " J o u r .
P h y s . Chem, 3 5 , 2 9 1 4 ( l 9 3 l )

9. E . A. M i t s c h e r l i c h , " I n v e s t i g a t i o n s C o n c e r n i n g t h e
P h y sical C h a ra c te ris tic s of S o ils ," Landw. J a h r b .
5 0 , 560 ( 1 9 0 1 ) , r e v ie w e d i n (23)
40. M. D. Thomas , " A a u e o u s V a u o r P r e s s u r e o f S o i l s , ”
S o i l S c i . 11 4 0 9 -3 4 ( 1 9 2 1 ) ; 1 7 , 1 - 1 8 ( 1 9 2 4 ) ; 2 5 ,
4 8 5 -9 3 (1928)

41. H. K u r o n , " A d s o r p t i o n v o n f ' a w p f e ^ u n d G a s e h a n BBcben

und T on en und i h r e Verwendung z u r O b e rfl& c h e n e i-- T
m ittlu n g d i e s e r S t o f f e , " K olloidchem . B e ih . 36,
178-256. •

42. S. Oden. T ra n s . F a ra d a y S o c. 17, 8 (1921) review ed

i n (23) - %

43. G. J . B o u y o u c o s , " R e l a t i o n s h i p b e t w e e n t h e U n f y e e
W ater and th e Heat o f W e ttin g o f S o i l s and T h e i r •
S i g n i f i c a n c e , ” M ich. A gr. Exp. S t a . Tech. B u l l .
42 (1 9 1 8 )

44. T . F . B u e h r e r a n d M. S . R o s e n b l u m , " D i l a t o m e t e r f o r
D e t e r m i n i n g Bound W a te r i n S o i l s and O t h e r C o l l o i d a l l v
D i s p e r s e d M a t e r i a l s , " J o u r . P h y s . Chem. 4 3 , 9 4 1 ( 1 9 3 9 ;

45. I * D. J o n e s a n d R . A. G o r t n e r , " F r e e a n d B ou nd W a t e r
i n E l a s t i c a n a R o n - e l a s t i c U e l s , " J . P h y s . Chem. 3 6 ,
3 8 7 -4 3 6 (1952)

46. L . T . A l e x a n d e r a n d T . M. S h a w , " D e t e r m i n a t i o n o f
I c e - W a t e r R e l a t i o n s h i p s by M easu rem en t of D i e l e c t r i c
C o n s t a n t C h a n g e s , " J o u r . P h y s . Chem. 4 1 , 9 55 ( 1 9 3 7 )

47. W. R o b i n s o n , " F r e e a n d b o u n d W a t e r D e t e r m i n a t i o n s
by t h e H eat o f F u s i o n o f I c e M e th o d ," J o u r . B i o l .
Chem. 9 2 , 6 9 9 - 7 0 9 ( 1 9 3 1 )

48. S . S . K i s t l e r , " T h e M e a s u r e m e n t o f ’ Bound W a t e r 1

b y t h e F r e e z i n g M e t h o d , " J o u r . A m e r . Chem. S o c .
5 3 , 901 (1936)

49. K u l m a n a n d G o l o s o v a , " B ou n d W a t e r i n Br e a d M a k i n g , ”
C e r e a l Chem. 1 3 , 2 0 2 - 2 1 7 ( 1 9 3 6 )

50. P . I . A n d r i a n o w , " D i e W J L r m e k a p a z i t f it d e s G e b u n d e n
W a s s e rs und d e s B o d e n s ," IC o llo id . Z 7 8 , 107 (1937)

51. B . M a l k o w e r , T . M. S h a w , L . T . A l e x a n d e r , " T h e
S p e c i f i c S u r f a c e a n d D e n s i t y o f Some S o i l s a n d T h e i r
C o l l o i d s , " S o i l S c i . S o c . A m e r. P r o c . 2 , 1 0 1 - 8 ( 1 9 3 7 )

52. W. W. P a t e , " T h e I n f l u e n c e o f t h e Am ount a n d N a t u r e

o f R e p la c e a b le Base upon th e Heat o f W ettin g o f S o i l s
a n d S o i l C o l l o i d s , " S o i l S c i . 2 0 , 329 (1925)
53. H. J a n e r t , " U n t e r s u c h u n g e n i l b e r d i e B e n e t z u n g s w a r m e
d e s B o d e n s , " Z . P f l a n z e n e r n a h r . DUngrng B o d e n k . A
1 9 , £31 (1931)

