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ADSORPTION STUDIES
OS CLAYS
bar
K a r l Cm t e n B r i n k , B* s л I n d u
S л , U* a *
A T h e s is P re s e n te d
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T he R ic e I n e t i t u t e o f H o u s to n , T e x a s ,
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D o c to r o f P h i l o s o p h y
The Rio* Inetitute
1940
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I N T R O D U C T I O N
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R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
In tro d u c tio n
H u a d s o r p t i v e p r o c e s s h a s b e e n s t u d i e d w i d e ly i n
e o l l o i d a l c h e m is try . s a d i t s
a p p l i c a t i o n h a s b e e s v e ry e x te n *
sirs e v e n th o u g h i t i s n o t f u l l y u n d e r s t o o d i n m any e a s e s *
It
now seems t o be g e n e r a l l y s s s s p t s d t h a t a d s o r p t i o n may b e d u e
t o a n y o n e o r a o o a b l a s t i o n o f s e v e r a l d i f f e r e n t m e c h a n ism s*
T he p r o c e s s o f a d s o r p t i o n e v o l v e s h e a t a n d c a n be e l a s s i f l e d
on t h i s
o a s i s a s b e in g s i m i l a r t o c h e m ic a l r e a c t i o n
in v o lv in g
c h e m ic a l f o r c e s o r a s b e in g s i m i l a r t o c o n d e n s a tio n in v o lv in g
van d e r ? a e l* s f o r c e s .
done d i r e c t l y
T he m e a s u r e m e n t o f t h i s h e a t may be
o r by t h e u s e o f " i s o s t e r e s " ? c u r v e s a n a l o g o u s
t o p r e s s u r e t e m p e r a t u r e e q u i l i b r i u m c u r v e s f o r v a p o r s an d
l i q u i d s ? a n d a p p l i c a t i o n o f th e f a m i l i a r C la u a iu s -C la y p c ro n
e q u a tio n *
O th e r g e n e r a l m e th o d s o f s t u d y i n g a d s o r p t i o n a r e t h e
is o th e rm s and is o b a rs *
T he i s o t h e r m s h a v e f o u n d w id e a p p l i e s *
t l o n b e c a u s e o f t h e e a s e o f a p p l y i n g t h i s m e th o d t o a d s o r p t i o n v
b o t h f r o m v a p o r s and f r o m s o l u t i o n s *
C u rv e s o f t h i s t y p e h a v e
l a d t o many i n t e r e s t i n g d i s c o v e r i e s i n t h e a d s o r p t i o n s t u d i e s *
and i t
i s t h i s ty p e o f c u rv e t h a t w i l l be c o n s id e r e d in th e
p r e s e n t work.*
M ost o f t h e w o rk t h a t haw b e e n d o n e o n a d s o r p t i o n
f r o m a t h e o r e t i c a l p o i n t o f v ie w h a s b e e n done o n s y n t h e t i c a l *
l y p r e p a r e d m a t e r i a l s an d t h e i r a d s o r p t io n o f w a te r v a p o r*
a! s o 9
b e c a u s e o f t h e i r w id e a p p l i c a t i o n a s c o m m e r c ia l a d s o r b *
a n t s , c h a r c o a l , s i l i c a , a n d a lu m i n a h a v e b e e n u s e d i n m o s t
e x te n s iv e a d s o rp tio n s tu d ie s *
T he n a t u r a l c l a y s * h o w e v e r*
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
! ?
lu m
been v id tljr a M d in m e a n t y e a rs u
d s e o l o r i s a t i o n o f o i l s o f a i l ty p e s *
a d s o rb e n ts f o r th e
F o r th e m ost p a r t t h i s
w o rk b e e b e e n p r i m a r i l y e o n e e rn e A w i t h t b s t e s t i n g a n d e n l a a *
t i o n o f n a t u r a l e l a y s f o r th e d e c o l o r i z a t io n o f o i l s a n d r e *
m o r a l o f g tm f o r m i n g m a t e r i a l s f r o m l u b r i c a t i n g o i l s *
c a l tre a tm e n t o f c la y s f o r th e
is
C hem iн
im p ro v e m e n t o f t h i s p r o p e r t y
fo u n d w id e ly i n t h e p a t e n t l i t e r a t u r e *
V e ry r e c e n t l y e l a y s h a r e f o u n d f u r t h e r u s e i n t h e
p e tro le u m r e f i n i n g
in d u s try as c a ta ly s ts in th e c a ta ly tic
c ra c k in g p ro c e s s f o r th e p r e p a r a tio n o f h ig h t e s t g a s o lin e s *
T h is c a t a l y t i c a c t i v i t y o f e la y s i s a ls o
th e i r a d s o rp tlre q u a litie s *
c lo s e l y a l l i e d w ith
Due t o t h e s e f a c t s ,
it
i s e v iн
d e n t t h a t a s tu d y o f th e e d s o r p tir e p r o p e r tie s o f e la y s o f
d i f f e r e n t t y p e s m ig h t b e o f h e l p i n t h e p r e p a r a t i o n o f m ore
e f f i c i e n t m a t e r i a l s f o r b o th d e c o l o r iz a t l o n a n d c a t a l y t i c
c ra c k in g *
am
h a s b e en p o in te d o u t, th e p ro c e s s o f a d s o rp tio n
may b e d i v i d e d i n t o
tw o c l a s s e s *
i n t h e p r o c e s s o f o h e m ie a l
a d s o r p t i o n , t h e b i n d i n g f a r e a s b e tw e e n t h e m o l e c u l e s o f t h e
a d s o r b e n t a n d t h e a d s o r b a t e a r e c o m p a r a b le t o t h e f o r e e s
w i t h i n th e m o le c u le s a n d h e n c e th e p r o c e s s i s
re v e rs ib le *
in g e n e ra l i r н
On t h e o t h e r h e a d , i n t h e e a s e o f p h y s i c a l o r
v an d e r ? a a l a d s o r p tio n , th e f o r e e s a re c o a p a ra b le to
th e
f o r c e s b e tw e e n m o l e c u l e s i n a l i q u i d o r h o a o p o l a r s o l i d *
T h is p r o c e s s i s r e v e r s i b l e *
C a lc u la tio n s in d ic a te t h a t th e
v a n d e r s e a l f o r c e s a r e su e h t h a t s u r f a c e c o n d e n s a tio n d e e s
n o t ta k e p la c e t o a n a p p re c ia b le e x te n t e x e e p t a t v a lu e s
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
8*
& ллr s a t u r a t i o n v a p o r p r e s s u r e *
H o w e v e r, a p p r e c i a b l e a d s o r p *
t l o n o f M a t e r i a l s n o t l i k e l y t o f a r m s u r f a c e com pounds h a s
b e en fo u n d ev en a t v e ry lo v p e rc e n ta g e s o f s a t u r a t io n p r e s *
s u r e a n d a n o t h e r e x p l a n a t i o n h a s b e e n f o r t h c o m in g *
I t is
w e l l know n t h a t t h e v a p o r p r e s s u r e a b o v e a l i q u i d i n a
c a p i l l a r y i s l e s s th a n th e n o rm al v a p o r p r e s s u r e above a
p la n e l i q u i d s u rfa c e *
T he q u a n t i t a t i v e s t a t e m e n t o f t h i s
f a c t i s t h e K e lv in e q u a tio n s
w h e re p a n d p* a r e t h e n o r m a l a n d c a p i l l a r y v a p o r p r e s s u r e s ,
<y is
t h e s u r f a c e t e n s i o n , T i s t h e v o lu m e o f l i q u i d , r i s
th e r a d i u s o f th e c a p illa r y *
I f one assu m es t h a t th e s u r f a c e
o f t h e a d s o r b e n t c o n s i s t s o f many v e r y f i n e c a p i l l a r i e s , i t
is
c l e a r t h a t t h e " s a t u r a t i o n v a p o r p r e s s u r e " may t a k e o n a s e r i e s
o f v a l u e s d e p e n d in g on t h o s e c a p i l l a r y
s iz e s *
T h is w o u ld e x *
p l a i n , t h e n , t h e v a n d e r V e a l a d s o r p t i o n t o t h e v e r y lo w p r e s *
su re s*
T h is e x p la n a tio n i s n o t s u i t a b l e , h o w e v e r, a s a g e n e r a l
e x p la n a tio n o f p h y s ic a l a d s o r p tio n b e c a u se c a l c u l a t i o n s fro m
t h e a b o v e e q u a tio n r e v e a l t h a t th e p o s t u l a t e d p o r e s m u st o f t e n
b e o f m o l e c u l a r s i z e s , i n many e a s e s l e s s t h a n t h a t o f t h e a d *
s o r b e d m o le c u le s *
U s o ,s im p le r e l a t i o n s h i p s o f t h i s ty p e can *
n o t b e e x p e c t e d t o h o l d f o r c a l c u l a t i o n s down a s l o v a s a to m ic
d im e n s i o n s *
I n a n y e v e n t , t h e e x p l a n a t i o n may s t i l l b e u s e *
f u l in a q u a lita tiv e sense*
O th e r f a c t o r s s u c h a s t h e s p e c i f i c
n a tu r e o f th e a d s o r b a n t w ith r e l a t i o n t o th e a d s o rb a te s n s t
a l s o b e t a k e n i n t o a c c o u n t w i t h t h e e x tr e m e e a s e b e i n g t h a t o f
c h e m ic a l a d s o r p tio n *
The a d s o r p tio n o f h y d ro c a rb o n v a p o re
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
4*
by ? la y
лu
n
t o ba a n w i l b l t p r o a e s s by m oat o f th a e x н
p e r i m e n t a l e v i d e n c e a n d m ig h t b a te r m e d p h y s i c a l a d s o r p t i o n ,
b u t t h a a a t i o n o f a l a y a a a w r a c k in g a a t a l y a t a m ig h t I n d i a n t a
t h a t t h a p ro e a a s in v o lv e s th a a o ra in ta n a a m o le c u la r f o r c e s *
I t la a g e n e ra l p r a e tic a to e x p re ss a d s o rp tio n a s
t h a w e ig h t o f n a t a r l a l a d s o r b a d , X , p a r u n i t w e ig h t o f a d s o rb н
i n g m a t e r i a l , M, a n d t h e a d s o r p t i o n i s o t h e r m s f o r v a p o r s may
* /y \ -
ba w rit ta n
th e fu n c tio n
?
Q u a n tita tiv e r e la tio n s h ip s f a r
-f C ?) h a v e b e a n f o r m u l a t e d s u c h a s t h e F r e u n d l i c h
e q u a tio n
-
K p /w
s h a re X and n a r e e m p ir ic a l conн
s ta n ts *
un t h e a s s u m p t io n o f o o n o a o l e c u l a r s u r f a c e l a y e r s ,
L a n g m u ir
(2 3 ) d e r iv e d th e e x p r e s s io n
*/г* ~ ? X
*
The
c o n s t a n t s a r e a g a in e m p ir ic a l and n e i t h e r e q u a tio n c a n a c c o u n t
f o r m any o f t h e m ore c o m p l i c a t e d a d s o r p t i o n i s o t h e r m s v h i c h
shoe
th e e f f e c t o f v a ry in g c a p i l l a r y s iz e s and v a r io u s ty p e s
o f " a c tiv e c e n te rs " *
T ha f o r m a t i o n o f t h a optim um , s i z e p o r e s o r t h e c r e н
a t i o n o f t h a c o r r e c t a c t i v e e e n t e r s se e m s t o b e t h e p r o b le m
in v o lv e d in th a a c t i v a t i o n o f e la y s f o r d e c o l o r iz a t i o n an d
? a ta ly a is *
T ha g e n e r a l t r e a t m e n t o f e l a y s i s a p r o c e s s o f
? a i d b o i l i n g i n w h ic h a l u m i n a , i r o n , a n d m o s t o f t h e b a s e s
e r a l a a a h a d o u t*
T ha e x p l a n a t i o n o f t h a a c t i v a t i o n b y t h i s
t r e a t m e n t i s t h a t by l e a s h i ng o u t A l^ O ^
a r e m ada i n t h e c l a y s t r u c t u r e *
and i r o n , p o re s
A ls o , re m o v a l o f t h a b a s e s
a n d t h e i r r e p l a c e m e n t b y h y d r o g e n g i v e s -OH g r o u p s o n a d J a a a n t s i a to m s w h ic h o n s p l i t t i n g
o u t w a te r g iv e s t r a i n s
in th a s i l i c a s t r u c tu r e , th u s c re a tin g a c tiv e a a n ta rs *
Much w o rk a p p e a r s i n t h e p a t e n t l i t e r a t u r e o n t h e
i
i
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
9.
a c t i v a t i o n o r c la y s ca a d s o rb e n ts *
By f a r t b c a o a t w i d e ly
u s e d a n d s e e m i n g ly a o a t c r f a e t l v e a a a n s o f a c t i v a t i o n h a s
b een tb c p ro e e sa o f a c id b o ilin g *
T h ere a r e s e v e r a l p a te n ts
w h ic h c o n s i s t o f t h e s i a p i s b o i l i n g o f c l a y s i n HC1 o r Ha SO^.
o f v a ry in g c o n c e n tr a tio n s and f a r v a r io u s le n g th s o f t i n s *
(5 )
(4 )
(S )
(7 )
(1 7 )
( I B ) (S B ) ( 3 0 ) *
T hese p a te n ts in d ic a te
t h a t th a o p tio n s c o n c e n tr a tio n and le n g th o f tre a tm e n t I s la r g e *
l y d e p e n d e n t on th a ty p e o f c la y and th a n a tu r e o f th e a d so rp *
t i o n w o rk f o r w h ic h t h e c l a y l a t o b e u s e d *
I n g e n e r a l , how*
e v e r , a c id c o n c e n tr a ti o n s o f 5 t o S0г and t r e a t i n g
th re e
to e ig h t h o u rs a r e used*
v ig o ro u s a e id tre a tm e n t*
T ie tig
tim e s o f
( 3 o ) u s e d a m ore
H i s m e th o d i n v o l v e s t h e b u r n i n g o f
E t a n d C l z i n t h e p r e s e n c e o f w a t e r v a p o r o v e r t h e c la y *
N u ttin g
(2 7 )
( 2 8 ) p o i n t s o u t t h a t m any e l a y s a r e p a r t i a l l y
le a c h e d i n n a tu r e by th a a c t i o n o f n a t u r a l l y o c c u rin g a c id s *
When a n a t t e m p t l a m ade t o a c t i v a t e
t h e s e c l a y s by a e i d b o i l *
l n g , a n e x c e s s l e a c h i n g t a k e s p l a c e t f i i o h se em s t o d e s t r o y
t h e p o r o s i t y o f t h e c l a y o r m ake p o r e s s o l a r g e t h a t t h e y a r e
n o t v e ry a c t i v e i n a d a o rp tio n *
S c k a r t (1 0 )*
T h i s I s a l s o r e c o g n i z e d by
T ha p r e v i o u a a d d i t i o n o f s t r o n g l y a d s o r b e d c a *
t i o n a s u c h a s A l* * * , P e * * * , o r Mg'** se e m s t o p l u g t h e n a t u r a l *
l y fo rm ed p o r e s an d s l o w
down l e a c h i n g a t t h o s e s p o t s d u r i n g
a c i d b o i l i n g , g i v i n g a r e s u l t a n t a d s o r b e n t w h ic h h a s b e e n
u n i f o r m l y e t c h e d a n d w h ic h i s g r e a t l y
im p ro v e d *
h a s a ls o b een re v e a le d in th a p a te n t l i t e r a t u r e
T h is p r o e e s a
(9 6 )*
I t h a s b e e n p a i n t e d o a t I n o n e w o rk ( S ) t h a t t h e
a d a o rp tio n p r o p e r t i e s o f e la y e i s d e p en d e n t on ( l )
th e am ount
o f s i l i c a t e s c a p a bl e o f b e in g c o n v e rte d by a c t i v a t i o n t o h y *
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
d ra te d s ilic a
I n t h a g e l f o r s , a n d (B ) t h a h y d r a t e d s i l i c a
c o n te n t o f th a n a t u r a l e la y *
I t la fu rth e r a ta ta d th a t a l╗
? o a t e v e r y a a a a o f m o t i v a t i o n o f e l a y a l a t h a a ante h a e a n a a
I t t a k a s a d v a n ta g e o f t h a s a f a c t a *
ix a a p le a o f a c t iv a t io n
by B a a a a o t h e r t h a n a e i d b o i l i n g a a a a t o b e a r t h l a o a t *
F e l i z a t ( 1 3 ) a c t i v e t e a e l a y f o r a d a o r p t i o n w o rk by t r e a t i n g
I t w ith a n a l k a l i m e ta l s i l i c a t e
a n d t h a n a d d in g e n o u g h
a e id to n e u tra lis e
f o r m in g a e l a y w i t h a l l i e a
th e s i l i c a t e ,
e lo a a ly a a a o e la te d w ith i t*
? a o d lf le a tio n o f t h l a p ro c e d u re
i n w h ic h t h a e l a y a n d a i l i e a t e m i x t u r e l a b o i l e d d u r i n g t h e
a d d itio n o f a e id h a s a la o been re v e a le d
(3 2 }*
o t h e r m e th o d s
o f e l a y a c t i v a t i o n se e m t o b e m e r e l y t h e p u r i f i c a t i o n o f
n a t u r a l l y a c t i v e c l a y s b y v a r i o u s m e th o d s*
( 1 1 ) a c t i v a t e c l a y b y a d d i n g CC^
E n d e ll an d O at
to a s lu r r y and th e n
e l e c t r o d i a l y s i n g t o re m o v e t h e e l e c t r o l y t e s a d s o r b e d *
s i m p le
e le c tr o d ia ly s is or e le e t r o f U t r a t l o n h a s a ls o been u sed
From. t h e s c a n t w o rk r e p o r t e d i n t h e l i t e r a t u r e
(2 9 )*
on
th e a c t iv a tio n o f c la y s by d e h y d ra tio n , i t a p p e a rs t h a t t h i s
p r o c e d u r e i s s o m e tim e s e f f e c t i v e
in g o n t h e c la y *
^ le x a n la n
a n d s o m e tim e s n o t , d e p e n d н
( 1 ) , C e r l s o h n ( 3 ) , a n d K au ffm an
( 1 9 ) c l a i m e l a y a c t i v a t i o n by d e h y d r a t i o n , a n d Z u b l i n ( 3 6 )
c la im s to f u r t h e r
a c t i v a t e a c i d t r e a t e d c la y by tr e a tm e n t
w i t h s u p e r h e a t e d s te a m i n o r d e r t o d r i v e o f f a l l w a t e r w i t h н
o u t r e m o v in g t h e w a t e r o f h y d r a t i o n s
S c k a rt re p o rta th a t th e re
On t h e o t h e r h e a d ,
I s n o r e l a t i o n b e tw e e n d e c o l o r i s н
in g a c t i o n o f a e la y and i t s l o s s o f w a te r on h e a tin g *
o u sw a ry o f O b je c tiv e s
T he o b j e c t o f t h e p r e s e n t w o rk h a s b e a n t o s t u d y
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
tl╗
a d s o r p tio n o f h y d ro e a rb o n v a p o rs o n v a r io u s ty p e s o f
d a y s , and to lo a m
fro m t h i s a d a o r p tio n s tu d y th a r e l a t i v e
im p o rta n c e o f v a r i o u s f e s t e r s , b o th c h e m ic a l a n d p h y s i c a l ,
w h io h d e t e r m i n e t h e a d a o r p t i v a phenom ena ?
T h a i n i t i a l w o rk w as d e s i g n s * t o l a a r n t h e r e l a t i v e
m a g n itu d e a n d f l e x i b i l i t y o f a d a o r p t i o n d u o t o t h e f o l l o w i n g
fa s to rs t
(1 )
T he a t o n l s e t r u e t u r e o f t h a m i n e r a l g r a i n *
(8 )
T he d e g r e e o f d i s p e r s i o n o f t h a s l a y g r a i n s ,
and th e r e l a t i v e
im p o r ta n c e o f t h e e x t e r n a l
su rfa c e s*
(3 )
T he r e l a t i v e
im p o r ta n c e o f t h e s p a c i n g o f
s e c o n d a r y a g g r e g a t e s , 1* e * , s p a c e s b e tw e e n
th e d a y g r a in s *
(4 )
T he e f f e c t o f e x c h a n g e a b le i o n s w i t h i n t h e
c la y g ra in s *
(5 )
T he e f f e c t o f i n t r a p a r t i c l e s p a c e s , o r c h a n *
n e l s o f n e a r m o le c u la r s i x e s i n th e p rim a ry
g ra in s tru c tu re *
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
E X P E R I M E N T A L
P-.HT
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
Adsorption M u v n u t c h s n teta made in many dif*
f e r e n t n y i , and th a la h s r a n t e r r o r s and l i m i t a t i o n s o f th s
s e v e r a l m e th o d s h a v e b e e n d i s c u s s e d b y M eB ain ( 8 4 ) *
M e B a in 's
im p ro v e d m e th o d o f a d s o r p t i o n s t u d y i a c o n v e n i e n t l y a p p l i e d
t o is o t h e r m . w o r k , b u t i n o r d e r t o g a i n a c c u r a c y i n m e a s u r e н
m e n t s , t h e q u a r t s f i b e r s o u s t b e made v e r y d e l i c a t e a n d h e n c e
t h e s i z e o f s a m p le s m u s t b e v e r y s m a ll*
re a liz in g
C h a m b e rs a n d Z in g ( 9 )
t h e d i f f i c u l t i e s o f u s i n g s m a l l s a m p le s a n d d e s i r н
i n g g r e a t e r a c c u r a c y h a v e d e s i g n e d a new a d s o r p t i o n b a l a n c e d
i n w h ic h t h e q u a r t z s p r i n g i a s u b s t i t u t e d by a f l o a t
(s im iн
l a r t o a h y d r o m e t e r ) s u s p e n d e d i n m e rc u ry *
f.'ith t h i s e q u i p н
m e n t , t h e a c c u r a c y o f t h e M eB ain b a l a n c e i s
t r i p l e d u s in g
s a m p le s a s l a r g e a s s i x g ra m s *
I n t h e p r e s e n t w o r k i t w as d e s i r e d t h a t s a m p le s o f
f o u r t o s i x g ra m s b e u s e d s o t h a t d i e a m o u n t o f a d s o r p t i o n
w o u ld be m e a s u r a b le *
H o w e v e r, a c c u r a c y a s g r e a t a s 1 p a r t
i n 8 0 ,0 0 0 w as n o t c o n s i d e r e d n e c e s s a r y s o t h a t t h e Z in g
m e th o d w as n o t u se d *
m at i c a l l y
in fig u re
T he a p p a r a t u s u s e d i s sh e w n d i a g r a m (1 )*
M sB eIn?T a n n e r b a l a n c e
a W e s tp h a l b a la n c e *
I t i s s im ila r in p r i n c i p l e t o th e
(2 4 )*
T he b a l a n c e p a r t w a s m ade from ,
The z e r o p o i n t w as o b ta in e d by p a s s in g
a c u r r e n t t h r o u g h t h e s o l e n o i d w h ic h a c t s on t h e
m a n e n t m a g n e t*
p e rн
The e l e c t r o m a g n e t i a c a l i b r a t e d a g a i n s t a
s t a n d ar d w e ig h t b e f o r e and a f t e r e a c h r u n i n o r d e r t o d e t e r н
m in e t h e v o l t a g e p e r g ram *
S in c e f a i r l y h ig h v o l ta g e s e r e
u s e d i n sam e e a s e s , t h e e l e c t r o m a g n e t i s t a p p e d f o r a fe w
t u r n s an d th s v o lta g e m e a su re d f o r th e s e t u r n s w ith a
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
p o tta tiflM tir*
It л u
v a r i e s v e ry l i t t l e
fo u n d t i n t t i n
w e ig h t
o v e r a p e r i o d o f t im e an d t h e v a r i a t i o n
w ith w e ig h t l a p r & e t le a ll y n e g l i g i b l e *
H o w e v e r, t h e c a l i b r e -
t l o n e w e re a lw a y s m ade o v e r t h e sam e w e ig h t r a n g e a s t h a t u e e d
i n th e a c t u a l e x p e rim e n t*
T he p r o c e d u r e f o r a n i e o t h e r m r a n l a a e f o l l o w s :
1
c o n v e n ie n tly
l a r g e s a m p le l a p l a c e d I n t h e s a m p le b u c k e t
a n d w e t w i t h t h e l i q u i d w hose v a p o r s a r e t o be a b s o r b e d
d e so rb e d )*
* lth fiv e
i n th e s y s te m , i t
e v a p o ra te *
(o r
to t e n c u b ic c e n tim e te r s o f th e l i q u i d
i s e v a c u a te d and th e l i q u i d
i s a llo w e d t o
T h is w a s h e s t h e s y s t e m f r e e o f a i r a n d i e e v e s
o n ly th e v a p o rs *
T he t u b e c o n t a i n i n g t h e s a m p le i s lo w e r e d
i n t o a c o n s t a n t t e m p e r a t u r e b a t h a n d i s a ll o w e d t o com e t o
e q u i l i b r i u m , t h e tim e r e q u i r e d u s u a l l y b e i n g o n e t o
h o u rs*
fo u r
In ru n n in g a d e s o r p tio n Is o th e rm th e p r e s s u r e i s
lo w e r e d I n s t e p s a n d t h e c o r r e s p o n d i n g w e i g h t i s o b s e r v e d
fro m th e p o te n tio m e te r a s o u t l i n e d above*
in o r d e r to fo llo w
t h e a d s o r p t i o n o f t h e v a p o r s , t h e s y s t e m i s e v a c u a t e d a s m uch
a s p o s s i b l e a n d s m a l l a m o u n ts o f l i q u i d a r e a d m i t t e d f r o m t h e
v a eu u m s i d e o f t h e a p p a r a t u s , t h e p r e s s u r e r i s i n g
ifte r
in s te p s *
th e is o th e r m h a s b e e n r u n , th e a b s o lu te am ount o f m a te r iн
a l a d s o r b e d o u s t b e d e te r m i n e d *
T h is i s done b y e v a c u a tin g
t h e e y a te m a s muc h a s p o s s i b l e a n d a t t h e sam e t i m e h e a t i n g
t h s s a m p le I n a n o i l b a t h t o 1 0 0 - 1 7 0 ░ C*
T he v o l t a g e r e a d i n g
t a k e n a t t h i s tim e i s a s s u m e d t o b e t h e r e a d i n g f o r t h e s a m p le
w ith no a d s o r p tio n , s in c e i t
h a s c e a s e d l o s i n g w e i g h t*
i s t a k e n o n l y a f t e r t h e s a m p le
H e n ce , t h e w e ig h t o f m a t e r i a l a d н
s o rb e d a t an y g iv e n p r e s s u r e w i l l b e re p re s e n te d by th e d l f -
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
10*
f i r t o t t b i t i H a th e T e l t a p re a d in g a t t h a t p r e s s o r s so d th a
l a s t m e n tio n e d v o l ta g e r e a d in g *
n s
a a th o d o sn b e s t b s d e a o a *
s t r a t e d b y a t a b l e o f d a t a f a r a t y p i c a l d e s o r p t i o n is o th e rm *
(s e e T a b le I * )
T n ~ * itin
v f " 1?