54. A. D u m a n s k i a n d M. C b a p e k , " U b e r B e n l t z u n g s w a r m e . I
E i n f l u s z d e r a d s o r b i e r t e n I o n e n a u f d i e B enet.zungs-
w a r m e ," K o l l o i d Z. 7 1 , 2 7 9 - 8 2 (1 9 3 5 )

56. C . G. H arm an a n d F . F r a u l i n i , "Some F u n d a m e n t a l P r o p ­

e r t i e s o f Raw C l a y s I n f l u e n c i n g T h e i r U s e s , " P h . D .
t h e s i s , U n i v e r s i t y o f I l l i n o i s , D e p a rtm e n t o f C eram ic
E n g i n e e r i n g (1939)

57. C . G. H a r m a n a n d F . F r a u l i n i , " P r o p e r t i e s o f K a o l i n i t e
a s a F u n c t i o n o f i t s P a r t i c l e S i z e , " J o u r . A m er.
Ceram . S o c . 2 3 , 252 (1940)

58. F . E. B a r t e l l and Y ing F u , "The S p e c i f i c S u r f a c e

A r e a o f A c t i v a t e d C a r b o n a n d S i l i c a , " C o l l . Sym. A n n .
7 , 1 9 3 5 -4 9 (1929) Chem. A b s t . 24* 3 4 1 2 .

59. G. B o u y o u c o s , " T h e H e a t o f W e t t i n g a s a New Means o f

E stim atin g C o llo id a l M a terial of S o ils ," S o il S c i.
1 9 , 1 5 3 -6 2 (1925)

60. L . C. K ap p , "The A p p r o x im a te S i z e a t W hich H eat o f

W e t ti n g i s m a n i f e s t e d , " S o i l S c i . 2 9 , 401-412 (1930)

61. H. R o d e w a l d , " U b e r Q u e l l u n g s - u n d B e n e t z u n g s e r s c h e i n -
un g en ," p h y s i k . Chemie 3 3 , 593 (1900)

62. M. H o s e h , " H e a t o f W e t t i n g o f Some S o i l C o l l o i d s a t

D i f f e r e n t M o istu re C o n te n ts ," S o i l S c i. 43, 257-75
(1937)

63. C . W. P a r m e l e e a n d V . D. F r e c h e t t e , " H e a t ~ o f - W e t t i n g
V a l u e s o f U n f i r e d a n d F i r e d C l a y s , " Join* . A m e r.
C eram . S o c . 2 5 , 1 0 8 -1 2 (1942)

64. H. A. W a d s w o r t h , "Som e F a c t o r s I n f l u e n c i n g t h e H e a t
o f W e ttin g o f S o i l s , " S o i l S c i . 4 7 , 3 8 5 -9 0 (1939)

65. A . N. P u r i a n d R . C . Ho o n , " P h y s i c a l C h a r a c t e r i s t i c s
o f S o i l s . I l l Heat o f W e t t i n g , " S o i l S c i . 4 7 , 41 5 -2 3
(1939)
66. F . A l t e n a n d B. K u r m i e s , " T h e P h y s i c a l C h e m i c a l R u l e s
f o r th e C a tio n Exchange i n M in e ra l S o i l , " T ra n s . 3 rd
I n t e r n . Cong. S o i l S c i . , O x fo rd , 1 , 59-62 (1 9 3 5 ).
C . A. 2 9 , 8 1 9 7
67. M. S . A n d e r s o n , " T h e H e a t o f 7 / e t t i n g o f S o i l C o l l o i d s , "
J o u r . A g r. R e s e a r c h 9 , 9 2 7 -3 5 (1924)

68. G. J . B o u y o u c o s , " D i f f e r e n c e s i n H e a t o f R e a c t i o n
B etw een A r t i f i c i a l and S o i l G e ls o f S i l i c a , A lum ina,
and I r o n , w i t h H y d ro x id e s ," S o i l S c i . 2 3 , 2 4 3 -7
( 1 9 2 7 ) . Chem. A b s t . 2 1 , 4002

69. W. S t r f i t l i n g , " T h e R e a c t i o n B e t w e e n B u r n t K a o l i n a n d
Lirne i n A q u e o u s S o l u t i o n , " B e r . D e u t . k e r a m . G e s .
2 0 , 5 2 2 —7 ( l , 9 3 9 ) Chem. A b s t . 2 1 4 7

70. W. S t r & t l i n g , " D e t e r m i n a t i o n o f t h e A c t i v i t y o f

K a o l i n C a l c i n e d a t V a r io u s T e m p e r a t u r e s ," Zement
2 9 . 4 0 1 - 5 , 4 1 3 - 1 5 . ( 1 9 4 0 ) Chem. A b s t . 5 6 , 4 2 9 9 .