? " * f f n t i f t t w r *? ? ? ?л
Za a o e t o f th a f o llo w in g e x p e rim e n ts , benzene
T s p o r a a t 9 0 ░ C w a re n e e d *
B enzene w as e h o se n b e c a u s e i t
p ro b a b ly th e m o st to n e s lo n e ly a d so rb e d o f th e lo v
ie
Itr
w e i g h t u n s a t u r a t e d co m p o u n d s w h o se n o l s e u l a r d i m e n s i o n s a r e
a c c u r a t e l y know n*
p e lle ts *
i l l t h e e l a y s a m p le s w e re i n t h e f o r m o f
T h e s e w e r e fo r m e d b y m a k in g a t h i c k p a s t e , e x t r u d н
in g t h i s p a s t e th r o u g h a a m i l tu b e a n d d r y in g th e r e s u l t a n t
c y li n d e r s o f c la y *
^*
Wyoming B e n t o n i t e w a s e h o s e n a s a t y p i c a l b a s e
s a t u r a t e d m o n tm o r illo n ite ty p e c la y *
th s n a tu r a l c la y
T hs h i g h pH ***Talus o f
in d ic a te s t h a t i t h a s n o t re c e iv e d su ch a e id
le a c h in g in n a tu r e
00
le a s h e d b e n to n ite *
i t n i g h t b e a g o o d e x a m p le o f a n u n н
T h e s a m p le u s e d i n t h i s e x p e r ix a e n t h a d b e e s
s w e l l e d i n w a t e r f o r s e v e r a l m o n th s , a n d t h e n e l e c t r o d i a l y s e d
t o re m o ra a l l t h s a x o n a n g s a b le b a s e s an d any n a t u r a l l y o c c u r in g
o
s a l t s w h ic h m i g h t b e a d s o r b e d * T h i s m a t e r i e l w as d r i e d i t 1 1 0
C*
T h s d e s o r p t i o n i s o t h e r m i s sh o w n i n f i g u r e
n o te d , th s c u rv e
(г } ?
a s w i l l be
i s v a r y f l a t u n t i l th s p r e s s u r e becom es l e s s
t h a n 109( e f t h s s a t u r a t e d v a p o r p r e s s u r e
a t w h ic h p o i n t t h e r e
(1 1 8 am* Hg a t 3 0 ░ C)
i s a s h a r p b r e a k t o th e z e r o v a lu e *
T h is
c u r v e i s t y p i c a l o f t h s F r e u n d l i c h o r L an g m u ir a d s o r p t i o n
c u r v e , a n d m i g h t i n d i c a t e t h a t t h e r e a r e r e l a t i v e l y fe w p o r e s p r e н
s e n t f o r c a p i l l a r y c o n d e n s a tio n o r i n t e n s e l y a c t i v e s p o ts
w h i c h
m i g h t
b e
r e s p o n s i b l e
1
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
11*
fo r t
o v r t o w ith , b r t t k i i a I t *
г?
P u r e w a sh e d k a o l i n a n a u s e d no o n e x a m p le o f a n o t h e r
fu n d a m e n ta l ty p o o f e la y s t r u c t u r e ?
Two s a m p le s o f t h i s a n *
o
t e r i a l w o re p r e p a r e d , o n e b e i n g h o o t e d a t 1 1 0 C t o re m o v e a d *
o
a o r b o d w a t e r a n d t h e o t h e r b e i n g h e a t e d a t 4 5 0 C t o re m o v e
th e " c r y s t a l w a te r"
i a fig u re
(2 ) ?
(SO )*
T he r e s u l t a n t i s o t h e r m s a r e a l s o
I t i s s e e a t h a t th e a d s o r p tio n i s v e ry s m a ll
i a t h i s e a s e u n t i l th e s a t u r a t i o n v a p o r p r e s s u r e i s a p p ro a c h e d *
B o th t h e k a o l i n s a m p le s a r e p r a c t i c a l l y
t h e sam e w n ea i t
is
n o t e d t h a t t h e d i f f e r e n c e s b e tw e e n th e m a r e v e r y s m a l l a n d may
be due to e x p e r im e n ta l e r r o r *
T he s h a r p r i s e
a t th e h ig h e r v a p o r p r e s s u r e s i s p ro b a b ly
th e p re se n c e c f f a i r l y
in th e s e c u rv e s
due e i t h e r
(1 } t o
l a r g e p o r e s e t c h e d i n t h e c l a y by n a t u r e ,
o r ( 2 ) t o som e e x t e n s i v e s p a c i n g b e tw e e n t h e p r i m a r y g r a i n s i n
th e s e c o n d a ry a g g re g a te *
I h i s f i r s t id e a i s c o n s is te n t w ith
t h e f a c t t h a t t h e n a t u r a l k a o l i n u s e d h a s a pH * v a l u e c o n s t *
d e r a b l y b e lo w s e v e n *
г?
a s a m p le
p e r i m e n t a w h ic h f o l l o w
a d s o rp tiv e q u a litie s *
o f T e x a s c l a y u s e d i n m o st o f t h e e x *
w as f o u n d t o h a v e q u i t e d i f f e r e n t
T he b u l k o f t h e n a t u r a l c l a y
m o n t m o r i l l o n i t s t y p e a s sh o w n b y X * ra d lo g ra m s *
i s o f th e
T he x ?r a y p a t *
t e r n f o r t h e e l a y a s r e c e i v e d sh o w s i m p u r i t i e s o f l a r g e p r i н
m a ry p a r t i c l e
s iz e s *
T h is i s a l s o n o t e d a n m i c r o s c o p i c
e x a m in a t io n *
In o rd e r to s tu d y th e c o ll o i d a l f r a c t io n and
h e n c e * t h e a l m o s t p u r e m o m t m s r i i l o n i t e p a r t o f t h i s c la y * a
l a r g e p o r t i o n o f i t w as d i s p e r s e d i n SaQH s o l u t i o n a n d a l l o w e d
t o s w e ll f o r s e v e r a l d ay s*
T h is s u s p e n s io n w as 3 9 г s o l i d s by
w e i g h t a n d h a d a pH * o f 1 0 * 5 *
Two l i t e r s o f t h e s u s p e n s i o n
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
w as d i l u t e d t o f i r e g a l l o n s and t h e o e e re e n o t a r i a l s e t t l e d
o u t a th e s u p e r n a t a n t s u s p e n s io n b e in g s u p e r - c e n t r l f u g e d ?
I - r e y p i c t u r e s o n t h e c o l l o i d a l f r a c t i o n show t h e
m o n ta o rlllo n ite p a tte rn *
t^ p le & l
The s u p e r - c e n tr if u g e d m a t e r i a l v a s
w a sh e d s a v e r e l t i n e s w i t h c o n c e n t r a t e d HE^QH i n o r d e r t o r e н
p l a c e m o st o f t h e a d s o r b e d m a t e r i a l s *
I t v as th e n d r ie d a t
o
1 5 0 C t o r e s t o r e a n y r e s i d u a l a n a e m ia l e a v i n g t h e p u r e a e i d
c la y *
A d e s o r p t i o n i s o t h e r m w as r u n o n t h i s m a t e r i a l *
c u rv e is sh o rn in f ig u r e
end u n lik e
(2)*
t h e Wyoming b e n t o n i t e , i t
f a m i li a r a d s o r p tio n is o th e rm s *
th is
T h is c u rv e i s r e l a t i v e l y
The
h ig h ,
i s n o t t y p i c a l o f th e
T he b r e a k s w h ic h o c c u r i n
c u rv e a p p e e r a t a p r e s s u r e w h ic h i s c o n s i s t e n t w i t h t h e
t h e o r y t h a t v e r y e m a i l c a p t i l e r i e s may b e fo rm e d w i t h i n t h e
p rim a ry g r a i n s by a c id le a c h in g o f th e c la y
in n a tu re *
A ls o ,
th e a c i d i t y o f th e n a tu r a l e la y i s f u r t h e r c o n firm a tio n
th is
f
id e a *
T he r e s u l t s o f t h e s e d a t a i n d i c a t e
d iffe re n c e
of p a r tic le
th ╗ t th e v id e
s i z e s and t h e fu n d a m e n ta l d i f f e r e n c e s
i n t h e c l a y t y p e s a r e m in o r f a c t o r s i n t h e a d s o r p t i v e p h e n o н
m ena*
i s a f i r s t ch eek on th e fo re g o in g i n t e r p r e t a t i o n
o f t h e a d s o r p t io n pow er o f n a t u r a l e l a y s , p u r e ly p h y s i c a l
m e a n s o f s p a c i n g t h e n a t u r a l e l a y g r a i n s w e re t r i e d
in o rd e r
t o d i s t i n g u i s h c a p i l l a r y a d s o r p t i o n i n c lu m p s o f g r a i n s f r o m
o t h e r a d s o r p t i v e p h e n o aw n a *
4*
K is tle r
(2 1 ) h a s p o in te d o u t t h a t o r d in a r y hyн
d r o g e ls c a n b e d e h y d ra te d w ith o u t a n y s h r in k in g i f
h y d r a tio n ta k e s p la c e abov e th e c r i t i c a l p o in t*
th e deн
I n m any
i n s t a nce s l i q u i d s o f lo w e r e r i t l e a l c o n s t a n t s t h a n w a t e r c a n
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
is *
b e substituted f o r the w a t e r i a a g a l e n d r e l e a s e o f t h i s
l i q u i d a l s o f o rm s a n u n s h r u n k " a e r o g e l * *
X l s t l e r *s a e r o g e l s
h a r e a v e r y lo w d e n s i t y a n d c o n s e q u e n t l y m u s t h a v e a v e r y
h ig h p o r o s ity *
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IT .
f o r t i l t a e id b o i li n g i o t t n o te
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t o th e c o n c e p ts o f c o l l o i d c h e m is tr y .
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The d e s o r p t i o n
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It*
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e x e e e s w ee a d d e d b e f o r e f i l t e r i n g *
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I
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m e f i r s t s t u d i e s o f a d e p o s i t o f S iO t o n t h e
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o r d e r t o s tu d y t h i s
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ta tio n *
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e l e c t r o d i a l y s e d f r e e o f a l l r e m a in i n g e l e c t r o l y t e s *
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b u t w as n o t f i l t e r e d *
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am o u n t a u e h t h a t 1 0 г o f t h e w e i g h t o f t h e c l a y w as ^ 1 C Z *
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IKTLE PHET*.? IC K OF RESULTS
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SUMMARY
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Inta╗nrлtatlon of HcKilfi
As w as s t a t e d i n t b s i n t r o d u c t i o n , th e o b j e c t o f
t h i s r e s e a r c h w as t o
s tu d y f a e t o r s g o v e rn in g th s a d s o r p tlo a
o f b en zen e v a p o r on s l a y s , s a d by t h i s a d s o r p tio n t o s tu d y
t h s o f f s e t o f c h e m ic a l and p h y s io s ! t r e a t m e n t s on c la y s *
Tbs
e x p e r i m e n t s show t h a t t h s a d s o r p t i o n o f b e n z e n e v a r i e s w i d e ly
w ith th e ty p e o f c la y s t r u c t u r e , th e ^ a o l i n i t e
in g o uch l e s s
th a n th e l o n t m o r i l i o n i t e ty p e *
e x p la in e d by th e f a c t t h a t i n lo n tm a r i l l o n i t e
ao x e s u r f a c e o f th e s i l i c a
c la y s *
ty p e a d so rb *
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is
th e re fo re a v a ila b le *
in
a n o t h e r i n t e r e s t i n g r e s u l t , w h ic h i s
a g re e m e n t w ith p r e v io u s e x p e r l o e n t e r s , i s
i n g t h e cam e s t r u c t u r e
te ris tic s .
th a t c la y s e x h ib it*
do n o t h a v e t h e sem e a d s o r p t i o n c h a r a c *
F o r e x a m p le , t h e Wyoming b e n t o n i t e & ud T e x a s b e n *
t o n i t e h a v in g i d e n t i c a l X * ra y p a t t e r n s h t.v e d i f f e r e n t a d s o r p t i o n
p r o p e r t i e s i n b e n z e n e v a p o r*
,-s p o i n t e d o u t i n t h e d e s c r i p t i o n
o f th e e x p e rim e n ts , th e g e o lo g ic a l h i s t o r y
o f th e T exas e la y
I s s u c h t h a t t h i s s t a t e r i a l h a s r e c e i v e d m uch n a t u r a l w e a t h e r *
in g and l e a c h i n g , an d h e n c e , f in e
c a p i l l a r i e s h a v e b e e n f a rm e d
b y t h e r e m o v a l o f a lu m i n a f r o m t h s s t r u c t u r e ?
p r e s e n t a l a r g e a r e a f o r a d s o r p tio n , and a ls o
T hese p o re s
o f f e r th e poo*
s i b i l l t y o f c a p i l l a r y c o n d e n s a t i o n w h ic h w a s d i s c u s s e d i n
a n o th e r p a r t o f t h i s p a p e r*
T hs c h a r a c t e r i s t i c b r e a k s i n t h e
a d s o r p t i o n i s o t h e r m s p o i n t s t r o n g l y to w a r d t h i s l a t t e r
id e a *
T h e fy o m in g b e n t o n i t e , u n l e a s h e d b y n a t u r e , g i v e s a n i s o t h e r m
t y p i c a l o f t h e F r e u n d lie h o r la n g m u ir ty p e *
n i l s ty p e c u rv e
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i s e x p la in e d o n t b s b a s i s o f m o le c u la r l a y e r s o a t h s a d s o r b e n t
su rfse a .
s i a s s t h i s c u rv e h a s v a ry le v T a llie s , i t
i s re a so n *
a b l e t o a s s u n s t h a t t h i s s i m p le e x p l a n a t i o n b a s e d o n a u n i f o r m
i
s u rfa e e i s n o t b ro a d enough to e x p la in a l l th e r e s u lts *
a s s u m in g s u r f a c e s o f d i f f e r e n t a c t i v i t y ,
By
th s i n f l e c t i o n p o in ts
c o u ld he a c c o u n te d f o r o a th e b a s i s o f t h s
th e o ry ,
b u t th e l i n e s v h ie h a r e s t e e p i n th e r e g i o n a p p ro a c h in g s e t u r a *
t i o n v ap o r p re s s u re s t i l l r e q u ir e an e x p la n a tio n su ch a s c a p il*
l a r y c o n d e n s a tio n *
T he c l e a n i n g o f c l a y s u r f a c e s b y w a s h in g o r e l s e t r o *
d i a l y s l n g re m o v e s s t r o n g l y a d s o r b e d i o n s l e a v i n g t h e a c t i v e
s p o ts fre e
to a d s o rb b e n sen e v a p o rs*
H o w e v e r, t h i s e f f e c t i s
s l i g h t an d i s f a r fro m b e in g a n im p o rta n t f a c t o r in th e v a p o r
a d s o r p t i o n , a s i s e v id e n c e d by th e e x p e r im e n ta l r e s u l t s *
I t i s w e l l icnovn t h a t th e p a r t i c l e s o f a c l a y a r e
v e ry l a r g e c o o p e re d t o m o le c u la r d im e n s io n s s o t h a t any p o r e s
in v o lv in g th e s p a c in g o f th e s e p a r t i c l e s m u st a ls o be l a r g e
b y c o m p a r is o n *
S p a c in g o f t h e c l a y p a r t i c l e s
in an a d so rb e n t
b y m ea n s o f a n a e r o g e l f o r m a t i o n d o e s n o t i n o r e a s e b e n z e n e
a d s o rp tio n *
I n o t h e r w o rd s t h e f o r m a t i o n o f l a r g e p o r e s o r a
g r e a t e r am ount o f a v a i l a b l e p a r t i c l e a r e a i s n o t e f f e c t i v e
in
g r e a t l y c h a n g in g th e a d s o r p tio n *
T he p r o c e s s o f a c i d b o i l i n g g r e a t l y
a d s o r p tio n by th e T exas b e n to n ite *
in c r e a s e s th e
I t w a s m e n tio n e d t h a t t h i s
e f f e c t i s p r o b a b ly due t o a l a r g e a r e a i n c r e a s e c a u se d by th e
f o r m a t i o n o f s m a l l s i l i c a c a p i l l a r l a s w h ic h a t t h e sam e tim e
? aha p o s s ib l e t h s c o n d e n s a tio n *
Ths s i l i c a t e t r a h s d r a h a v e
a g r e a t e r a m o u n t o f u n s a t u r a t i o n , b u t t h s a to m s p r o b a b l y
h a v e t h e sem e a r r a n g e m e n t a s t h e y d o i n t h e c l a y s o t h a t
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
1
a n o r d e r ly a rra n g e m e n t s t i l l o b ta in s *
T he hind o f aeld need
en d th e s u b s ta n c e s p r e s e n t in th e b o i l i n g s o l u t i o n g o v e rn
t h e n a t u r e o f t h e c a p i l l a r i e s fo rm ed *
a d so rb ed m e ta llic
m e a d d itio n o f h ig h ly
io n s o r a o le e u l e s t o th e s o ld c a u s e s in *
c re a s e d a d s o r p tio n f o r ben zen e in c e r t a i n p r e s s u r e re g io n s *
T h is a ls o s c a n s to be a m a tte r o f g o v e rn in g th e n a tu r e o f
t h e c a p i l l a r l e a fo rm e d * o r o f f o r m in g a s y s te m o f m o re u n i *
fo rm c a p i l l a r i e s *
The p r e s e n t e x p e rim e n ts sh o e t h a t th e a d d i t i o n o f
A ljO ^ a n d - i C j t o a c i d b o i l e d c l a y u n d e r c e r t a i n c o n d i t i o n s
g re a tly
in c r e a s e s th e a d s o rp tio n *
T h i s may b e due t o t h e
p re s e n c e o f a h ig h ly a c tiv e m a te r ia l in
th e l a r g e r p o re s o f
t h e o l a y e n h a n c e d b y t h e a c t i o n o f t h e c l a y ? s own s m a l l o a *
p illa rie s *
I n c e r t a i n o th e r c a s e s л h o w e v er, th 6 a d d it i o n o f
S iO x o r o t h e r o x i d e s a c t u a l l y d e c r e a s e t h e a d s o r p t i o n b e c a u s e
a p p a r e n t l y t h e i r m e th o d s o f f o r m a t i o n a r e s u o h t h a t a d s o r p *
t i v e a r e a s a r e b lo c k e d o f f *
I n th e p re c e d in g p a ra g ra p h s i t
d is tin c tio n
nay ap p ear th a t a
i s b e i n g made b e tw e e n " c a p i l l a r y c o n d e n s a t i o n "
and s u r f a c e a d s o rp tio n *
The i n d i c a t i o n s fro m e x p e rim e n t a r e
t h a t t h e s e d i f f e r e n c e s a r e o f d e g r e e r a t h e r t h a n k in d * h e n c e *
w hen a n a o t l v e s u r f a c e i n a c a p i l l a r y a d s o r b s e n o u g h v a p o r
s o t h a t n o m o re m a t e r i a l c a n e n t e r * c a p i l l a r y c o n d e n s a t i o n
may b e s a i d t o h a v e s e c u r e d *
I n o t h e r w o rd s* t h e s u r f a c e
f o r c e s may b e f u n d a m e n t a l l y t h e sam e* b a t t h e i r a v a i l a b i l i t y
a n d r e l a t i v e a m o u n ts p r e s e n t u n d e r d i f f e r e n t t r e a t m e n t s
may impend upon s t r u c t u r e *
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
A. r e v i s e d a p p a r a t u s f o r t b s m e a s u re m e n t o f v a p o r a d *
s o r p t i o n o n r e l a t i v e l y l a r g e s a m p le s h a s b e e n p r e s e n t e d .
7 1 th
t h i s e q u ip m e n t t h e a d s o r p t i o n I s o t h e r m s o f b e n z e n e v a p o r s f o r
v a r io u s n a t u r a l and t r e a t e d c la y s h av e b e e n s tu d ie d and in *
t e r p x e t e d o n a b a s i s o f know n f a c t s a b o u t c l a ; c o m p o s i t i o n e n d
s tru c tu re *
The r e s u l t s show t h a t t h e
fo llo w in g g e n e r a l i z a t i o n s
m ay b e m ad e :
1*
th e
is
T he a d s o r p t i o n o f b e n z e n e v a r i e s so m ew h at w i t h
i n t e r n a l s t r u c t u r e o f th e
s l i g h t and i s
c la y p a r tic le s *
T h is d i f f e r e n c e
i m p o r t a n t o n ly i n t h a t t h e s t r u c t u r e may
g o v e r n o t h e r p r o p e r t i e s o f t h e c la y *
T he n o a t m o r i l l o n l t e t y p e
c l a y se e m s t o h a v e a g r e a t e r a d s o r p t i v e p o w e r t h e n t h e h a o l i *
n ite
ty p e *
2m
C l a y s w h ic h h a v e a h i g h d e g r e e o f d i s p e r s i o n *
1* e * ╗ t h o s e w h ic h h a v e a l a r g e p e r c e n t a g e o f p a r t i c l e s
c o ll o i d a l re g io n e x h ib it a g r e a te r
la rg e p a rtic le s *
in th e
a d s o r p tio n th a n th o s e w ith
H e re a g a i n t h e d i f f e r e n c e s a r e s m a ll* a n d
th e in c re a s e d e x te r n a l s u rfa c e
i s a m in o r f a c t o r i n r e l a t i o n
t o o th e r f a c t o r s s tu d ie d *
3*
The s p a c i n g o f c l a y g r a i n s t o fo rm a l a r g e - s c a l e
s p o n g e l i k e s t r u c t u r e i s a n o t h e r f a c t o r o f s e c o n d a r y im p o r t a n c e
i n v a p o r a d s o rp tio n *
The p r e s e n c e o f r e l a t i v e l y l a r g e c a p i l *
l e r l e a b e tw e e n g r a i n s a n d t h e i n c r e a s e d p a r t i c l e s u r f a c e s w h ic h
o u s t b e a v a i l a b l e d o n o t e x e r t f o r c e s w h ic h a r e n o t i c e a b l y
d i f f e r e n t fro m th o s e i n th e u n ch an g ed d a y s *
4*
am
m ig h t b e e x p e c t e d f r o m o t h e r a d s o r p t i o n s t u d i e s *
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
8F*
tin
p ru M M
o f e x c h a n g e a b le i o a o o a t h e c l a y g r a i n s r e d u c e s
th e a d s o rp tio n o f benzene*
F o r u n iv a le n t and d l n l i n t lo a s
t n l s o f f s e t I s T o ry s m a l l a n d b e c o m e s r e l a t i v e l y
i n th e e a s e o f th e t e t r a v a l e n t io n s *
im p o rta n t
H o w e v e r, t h e e f f e c t i s
s t i l l o f m a l l c o n s e q u e n c e w hen c e r t a i n o t h e r f a c t o r s a r e c o n *
c id e r ed*
5*
By f a r t h e g r e a t e s t c h a n g e s i n a d s o r p t i o n by c l a y s
a r e e f f e c t e d b y f o r m in g c a p i l l a r i e s o r c h a n n e l s o f n e a r s o l e *
e u l e r s i z e s I n th e p rim a ry g r a i n s t r u c t u r e s *
T he s e l e c t i v e r e *
m o v a l o f i r o n a n d a lu m i n a b y a c i d f r o m t h e c r y s t a l s t r u c t u r e
o f t h e c l a y s l e a v e s p o r e s w i t h a c t i v e s i l i c a s u r f a c e s i n w h ic h
g r e a t a m o u n ts o f v a p o r a r e a d s o r b e d *
T h i s se e m s t o b e t h e
f a c t o r o f g r e a t e s t m a g n itu d e i n c l a y a d s o r p t i o n *
la r g e s t p o r tio n o f th e
h ln e e th e
a d s o r p t i o n i s g o v e r n e d by t h i s f a c t o r a
a p p r e c i a b l e d i f f e r e n c e s c a n be o b t a i n e d u n d e r d i f f e r e n t c o n d i н
tio n s t
a*
D i f f e r e n t a c i d s seem t o fo rm c a p i l l a r i e s o f
d i f f e r e n t s i z e s o r o f d i f f e r e n t n a tu r e so t h a t
u n d e r i d e n t i c a l c o n d itio n s th e e f f e c t o f one
a c i d i s n o t th e s a n e a s t h a t o f a n o th e r*
&?