71. P. I . A n d ria n o w , "H e ats o f W e ttin g and t h e P h y s i c a l

S ig n if ic a n c e of th e C o n sta n ts in th e E q u atio n of
R o d e w a ld ," K o l l o i d Z. 7 3 , 3 2 8 - 3 4 (1935)

73, H. S . T a y l o r , "A T r e a t i s e o n P h y s i c a l C h e m i s t r y , "

V o l . I I . S e c o n d E d i t i o n . New Y o r k ( 1 9 3 0 )

74. F . H. N o r t o n , " C r i t i c a l S t u d y - o f t h e D i f f e r e n t i a l
T h e rm a l M ethod f o r t h e I d e n t i f i c a t i o n o f t h e C lay
M i n e r a l s , " J o u r . A m e r . C e r a m . S o c . 2 2 , (.2) 5 4 - 6 3
(1939)

7 5* L, M i t c h e l l , "M in eral and C o llo id a l C o n s t i t u ti o n

o f Some G e o r g i a K a o l i n s , " P h . D . t h e s i s , T h e P e n n s y l ­
v a n i a S t a t e C o l l e g e (1941)

76. G. J . B o u y o u c o s , "A M e t h o d f o r M a k i n g M e c h a n i c a l
A nalyses of th e U ltim a te N a tu ra l S tr u c tu r e of S o i ls ,"
S o i l S c i . 4 0 , 4 8 1 -8 5 (1935)

77. A. C a s a g r a n d e , " T h e H y d r o m e t e r M e t h o d f o r M e c h a n i c a l
A n a ly s is o f S o i l s and o th e r G ra n u la r M a t e r i a l s ,"
M a s s . I n s t . T e c h . , J u n e 1931

78. A. L . J o h n s o n a n d F . II* N o r t o n , " F u n d a m e n t a l S t u d y

of C lay: P r e p a ra tio n of a P u r if ie d K a o lin ite Suspen­
s i o n I , " J o u r . Am er, C e ram , Soc* 2 4 , 6 4 - 6 9 (1 9 4 1 )

79. L . D. B a v e r a n d N. S . H a l l , “ C o l l o i d a l P r o p e r t i e s o f
S o i l O r g a n i c M a t t e r , " R e s . BU11. 2 8 7 , U n i v . Mo. A g .
E x p t . S t a . (1937)
80. W. P . W h i t e , " T h e M o d e r n C a l o r i m e t e r , " M o n o g r a p h .
C h e m i c a l C a t a l o g Company (1 9 2 8 )
H. C . D i c k i n s o n . B u l l * Bur* S t a n d a r d s , 1 1 , 1 9 1 (1915)
C ite d in (73)

M. S . A n d e r s o n , " T h e I n f l u e n c e o f S u b s t i t u t e d C a t i o n s
on t h e P r o p e r t i e s of S o i l C o l l o i d s ,” J o u r . A g r .
R e s e a r c h 3 8 , 5 6 5 - 8 4 ( 1 9 2 9 ) Chem. A b s t . 2 3 , 5 5 3 3 .

W. D» H a r k i n s a n d E w i n g , ” H e a t o f W e t t i n g o f C h a r c o a l
a n d F u l l e r s E a r t h w i t h W a t e r , ” Proc* N a t . Acad* S c i .
6 , 49 (1 9 2 0 )

A l f r e d C l a r k an d B. D. T h om as, " A d s o r p t i o n o n He t e r o -
p o l a r S u r f a c e s , ” J o u r . P h y s . Chem. 4 3 , 579 ( 1 9 3 9 )

L ew is, S q u i r e s , B roughton, " I n d u s t r i a l C h em istry of

C o l l o i d a l a n d A m o r p h o u s M a t e r i a l , ” M a c m i l l a n . New
Y ork (1942)

R . E . W i l s o n , " H u m i d i t y C o n t r o l by Me ans o f S u l f u r i c
A cid S o l u t i o n s , w i t h C r i t i c a l C om pilation o f V apor
P r e s s u r e D a t a , " J o u r , I n d . E n g . Chem. 1 3 , 3 2 6 ( 1 9 2 1 )

S . S p e i l , " E ffe c t, of A dsorbed E l e c t r o l y t e s on P r o p e r ­

t i e s o f M o nodispersed C lay-w ater S y stem s,” J o u r .
A m e r . C e r a m . S o c . .23, 3 3 - 3 8 ( 1 9 4 0 )