T he a d d i t i o n o f h i g h l y a d s o r b e d m e t a l l i c i o n s
t o t h e a c i d t r e a t i n g s o l u t i o n se e m s t o p ro m o te
th e fo rm a tio n o f u n ifo rm ly a c t i v e s p a c e s g iv *
la g g r e a te r a d s o rp tio n i n c e r t a i n p r e s s u r e
re g io n s *
C*
T h e a d d i t i o n o f s i l i c a o r a lu m in a g e l s t o a n
a e id t r e a t e d c la y a l t e r th e a d s o rp tio n *
If
t h e g e l i s a llo w e d t o fo rm i n t h e s p o n g e * lik e
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
s t r u c t u r e , th s a d s o r p tio n i s re d u c e d , p ro b a b ly
b e c a u se th e a c tiv e s ir f & e e i have b een p a r t i a l l y
c o v e re d .
I f th e s t a t e o f s u b d iv is io n o f th e
a n t a x i a l added i s c o n t r o l l e d , th e a c t i v i t y o f
th e tr e a te d c la y i s e n h an c ed .
th a t th is
I t is lik e ly
Is due t o th e fo rm a tio n o f a c tiv e
s p a c e s s fc lo h o p e r a t e i n c o n j u n c t io n w i t h t h e
a c tiv e sp a c e s on th e c l a y ,
3,
C e r ta in n a tu r a l d a y s h a v e h ig h e r a d s o rp tio n
c u r v e s t h a n o t h e r n a t u r a l c l a y s h a v in g t h e s a n e
in te r n a l s tru c tu re
and g r a in s i z e .
T h i s , end
th e f a c t t h a t i n f l e c t i o n p o in ts o ccu r in t h e i r
i s o t h e r m s seem t o
in d ic a te
th a t th e c a p illa r y
f o r m a t i o n h a s t a ic e a p l a c e p a r t i a l l y
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
la n a tu re .
89*
EIBUOSfiAFHT
I*
C* L* A l e x o a l a n , Z I C e n g r t M o n d ia l P e t r o l e ,
5 6 9 (1 9 5 T )
8*
C* i.* A l e x o a l a n ,
(1 9 3 9 )
3*
V* S* B a y l l a , U*S*P*
1 ,7 7 8 ,5 1 7 *
4*
V* S* B a y l l a , U .S * P .
1 ,8 1 9 ,4 9 6 *
5*
? ? S . Boy H o , U*S*P*
1 ,8 1 8 ,4 5 3 *
6*
D* 8* B e i d e r a n d V* K o l l o y , U*8*P*
7*
o* B u r g h a r d t , In d * Bug* C h e n * ,
6*
H* C o r l o o h n , Z* A ngev* C h e a * , 5 1 , 6 9 9
(1 9 3 8 )
9*
C b a s b e r e a n d K in g , J * Cham* o o e * * 1 3 9
(1 9 3 9 )
rot*
P e tro llfe ra , 641,
761
1 ,9 8 0 ,5 6 9 *
8 0 0 (1 9 3 1 )
10*
C* Eckert, Z* Angew* C h e s u , 4 4 , 3 2 6 , (1 9 3 8 )
11*
K* bndoll and
12*
5 * F* B rm o le n k o , l e l a r u o k a y a xJcad* Z exuk* i n a t * r3iim*
Col, D*H*P* 622,356*
s n a ra ik P ra to , i ,
5 (1 9 3 4 )
13*
G* L* F e l l s a t , F r . P o t* 3 0 6 ,7 7 8 *
24*
R* F u o a t e l g , P e t r o l e u m E n g in e ex * г ╗ * 5 , 9 8 | if 6 * 6 4 {
# 1 3 , 58 (1 9 3 7 ).
IS*
A* F* Hogner, лa* mineral*, 2^t 67 (1939)
16*
T* L* H e a d e r e o n a n d 2* K e lle y * U .S *P *
17*
F * W* HUbOT, U*S*P*
1 ,9 8 6 ,1 4 8 *
18*
F* W* H u b e r , U*S*P*
1 ,9 7 6 ,1 8 7 *
19*
H* L* K au ffm an * U *г*P*
80*
K e lle y , Jo a n y , and B ro ra , s o i l s c ie n c e ,
81*
S* S* K l o t l s r , J ? F&ya* C h a n * , 3 6 , 5 8 , ( 1 9 3 8 )
88*
K* K o b e y a o h i a n d S* Y a n a n o t e , J * so o * C h ea* Xnd* J a p a n ,
1 ,6 0 0 ,6 8 7 *
2 ,1 1 6 ,3 1 0 *
8 5 6 , (1 9 5 6 )
| 7 , 1 8 1 (1 9 3 4 )
83a
I * Im o g en l r , J *
An*
C bon* s e e * , j g , 1 3 6 4 ( 1 9 1 8 )
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
SO#
24#
J # w# L lc B e in , "T ile S o r p t i o n o f G a s e s a n d T o p e r s b y S o l i d s '*
p l7 f #
ES. 3# E#
C o n le y a n d M# L# L a n g w c r th y , U#S#P# 1 ,7 9 6 ,7 9 9 #
26.
J# C. Morrell, U#г*P. 1*344,476#
27#
P* G# C u t t i n g , IT# S# G e o lo g l e a l s u r # C i r c # , г, ( 1 9 3 3 )
28#
P# G# n u t t i n g , H e f l a e r H a t u r a l G a s o l i n e ! г f r # ,
(1 9 3 3 )
2 9#
P o s a e h l s ^ p p a r a t e b a u , F r # P a t # 7 6 0 ,6 4 6 #
30#
ft# ~# l i a i s e a n d Hл C . P o l l o c k , 7 # 3 # P # 1 ,7 3 9 ,7 3 4 #
31.
Z# X#
32#
3o o # d e l a M a l H e r a g e , P r . P a t # 7 9 1 ,1 4 3 #
33.
3 . T ie t i g , U #3#P# 1 ,3 9 0 ,4 7 4 #
34#
3# 3# J r a z o r a i c u a n d 3 # 11# S lic iie rb a ic , T k r a l n . H ien#
S l o c u a , 7#S #P # 2 ,0 3 4 ,9 9 6 #
Zbur ?,
155 (1934 )#
35#
wiiton flrznniller, T#5.P# 2,013,987#
36#
3# G# 2 a p r o a ╗ t o v and. B# X o lm a k o r, 3 o l l # 7niv# As l e
C e n tra ls ,
/2 1 л 2 1 (1 9 3 5 )
37#
0# T# S o u l , 7 . 3 . P # 1 ,8 8 4 ,9 5 4 #
38#
г? 'л? Z n b l l a , 7 # S #P # 2,090,741#
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
80
,
<y is
t h e s u r f a c e t e n s i o n , T i s t h e v o lu m e o f l i q u i d , r i s
th e r a d i u s o f th e c a p illa r y *
I f one assu m es t h a t th e s u r f a c e
o f t h e a d s o r b e n t c o n s i s t s o f many v e r y f i n e c a p i l l a r i e s , i t
is
c l e a r t h a t t h e " s a t u r a t i o n v a p o r p r e s s u r e " may t a k e o n a s e r i e s
o f v a l u e s d e p e n d in g on t h o s e c a p i l l a r y
s iz e s *
T h is w o u ld e x *
p l a i n , t h e n , t h e v a n d e r V e a l a d s o r p t i o n t o t h e v e r y lo w p r e s *
su re s*
T h is e x p la n a tio n i s n o t s u i t a b l e , h o w e v e r, a s a g e n e r a l
e x p la n a tio n o f p h y s ic a l a d s o r p tio n b e c a u se c a l c u l a t i o n s fro m
t h e a b o v e e q u a tio n r e v e a l t h a t th e p o s t u l a t e d p o r e s m u st o f t e n
b e o f m o l e c u l a r s i z e s , i n many e a s e s l e s s t h a n t h a t o f t h e a d *
s o r b e d m o le c u le s *
U s o ,s im p le r e l a t i o n s h i p s o f t h i s ty p e can *
n o t b e e x p e c t e d t o h o l d f o r c a l c u l a t i o n s down a s l o v a s a to m ic
d im e n s i o n s *
I n a n y e v e n t , t h e e x p l a n a t i o n may s t i l l b e u s e *
f u l in a q u a lita tiv e sense*
O th e r f a c t o r s s u c h a s t h e s p e c i f i c
n a tu r e o f th e a d s o r b a n t w ith r e l a t i o n t o th e a d s o rb a te s n s t
a l s o b e t a k e n i n t o a c c o u n t w i t h t h e e x tr e m e e a s e b e i n g t h a t o f
c h e m ic a l a d s o r p tio n *
The a d s o r p tio n o f h y d ro c a rb o n v a p o re
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
4*
by ? la y
лu
n
t o ba a n w i l b l t p r o a e s s by m oat o f th a e x н
p e r i m e n t a l e v i d e n c e a n d m ig h t b a te r m e d p h y s i c a l a d s o r p t i o n ,
b u t t h a a a t i o n o f a l a y a a a w r a c k in g a a t a l y a t a m ig h t I n d i a n t a
t h a t t h a p ro e a a s in v o lv e s th a a o ra in ta n a a m o le c u la r f o r c e s *
I t la a g e n e ra l p r a e tic a to e x p re ss a d s o rp tio n a s
t h a w e ig h t o f n a t a r l a l a d s o r b a d , X , p a r u n i t w e ig h t o f a d s o rb н
i n g m a t e r i a l , M, a n d t h e a d s o r p t i o n i s o t h e r m s f o r v a p o r s may
* /y \ -
ba w rit ta n
th e fu n c tio n
?
Q u a n tita tiv e r e la tio n s h ip s f a r
-f C ?) h a v e b e a n f o r m u l a t e d s u c h a s t h e F r e u n d l i c h
e q u a tio n
-
K p /w
s h a re X and n a r e e m p ir ic a l conн
s ta n ts *
un t h e a s s u m p t io n o f o o n o a o l e c u l a r s u r f a c e l a y e r s ,
L a n g m u ir
(2 3 ) d e r iv e d th e e x p r e s s io n
*/г* ~ ? X
*
The
c o n s t a n t s a r e a g a in e m p ir ic a l and n e i t h e r e q u a tio n c a n a c c o u n t
f o r m any o f t h e m ore c o m p l i c a t e d a d s o r p t i o n i s o t h e r m s v h i c h
shoe
th e e f f e c t o f v a ry in g c a p i l l a r y s iz e s and v a r io u s ty p e s
o f " a c tiv e c e n te rs " *
T ha f o r m a t i o n o f t h a optim um , s i z e p o r e s o r t h e c r e н
a t i o n o f t h a c o r r e c t a c t i v e e e n t e r s se e m s t o b e t h e p r o b le m
in v o lv e d in th a a c t i v a t i o n o f e la y s f o r d e c o l o r iz a t i o n an d
? a ta ly a is *
T ha g e n e r a l t r e a t m e n t o f e l a y s i s a p r o c e s s o f
? a i d b o i l i n g i n w h ic h a l u m i n a , i r o n , a n d m o s t o f t h e b a s e s
e r a l a a a h a d o u t*
T ha e x p l a n a t i o n o f t h a a c t i v a t i o n b y t h i s
t r e a t m e n t i s t h a t by l e a s h i ng o u t A l^ O ^
a r e m ada i n t h e c l a y s t r u c t u r e *
and i r o n , p o re s
A ls o , re m o v a l o f t h a b a s e s
a n d t h e i r r e p l a c e m e n t b y h y d r o g e n g i v e s -OH g r o u p s o n a d J a a a n t s i a to m s w h ic h o n s p l i t t i n g
o u t w a te r g iv e s t r a i n s
in th a s i l i c a s t r u c tu r e , th u s c re a tin g a c tiv e a a n ta rs *
Much w o rk a p p e a r s i n t h e p a t e n t l i t e r a t u r e o n t h e
i
i
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
9.
a c t i v a t i o n o r c la y s ca a d s o rb e n ts *
By f a r t b c a o a t w i d e ly
u s e d a n d s e e m i n g ly a o a t c r f a e t l v e a a a n s o f a c t i v a t i o n h a s
b een tb c p ro e e sa o f a c id b o ilin g *
T h ere a r e s e v e r a l p a te n ts
w h ic h c o n s i s t o f t h e s i a p i s b o i l i n g o f c l a y s i n HC1 o r Ha SO^.
o f v a ry in g c o n c e n tr a tio n s and f a r v a r io u s le n g th s o f t i n s *
(5 )
(4 )
(S )
(7 )
(1 7 )
( I B ) (S B ) ( 3 0 ) *
T hese p a te n ts in d ic a te
t h a t th a o p tio n s c o n c e n tr a tio n and le n g th o f tre a tm e n t I s la r g e *
l y d e p e n d e n t on th a ty p e o f c la y and th a n a tu r e o f th e a d so rp *
t i o n w o rk f o r w h ic h t h e c l a y l a t o b e u s e d *
I n g e n e r a l , how*
e v e r , a c id c o n c e n tr a ti o n s o f 5 t o S0г and t r e a t i n g
th re e
to e ig h t h o u rs a r e used*
v ig o ro u s a e id tre a tm e n t*
T ie tig
tim e s o f
( 3 o ) u s e d a m ore
H i s m e th o d i n v o l v e s t h e b u r n i n g o f
E t a n d C l z i n t h e p r e s e n c e o f w a t e r v a p o r o v e r t h e c la y *
N u ttin g
(2 7 )
( 2 8 ) p o i n t s o u t t h a t m any e l a y s a r e p a r t i a l l y
le a c h e d i n n a tu r e by th a a c t i o n o f n a t u r a l l y o c c u rin g a c id s *
When a n a t t e m p t l a m ade t o a c t i v a t e
t h e s e c l a y s by a e i d b o i l *
l n g , a n e x c e s s l e a c h i n g t a k e s p l a c e t f i i o h se em s t o d e s t r o y
t h e p o r o s i t y o f t h e c l a y o r m ake p o r e s s o l a r g e t h a t t h e y a r e
n o t v e ry a c t i v e i n a d a o rp tio n *
S c k a r t (1 0 )*
T h i s I s a l s o r e c o g n i z e d by
T ha p r e v i o u a a d d i t i o n o f s t r o n g l y a d s o r b e d c a *
t i o n a s u c h a s A l* * * , P e * * * , o r Mg'** se e m s t o p l u g t h e n a t u r a l *
l y fo rm ed p o r e s an d s l o w
down l e a c h i n g a t t h o s e s p o t s d u r i n g
a c i d b o i l i n g , g i v i n g a r e s u l t a n t a d s o r b e n t w h ic h h a s b e e n
u n i f o r m l y e t c h e d a n d w h ic h i s g r e a t l y
im p ro v e d *
h a s a ls o b een re v e a le d in th a p a te n t l i t e r a t u r e
T h is p r o e e s a
(9 6 )*
I t h a s b e e n p a i n t e d o a t I n o n e w o rk ( S ) t h a t t h e
a d a o rp tio n p r o p e r t i e s o f e la y e i s d e p en d e n t on ( l )
th e am ount
o f s i l i c a t e s c a p a bl e o f b e in g c o n v e rte d by a c t i v a t i o n t o h y *
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
d ra te d s ilic a
I n t h a g e l f o r s , a n d (B ) t h a h y d r a t e d s i l i c a
c o n te n t o f th a n a t u r a l e la y *
I t la fu rth e r a ta ta d th a t a l╗
? o a t e v e r y a a a a o f m o t i v a t i o n o f e l a y a l a t h a a ante h a e a n a a
I t t a k a s a d v a n ta g e o f t h a s a f a c t a *
ix a a p le a o f a c t iv a t io n
by B a a a a o t h e r t h a n a e i d b o i l i n g a a a a t o b e a r t h l a o a t *
F e l i z a t ( 1 3 ) a c t i v e t e a e l a y f o r a d a o r p t i o n w o rk by t r e a t i n g
I t w ith a n a l k a l i m e ta l s i l i c a t e
a n d t h a n a d d in g e n o u g h
a e id to n e u tra lis e
f o r m in g a e l a y w i t h a l l i e a
th e s i l i c a t e ,
e lo a a ly a a a o e la te d w ith i t*
? a o d lf le a tio n o f t h l a p ro c e d u re
i n w h ic h t h a e l a y a n d a i l i e a t e m i x t u r e l a b o i l e d d u r i n g t h e
a d d itio n o f a e id h a s a la o been re v e a le d
(3 2 }*
o t h e r m e th o d s
o f e l a y a c t i v a t i o n se e m t o b e m e r e l y t h e p u r i f i c a t i o n o f
n a t u r a l l y a c t i v e c l a y s b y v a r i o u s m e th o d s*
( 1 1 ) a c t i v a t e c l a y b y a d d i n g CC^
E n d e ll an d O at
to a s lu r r y and th e n
e l e c t r o d i a l y s i n g t o re m o v e t h e e l e c t r o l y t e s a d s o r b e d *
s i m p le
e le c tr o d ia ly s is or e le e t r o f U t r a t l o n h a s a ls o been u sed
From. t h e s c a n t w o rk r e p o r t e d i n t h e l i t e r a t u r e
(2 9 )*
on
th e a c t iv a tio n o f c la y s by d e h y d ra tio n , i t a p p e a rs t h a t t h i s
p r o c e d u r e i s s o m e tim e s e f f e c t i v e
in g o n t h e c la y *
^ le x a n la n
a n d s o m e tim e s n o t , d e p e n d н
( 1 ) , C e r l s o h n ( 3 ) , a n d K au ffm an
( 1 9 ) c l a i m e l a y a c t i v a t i o n by d e h y d r a t i o n , a n d Z u b l i n ( 3 6 )
c la im s to f u r t h e r
a c t i v a t e a c i d t r e a t e d c la y by tr e a tm e n t
w i t h s u p e r h e a t e d s te a m i n o r d e r t o d r i v e o f f a l l w a t e r w i t h н
o u t r e m o v in g t h e w a t e r o f h y d r a t i o n s
S c k a rt re p o rta th a t th e re
On t h e o t h e r h e a d ,
I s n o r e l a t i o n b e tw e e n d e c o l o r i s н
in g a c t i o n o f a e la y and i t s l o s s o f w a te r on h e a tin g *
o u sw a ry o f O b je c tiv e s
T he o b j e c t o f t h e p r e s e n t w o rk h a s b e a n t o s t u d y
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
tl╗
a d s o r p tio n o f h y d ro e a rb o n v a p o rs o n v a r io u s ty p e s o f
d a y s , and to lo a m
fro m t h i s a d a o r p tio n s tu d y th a r e l a t i v e
im p o rta n c e o f v a r i o u s f e s t e r s , b o th c h e m ic a l a n d p h y s i c a l ,
w h io h d e t e r m i n e t h e a d a o r p t i v a phenom ena ?
T h a i n i t i a l w o rk w as d e s i g n s * t o l a a r n t h e r e l a t i v e
m a g n itu d e a n d f l e x i b i l i t y o f a d a o r p t i o n d u o t o t h e f o l l o w i n g
fa s to rs t
(1 )
T he a t o n l s e t r u e t u r e o f t h a m i n e r a l g r a i n *
(8 )
T he d e g r e e o f d i s p e r s i o n o f t h a s l a y g r a i n s ,
and th e r e l a t i v e
im p o r ta n c e o f t h e e x t e r n a l
su rfa c e s*
(3 )
T he r e l a t i v e
im p o r ta n c e o f t h e s p a c i n g o f
s e c o n d a r y a g g r e g a t e s , 1* e * , s p a c e s b e tw e e n
th e d a y g r a in s *
(4 )
T he e f f e c t o f e x c h a n g e a b le i o n s w i t h i n t h e
c la y g ra in s *
(5 )
T he e f f e c t o f i n t r a p a r t i c l e s p a c e s , o r c h a n *
n e l s o f n e a r m o le c u la r s i x e s i n th e p rim a ry
g ra in s tru c tu re *
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
E X P E R I M E N T A L
P-.HT
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
Adsorption M u v n u t c h s n teta made in many dif*
f e r e n t n y i , and th a la h s r a n t e r r o r s and l i m i t a t i o n s o f th s
s e v e r a l m e th o d s h a v e b e e n d i s c u s s e d b y M eB ain ( 8 4 ) *
M e B a in 's
im p ro v e d m e th o d o f a d s o r p t i o n s t u d y i a c o n v e n i e n t l y a p p l i e d
t o is o t h e r m . w o r k , b u t i n o r d e r t o g a i n a c c u r a c y i n m e a s u r e н
m e n t s , t h e q u a r t s f i b e r s o u s t b e made v e r y d e l i c a t e a n d h e n c e
t h e s i z e o f s a m p le s m u s t b e v e r y s m a ll*
re a liz in g
C h a m b e rs a n d Z in g ( 9 )
t h e d i f f i c u l t i e s o f u s i n g s m a l l s a m p le s a n d d e s i r н
i n g g r e a t e r a c c u r a c y h a v e d e s i g n e d a new a d s o r p t i o n b a l a n c e d
i n w h ic h t h e q u a r t z s p r i n g i a s u b s t i t u t e d by a f l o a t
(s im iн
l a r t o a h y d r o m e t e r ) s u s p e n d e d i n m e rc u ry *
f.'ith t h i s e q u i p н
m e n t , t h e a c c u r a c y o f t h e M eB ain b a l a n c e i s
t r i p l e d u s in g
s a m p le s a s l a r g e a s s i x g ra m s *
I n t h e p r e s e n t w o r k i t w as d e s i r e d t h a t s a m p le s o f
f o u r t o s i x g ra m s b e u s e d s o t h a t d i e a m o u n t o f a d s o r p t i o n
w o u ld be m e a s u r a b le *
H o w e v e r, a c c u r a c y a s g r e a t a s 1 p a r t
i n 8 0 ,0 0 0 w as n o t c o n s i d e r e d n e c e s s a r y s o t h a t t h e Z in g
m e th o d w as n o t u se d *
m at i c a l l y
in fig u re
T he a p p a r a t u s u s e d i s sh e w n d i a g r a m (1 )*
M sB eIn?T a n n e r b a l a n c e
a W e s tp h a l b a la n c e *
I t i s s im ila r in p r i n c i p l e t o th e
(2 4 )*
T he b a l a n c e p a r t w a s m ade from ,
The z e r o p o i n t w as o b ta in e d by p a s s in g
a c u r r e n t t h r o u g h t h e s o l e n o i d w h ic h a c t s on t h e
m a n e n t m a g n e t*
p e rн
The e l e c t r o m a g n e t i a c a l i b r a t e d a g a i n s t a
s t a n d ar d w e ig h t b e f o r e and a f t e r e a c h r u n i n o r d e r t o d e t e r н
m in e t h e v o l t a g e p e r g ram *
S in c e f a i r l y h ig h v o l ta g e s e r e
u s e d i n sam e e a s e s , t h e e l e c t r o m a g n e t i s t a p p e d f o r a fe w
t u r n s an d th s v o lta g e m e a su re d f o r th e s e t u r n s w ith a
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
p o tta tiflM tir*
It л u
v a r i e s v e ry l i t t l e
fo u n d t i n t t i n
w e ig h t
o v e r a p e r i o d o f t im e an d t h e v a r i a t i o n
w ith w e ig h t l a p r & e t le a ll y n e g l i g i b l e *
H o w e v e r, t h e c a l i b r e -
t l o n e w e re a lw a y s m ade o v e r t h e sam e w e ig h t r a n g e a s t h a t u e e d
i n th e a c t u a l e x p e rim e n t*
T he p r o c e d u r e f o r a n i e o t h e r m r a n l a a e f o l l o w s :
1
c o n v e n ie n tly
l a r g e s a m p le l a p l a c e d I n t h e s a m p le b u c k e t
a n d w e t w i t h t h e l i q u i d w hose v a p o r s a r e t o be a b s o r b e d
d e so rb e d )*
* lth fiv e
i n th e s y s te m , i t
e v a p o ra te *
(o r
to t e n c u b ic c e n tim e te r s o f th e l i q u i d
i s e v a c u a te d and th e l i q u i d
i s a llo w e d t o
T h is w a s h e s t h e s y s t e m f r e e o f a i r a n d i e e v e s
o n ly th e v a p o rs *
T he t u b e c o n t a i n i n g t h e s a m p le i s lo w e r e d
i n t o a c o n s t a n t t e m p e r a t u r e b a t h a n d i s a ll o w e d t o com e t o
e q u i l i b r i u m , t h e tim e r e q u i r e d u s u a l l y b e i n g o n e t o
h o u rs*
fo u r
In ru n n in g a d e s o r p tio n Is o th e rm th e p r e s s u r e i s
lo w e r e d I n s t e p s a n d t h e c o r r e s p o n d i n g w e i g h t i s o b s e r v e d
fro m th e p o te n tio m e te r a s o u t l i n e d above*
in o r d e r to fo llo w
t h e a d s o r p t i o n o f t h e v a p o r s , t h e s y s t e m i s e v a c u a t e d a s m uch
a s p o s s i b l e a n d s m a l l a m o u n ts o f l i q u i d a r e a d m i t t e d f r o m t h e
v a eu u m s i d e o f t h e a p p a r a t u s , t h e p r e s s u r e r i s i n g
ifte r
in s te p s *
th e is o th e r m h a s b e e n r u n , th e a b s o lu te am ount o f m a te r iн
a l a d s o r b e d o u s t b e d e te r m i n e d *
T h is i s done b y e v a c u a tin g
t h e e y a te m a s muc h a s p o s s i b l e a n d a t t h e sam e t i m e h e a t i n g
t h s s a m p le I n a n o i l b a t h t o 1 0 0 - 1 7 0 ░ C*
T he v o l t a g e r e a d i n g
t a k e n a t t h i s tim e i s a s s u m e d t o b e t h e r e a d i n g f o r t h e s a m p le
w ith no a d s o r p tio n , s in c e i t
h a s c e a s e d l o s i n g w e i g h t*
i s t a k e n o n l y a f t e r t h e s a m p le
H e n ce , t h e w e ig h t o f m a t e r i a l a d н
s o rb e d a t an y g iv e n p r e s s u r e w i l l b e re p re s e n te d by th e d l f -
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
10*
f i r t o t t b i t i H a th e T e l t a p re a d in g a t t h a t p r e s s o r s so d th a
l a s t m e n tio n e d v o l ta g e r e a d in g *
n s
a a th o d o sn b e s t b s d e a o a *
s t r a t e d b y a t a b l e o f d a t a f a r a t y p i c a l d e s o r p t i o n is o th e rm *
(s e e T a b le I * )
T n ~ * itin
v f " 1?
? " * f f n t i f t t w r *? ? ? ?л
Za a o e t o f th a f o llo w in g e x p e rim e n ts , benzene
T s p o r a a t 9 0 ░ C w a re n e e d *
B enzene w as e h o se n b e c a u s e i t
p ro b a b ly th e m o st to n e s lo n e ly a d so rb e d o f th e lo v
ie
Itr
w e i g h t u n s a t u r a t e d co m p o u n d s w h o se n o l s e u l a r d i m e n s i o n s a r e
a c c u r a t e l y know n*
p e lle ts *
i l l t h e e l a y s a m p le s w e re i n t h e f o r m o f
T h e s e w e r e fo r m e d b y m a k in g a t h i c k p a s t e , e x t r u d н
in g t h i s p a s t e th r o u g h a a m i l tu b e a n d d r y in g th e r e s u l t a n t
c y li n d e r s o f c la y *
^*
Wyoming B e n t o n i t e w a s e h o s e n a s a t y p i c a l b a s e
s a t u r a t e d m o n tm o r illo n ite ty p e c la y *
th s n a tu r a l c la y
T hs h i g h pH ***Talus o f
in d ic a te s t h a t i t h a s n o t re c e iv e d su ch a e id
le a c h in g in n a tu r e
00
le a s h e d b e n to n ite *
i t n i g h t b e a g o o d e x a m p le o f a n u n н
T h e s a m p le u s e d i n t h i s e x p e r ix a e n t h a d b e e s
s w e l l e d i n w a t e r f o r s e v e r a l m o n th s , a n d t h e n e l e c t r o d i a l y s e d
t o re m o ra a l l t h s a x o n a n g s a b le b a s e s an d any n a t u r a l l y o c c u r in g
o
s a l t s w h ic h m i g h t b e a d s o r b e d * T h i s m a t e r i e l w as d r i e d i t 1 1 0
C*
T h s d e s o r p t i o n i s o t h e r m i s sh o w n i n f i g u r e
n o te d , th s c u rv e
(г } ?
a s w i l l be
i s v a r y f l a t u n t i l th s p r e s s u r e becom es l e s s
t h a n 109( e f t h s s a t u r a t e d v a p o r p r e s s u r e
a t w h ic h p o i n t t h e r e
(1 1 8 am* Hg a t 3 0 ░ C)
i s a s h a r p b r e a k t o th e z e r o v a lu e *
T h is
c u r v e i s t y p i c a l o f t h s F r e u n d l i c h o r L an g m u ir a d s o r p t i o n
c u r v e , a n d m i g h t i n d i c a t e t h a t t h e r e a r e r e l a t i v e l y fe w p o r e s p r e н
s e n t f o r c a p i l l a r y c o n d e n s a tio n o r i n t e n s e l y a c t i v e s p o ts
w h i c h
m i g h t
b e
r e s p o n s i b l e
1
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
11*
fo r t
o v r t o w ith , b r t t k i i a I t *
г?
P u r e w a sh e d k a o l i n a n a u s e d no o n e x a m p le o f a n o t h e r
fu n d a m e n ta l ty p o o f e la y s t r u c t u r e ?
Two s a m p le s o f t h i s a n *
o
t e r i a l w o re p r e p a r e d , o n e b e i n g h o o t e d a t 1 1 0 C t o re m o v e a d *
o
a o r b o d w a t e r a n d t h e o t h e r b e i n g h e a t e d a t 4 5 0 C t o re m o v e
th e " c r y s t a l w a te r"
i a fig u re
(2 ) ?
(SO )*
T he r e s u l t a n t i s o t h e r m s a r e a l s o
I t i s s e e a t h a t th e a d s o r p tio n i s v e ry s m a ll
i a t h i s e a s e u n t i l th e s a t u r a t i o n v a p o r p r e s s u r e i s a p p ro a c h e d *
B o th t h e k a o l i n s a m p le s a r e p r a c t i c a l l y
t h e sam e w n ea i t
is
n o t e d t h a t t h e d i f f e r e n c e s b e tw e e n th e m a r e v e r y s m a l l a n d may
be due to e x p e r im e n ta l e r r o r *
T he s h a r p r i s e
a t th e h ig h e r v a p o r p r e s s u r e s i s p ro b a b ly
th e p re se n c e c f f a i r l y
in th e s e c u rv e s
due e i t h e r
(1 } t o
l a r g e p o r e s e t c h e d i n t h e c l a y by n a t u r e ,
o r ( 2 ) t o som e e x t e n s i v e s p a c i n g b e tw e e n t h e p r i m a r y g r a i n s i n
th e s e c o n d a ry a g g re g a te *
I h i s f i r s t id e a i s c o n s is te n t w ith
t h e f a c t t h a t t h e n a t u r a l k a o l i n u s e d h a s a pH * v a l u e c o n s t *
d e r a b l y b e lo w s e v e n *
г?
a s a m p le
p e r i m e n t a w h ic h f o l l o w
a d s o rp tiv e q u a litie s *
o f T e x a s c l a y u s e d i n m o st o f t h e e x *
w as f o u n d t o h a v e q u i t e d i f f e r e n t
T he b u l k o f t h e n a t u r a l c l a y
m o n t m o r i l l o n i t s t y p e a s sh o w n b y X * ra d lo g ra m s *
i s o f th e
T he x ?r a y p a t *
t e r n f o r t h e e l a y a s r e c e i v e d sh o w s i m p u r i t i e s o f l a r g e p r i н
m a ry p a r t i c l e
s iz e s *
T h is i s a l s o n o t e d a n m i c r o s c o p i c
e x a m in a t io n *
In o rd e r to s tu d y th e c o ll o i d a l f r a c t io n and
h e n c e * t h e a l m o s t p u r e m o m t m s r i i l o n i t e p a r t o f t h i s c la y * a
l a r g e p o r t i o n o f i t w as d i s p e r s e d i n SaQH s o l u t i o n a n d a l l o w e d
t o s w e ll f o r s e v e r a l d ay s*
T h is s u s p e n s io n w as 3 9 г s o l i d s by
w e i g h t a n d h a d a pH * o f 1 0 * 5 *
Two l i t e r s o f t h e s u s p e n s i o n
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
w as d i l u t e d t o f i r e g a l l o n s and t h e o e e re e n o t a r i a l s e t t l e d
o u t a th e s u p e r n a t a n t s u s p e n s io n b e in g s u p e r - c e n t r l f u g e d ?
I - r e y p i c t u r e s o n t h e c o l l o i d a l f r a c t i o n show t h e
m o n ta o rlllo n ite p a tte rn *
t^ p le & l
The s u p e r - c e n tr if u g e d m a t e r i a l v a s
w a sh e d s a v e r e l t i n e s w i t h c o n c e n t r a t e d HE^QH i n o r d e r t o r e н
p l a c e m o st o f t h e a d s o r b e d m a t e r i a l s *
I t v as th e n d r ie d a t
o
1 5 0 C t o r e s t o r e a n y r e s i d u a l a n a e m ia l e a v i n g t h e p u r e a e i d
c la y *
A d e s o r p t i o n i s o t h e r m w as r u n o n t h i s m a t e r i a l *
c u rv e is sh o rn in f ig u r e
end u n lik e
(2)*
t h e Wyoming b e n t o n i t e , i t
f a m i li a r a d s o r p tio n is o th e rm s *
th is
T h is c u rv e i s r e l a t i v e l y
The
h ig h ,
i s n o t t y p i c a l o f th e
T he b r e a k s w h ic h o c c u r i n
c u rv e a p p e e r a t a p r e s s u r e w h ic h i s c o n s i s t e n t w i t h t h e
t h e o r y t h a t v e r y e m a i l c a p t i l e r i e s may b e fo rm e d w i t h i n t h e
p rim a ry g r a i n s by a c id le a c h in g o f th e c la y
in n a tu re *
A ls o ,
th e a c i d i t y o f th e n a tu r a l e la y i s f u r t h e r c o n firm a tio n
th is
f
id e a *
T he r e s u l t s o f t h e s e d a t a i n d i c a t e
d iffe re n c e
of p a r tic le
th ╗ t th e v id e
s i z e s and t h e fu n d a m e n ta l d i f f e r e n c e s
i n t h e c l a y t y p e s a r e m in o r f a c t o r s i n t h e a d s o r p t i v e p h e n o н
m ena*
i s a f i r s t ch eek on th e fo re g o in g i n t e r p r e t a t i o n
o f t h e a d s o r p t io n pow er o f n a t u r a l e l a y s , p u r e ly p h y s i c a l
m e a n s o f s p a c i n g t h e n a t u r a l e l a y g r a i n s w e re t r i e d
in o rd e r
t o d i s t i n g u i s h c a p i l l a r y a d s o r p t i o n i n c lu m p s o f g r a i n s f r o m
o t h e r a d s o r p t i v e p h e n o aw n a *
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f o r t i l t a e id b o i li n g i o t t n o te
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The d e s o r p t i o n
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w as r u n , g i v i n g t h e c u r v e i n f i g u r e
(5 )*
i t h ig h p r e s s u r e s
the a d s o r p t i o n i s h i g h b u t d r o p s o f f r a p i d l y a t lo w e r p r e s н
sures*
T h i s se em s t o i n d i c a t e t h a t t h e S iO t b l o c k s t h e
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It*
s m a lle r
p o r e s , b u t d u e t o i t s own a d s o r p t i v e n a t u r e e a u a e s
an in c re a s e d a d a o rp tio a a t h ig h e r p re s s u re s *
14*
a n a f u r t h e r s tu d y o f t h e e f f e e t o f a d d itio n
a g e n ts t o a s id b o ile d c la y ,
scn ce*
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in i t s p ro *
a s a m p le o f t h e o o l l i d a l f r a c t i o n o f t h e T e x a s c l a y
w as b o i l e d i n HC1 u n d e r t h e s t a n d a r d c o n d i t i o n s t e n d NH^OH i n
e x e e e s w ee a d d e d b e f o r e f i l t e r i n g *
T h in p r e c i p i t a t e d b o t h t h e
i r o n e n d a lu m in u m i n t h e p r e s e n c e o f t h e s i l i c a c a p i l l a r i e s
o f th e c la y *
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ra n g e *
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t h a t th e o r i g i n a l c a p i l н
l a r i e s a r e n o t b l o c k e d o f f b y t h e * 1 ^ 0 ^ a n d Z e xC3 a n d t h e s e
s u b s ta n o e s c a u s e a s p e c i f i c c h a n g e i n th e n a tu r e o f th e s u r н
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15*
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o r d e c re a s e d th e a d s o rp tio n *
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t h e a lu m in a *
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u n t i l f r e e o f C l a n d d r i e d a t 1 2 0 C* T h e d e s o r p t i o n i s o t h e r m
o n t h i s m a t e r i a l w as a l m o s t i d e n t i c a l w i t h t h e o n e d e s c r i b e d
i n s e c t i o n 1 4 a s earn b e s e e n f r o m t h e c u r v e i n f i g u r e
n i l s seem s t o b e p r o o f t h a t t h e
(d )*
iro n p re s e n t a s a p r e c ip ita te
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o f 7 л t 6 ) d o ts n o t a l t e r th e a d s o r p tio n a g r e a t d e a l*
I
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m e f i r s t s t u d i e s o f a d e p o s i t o f S iO t o n t h e
s a id b o ile d d a y
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sh o w ed a d e e r e a s e i n a d s o r p t i o n *
a s w as
t h e S iG * w as f o r a s d i n c o n t a c t w i t h t h e d a y
a n d h ad o p p o r tu n ity t o b lo c k any h ig h ly a c t i v e a r e a s *
o r d e r t o s tu d y t h i s
In
f u r t h e r b y c h a n g in g t h e m e th o d o f f b r m a ?
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t h i s s o lu tio n w ith v i o le n t
a g i t a t i o n u n t i l t h e s o l u t i o n becam e t u r b i d w i t h o u t t h e f o r н
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t o t a l ftm ount o f
d ry c la y *
w o u ld b e a b o u t 2 0 # o f t h e w e i g h t o f t h e
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t h e c l a y a d d i t i o n b u t w as b r o k e n im m e d ia te ly b y v i o l e n t a g i н
ta tio n *
T h i s m i x t u r e w as w a sh e d s e v e r a l t i m e s a n d t h e n
e l e c t r o d i a l y s e d f r e e o f a l l r e m a in i n g e l e c t r o l y t e s *
d r i e d a t 5 4 0 ░ C*
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b u t m e r e ly e n h a n c e d t h e i r a c t i v i t y *
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d e p o s i te d i n t h i s m an n er c o u ld b e due t o
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c r e a s e d nu m b er o f p o r e s o f a c e r t a i n s i z e * o r ( 2 ) a d e p o s i t
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SI*
a d d i t i o n t o a c i d b o i l e d s l a y * a c l e a r s i l i c a g a l aaa ^ r t p a r t d
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b u t w as n o t f i l t e r e d *
T o t h i s t h e S iC t g e l w as a d d e d i n a n
am o u n t a u e h t h a t 1 0 г o f t h e w e i g h t o f t h e c l a y w as ^ 1 C Z *
. a f t e r t h i s m i x t u r e w a s m ade h o m o g en o u s b y v i o l e n t a g i t a t i o n *
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o
5 4 0 C* T he d e s o r p t i o n i s o t h e r m f o r t h i s m a t e r i a l sh o w n i n
fig u re
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a n d 15 and n o t q u i t e a s h i g h i n c e r t a i n r e g i o n s as t h e o n e
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IKTLE PHET*.? IC K OF RESULTS
aKD
SUMMARY
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
Inta╗nrлtatlon of HcKilfi
As w as s t a t e d i n t b s i n t r o d u c t i o n , th e o b j e c t o f
t h i s r e s e a r c h w as t o
s tu d y f a e t o r s g o v e rn in g th s a d s o r p tlo a
o f b en zen e v a p o r on s l a y s , s a d by t h i s a d s o r p tio n t o s tu d y
t h s o f f s e t o f c h e m ic a l and p h y s io s ! t r e a t m e n t s on c la y s *
Tbs
e x p e r i m e n t s show t h a t t h s a d s o r p t i o n o f b e n z e n e v a r i e s w i d e ly
w ith th e ty p e o f c la y s t r u c t u r e , th e ^ a o l i n i t e
in g o uch l e s s
th a n th e l o n t m o r i l i o n i t e ty p e *
e x p la in e d by th e f a c t t h a t i n lo n tm a r i l l o n i t e
ao x e s u r f a c e o f th e s i l i c a
c la y s *
ty p e a d so rb *
T h is m ig h t b e
th e re
ty p e a v a i l a b l e th a n i n
is ouch
th e o th e r
r .ls o , th e d e g re e o f d is p e r s io n o f ra o n tE o rlllo n ite
is
g r e a te r th e n t h a t o f h a o lin and a g r e a te r e x te r n a l s u r f a c e
is
th e re fo re a v a ila b le *
in
a n o t h e r i n t e r e s t i n g r e s u l t , w h ic h i s
a g re e m e n t w ith p r e v io u s e x p e r l o e n t e r s , i s
i n g t h e cam e s t r u c t u r e
te ris tic s .
th a t c la y s e x h ib it*
do n o t h a v e t h e sem e a d s o r p t i o n c h a r a c *
F o r e x a m p le , t h e Wyoming b e n t o n i t e & ud T e x a s b e n *
t o n i t e h a v in g i d e n t i c a l X * ra y p a t t e r n s h t.v e d i f f e r e n t a d s o r p t i o n
p r o p e r t i e s i n b e n z e n e v a p o r*
,-s p o i n t e d o u t i n t h e d e s c r i p t i o n
o f th e e x p e rim e n ts , th e g e o lo g ic a l h i s t o r y
o f th e T exas e la y
I s s u c h t h a t t h i s s t a t e r i a l h a s r e c e i v e d m uch n a t u r a l w e a t h e r *
in g and l e a c h i n g , an d h e n c e , f in e
c a p i l l a r i e s h a v e b e e n f a rm e d
b y t h e r e m o v a l o f a lu m i n a f r o m t h s s t r u c t u r e ?
p r e s e n t a l a r g e a r e a f o r a d s o r p tio n , and a ls o
T hese p o re s
o f f e r th e poo*
s i b i l l t y o f c a p i l l a r y c o n d e n s a t i o n w h ic h w a s d i s c u s s e d i n
a n o th e r p a r t o f t h i s p a p e r*
T hs c h a r a c t e r i s t i c b r e a k s i n t h e
a d s o r p t i o n i s o t h e r m s p o i n t s t r o n g l y to w a r d t h i s l a t t e r
id e a *
T h e fy o m in g b e n t o n i t e , u n l e a s h e d b y n a t u r e , g i v e s a n i s o t h e r m
t y p i c a l o f t h e F r e u n d lie h o r la n g m u ir ty p e *
n i l s ty p e c u rv e
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
**╗
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i s e x p la in e d o n t b s b a s i s o f m o le c u la r l a y e r s o a t h s a d s o r b e n t
su rfse a .
s i a s s t h i s c u rv e h a s v a ry le v T a llie s , i t
i s re a so n *
a b l e t o a s s u n s t h a t t h i s s i m p le e x p l a n a t i o n b a s e d o n a u n i f o r m
i
s u rfa e e i s n o t b ro a d enough to e x p la in a l l th e r e s u lts *
a s s u m in g s u r f a c e s o f d i f f e r e n t a c t i v i t y ,
By
th s i n f l e c t i o n p o in ts
c o u ld he a c c o u n te d f o r o a th e b a s i s o f t h s
th e o ry ,
b u t th e l i n e s v h ie h a r e s t e e p i n th e r e g i o n a p p ro a c h in g s e t u r a *
t i o n v ap o r p re s s u re s t i l l r e q u ir e an e x p la n a tio n su ch a s c a p il*
l a r y c o n d e n s a tio n *
T he c l e a n i n g o f c l a y s u r f a c e s b y w a s h in g o r e l s e t r o *
d i a l y s l n g re m o v e s s t r o n g l y a d s o r b e d i o n s l e a v i n g t h e a c t i v e
s p o ts fre e
to a d s o rb b e n sen e v a p o rs*
H o w e v e r, t h i s e f f e c t i s
s l i g h t an d i s f a r fro m b e in g a n im p o rta n t f a c t o r in th e v a p o r
a d s o r p t i o n , a s i s e v id e n c e d by th e e x p e r im e n ta l r e s u l t s *
I t i s w e l l icnovn t h a t th e p a r t i c l e s o f a c l a y a r e
v e ry l a r g e c o o p e re d t o m o le c u la r d im e n s io n s s o t h a t any p o r e s
in v o lv in g th e s p a c in g o f th e s e p a r t i c l e s m u st a ls o be l a r g e
b y c o m p a r is o n *
S p a c in g o f t h e c l a y p a r t i c l e s
in an a d so rb e n t
b y m ea n s o f a n a e r o g e l f o r m a t i o n d o e s n o t i n o r e a s e b e n z e n e
a d s o rp tio n *
I n o t h e r w o rd s t h e f o r m a t i o n o f l a r g e p o r e s o r a
g r e a t e r am ount o f a v a i l a b l e p a r t i c l e a r e a i s n o t e f f e c t i v e
in
g r e a t l y c h a n g in g th e a d s o r p tio n *
T he p r o c e s s o f a c i d b o i l i n g g r e a t l y
a d s o r p tio n by th e T exas b e n to n ite *
in c r e a s e s th e
I t w a s m e n tio n e d t h a t t h i s
e f f e c t i s p r o b a b ly due t o a l a r g e a r e a i n c r e a s e c a u se d by th e
f o r m a t i o n o f s m a l l s i l i c a c a p i l l a r l a s w h ic h a t t h e sam e tim e
? aha p o s s ib l e t h s c o n d e n s a tio n *
Ths s i l i c a t e t r a h s d r a h a v e
a g r e a t e r a m o u n t o f u n s a t u r a t i o n , b u t t h s a to m s p r o b a b l y
h a v e t h e sem e a r r a n g e m e n t a s t h e y d o i n t h e c l a y s o t h a t
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
1
a n o r d e r ly a rra n g e m e n t s t i l l o b ta in s *
T he hind o f aeld need
en d th e s u b s ta n c e s p r e s e n t in th e b o i l i n g s o l u t i o n g o v e rn
t h e n a t u r e o f t h e c a p i l l a r i e s fo rm ed *
a d so rb ed m e ta llic
m e a d d itio n o f h ig h ly
io n s o r a o le e u l e s t o th e s o ld c a u s e s in *
c re a s e d a d s o r p tio n f o r ben zen e in c e r t a i n p r e s s u r e re g io n s *
T h is a ls o s c a n s to be a m a tte r o f g o v e rn in g th e n a tu r e o f
t h e c a p i l l a r l e a fo rm e d * o r o f f o r m in g a s y s te m o f m o re u n i *
fo rm c a p i l l a r i e s *
The p r e s e n t e x p e rim e n ts sh o e t h a t th e a d d i t i o n o f
A ljO ^ a n d - i C j t o a c i d b o i l e d c l a y u n d e r c e r t a i n c o n d i t i o n s
g re a tly
in c r e a s e s th e a d s o rp tio n *
T h i s may b e due t o t h e
p re s e n c e o f a h ig h ly a c tiv e m a te r ia l in
th e l a r g e r p o re s o f
t h e o l a y e n h a n c e d b y t h e a c t i o n o f t h e c l a y ? s own s m a l l o a *
p illa rie s *
I n c e r t a i n o th e r c a s e s л h o w e v er, th 6 a d d it i o n o f
S iO x o r o t h e r o x i d e s a c t u a l l y d e c r e a s e t h e a d s o r p t i o n b e c a u s e
a p p a r e n t l y t h e i r m e th o d s o f f o r m a t i o n a r e s u o h t h a t a d s o r p *
t i v e a r e a s a r e b lo c k e d o f f *
I n th e p re c e d in g p a ra g ra p h s i t
d is tin c tio n
nay ap p ear th a t a
i s b e i n g made b e tw e e n " c a p i l l a r y c o n d e n s a t i o n "
and s u r f a c e a d s o rp tio n *
The i n d i c a t i o n s fro m e x p e rim e n t a r e
t h a t t h e s e d i f f e r e n c e s a r e o f d e g r e e r a t h e r t h a n k in d * h e n c e *
w hen a n a o t l v e s u r f a c e i n a c a p i l l a r y a d s o r b s e n o u g h v a p o r
s o t h a t n o m o re m a t e r i a l c a n e n t e r * c a p i l l a r y c o n d e n s a t i o n
may b e s a i d t o h a v e s e c u r e d *
I n o t h e r w o rd s* t h e s u r f a c e
f o r c e s may b e f u n d a m e n t a l l y t h e sam e* b a t t h e i r a v a i l a b i l i t y
a n d r e l a t i v e a m o u n ts p r e s e n t u n d e r d i f f e r e n t t r e a t m e n t s
may impend upon s t r u c t u r e *
R eproduced with permission of the copyright owner. Further reproduction prohibited without permission.
A. r e v i s e d a p p a r a t u s f o r t b s m e a s u re m e n t o f v a p o r a d *
s o r p t i o n o n r e l a t i v e l y l a r g e s a m p le s h a s b e e n p r 
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