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O.G.Larionov, Yu.A.Eltekov
I n s t l t u t e of P h y s i c a l C h e m i s t r y of t h e Academy of Sciences
of t h e USSR, L e n i n s k i prosp., 31, MOSCOW,
USSR
ABSTRACT
The c r i t e r i o n of e q u i l i b r i u m i n t h e a d s o r p t i o n thermodynamics is t h e
e q u a l i t y of t h e G i b b s e n e r g y c h a n g e t o z e r o
(dG)
( 1 )
( 2 )
m i = m i o + R T ln(xiyi)
From e q u a t i o n (2) it follows t h a t :
(3)
A f t e r d i v i d i n g s u c h a n e q u a t i o n f o r component 1 by a S i m i l a r e q u a t i o n f o r
component 2 r e o b t a i n :
E q u a t i o n (5) is v a l i d f o r t h e c a s e of molecule s i z e e q u a l i t y of s o l u t i o n
components. T h i s e q u a t i o n d e s c r i b e s a n a d s o r p t i o n i s o t h e r m of s o l u t i o n s .
From eqn. (5) w e can d e r i v e e n e q u a t i o n f o r xis i.e. a n i s o t h e r m of t h e
whole c o n t e n t a n d a l s o G l b b s excess a d s o r p t i o n i s o t h e r m a s t h e d i f f e r e n c e
xis-xiLr
m G K Y -
r yo c x -
c h e m l c a l p o t e n t i a l s of s o l u t i o n
components (dG/dxi);
G i b b s f r e e energy;
adsorption equilibrium constant;
a c t i v i t y coefficlent;
G i b b s excess a d s o r p t i o n ;
dead volume o f c h r o m a t o g r a p h i c
column;
c o n c e n t r a t i o n (mole/l)
mole f r a c t i o n of s o l u t l o n
component;
S - adsorbent
Va - volume of
surface area;
adsorption layer;
w - e l u e n t flow r a t e ;
V r - r e t e n t l o n volume;
k - c a p a c i t y f a c t o r ;
subscript i
1-th s o l u t i o n component;
2038
vr
--- w
( 8 )
UC
combining e q u a t i o n s ( 7 ) a n d
we get:
(8)
Vr
dr
Vo + S(--Ic
( 9 )
dC
__
= (K -
1)
dx
obviously
if
(1
X)2
[i
(K
- Kx2
_____________
t h e n dr/dx
- 1)Xl2
V r = V o + V a ( K - 1)
hence
or
Va/Vo(K - 1)
k' = ( V r - Vo)/Vo
Theref o r e
K = k'Vo/Va
lC'VoW/S
+ i
= V o - Va -- k'
-Vo/Va -- K = 0
(14)
------ f =
XilX2S
( G )
-____ 1
= exp(
( 15
RT
combining eqn.'s
(13)
and
In K = ln(Vo/Va k' +
(16):
N o w consider c a p a c i t y f a c t o r , k':
In K = ln(Vo/Vak' +
2039
1)
1)
= a + nb
= a + nb
(17)
(18)
YO
(19)
In(---k' + 1) = In -- + In k'
Va
Va
or
In k' = a' + n b
(20)
S u n equations a r e v e r y o f t e n mentioned i n published a r t i c l e s .
The h i g h e r members of t h e homologous s e r i e s h a v e more conformational
degrees of freedom a n d f o r m innermolecular connections, a s f o r example
oxyethylated phenols, b u t i t occurs only f o r n I 6 . The d e v i a t i o n s f o r t h e
lower homologous s e r i e s members a r e now explained b y i n s u f f i c i e n t accuracy
i n V o d e t e r m i n a t i o n , because a t l o w r e t e n t i o n values t h e i n f l u e n c e of V,
d e t e r m i n a t i o n e r r o r increases.
The problem of dead volume d e t e r m i n a t i o n is not a s easy a s one can
For example, for t h e s y s t e m acetonitrile-water-Separon-C18
think.
p r a c t i c a l l y a l l t h e known methods gave t h e dead volume value f o r one column
(100x3 mm) not less t h a n 1.03 m l , b u t compounds l i k e 4,6-dioxypyrimidine or
u r i c a c i d h a d n o t i c a b l y l e s s r e t e n t i o n volumes, a n d consequently t h e i r
values of k' were less t h a n zero. However, it does not correspond t o t h e
opinion t h a t lnk' is t h e e n e r g e t i c p a r a m e t e r o f a chromatographic System.
T h i s opinion i s based on t h e well known e q u a t i o n o f f e r e d b y S c k o t t and
Kucera [3]
k' = V o / V a K i
( 2 1 )
dx
vr
0
dl?
[[V
J
--I
" d x
dx
( 2 2 )
2040
(28)
Ki
Vo/Va
In k' = A - n lnc
In t h e e l u t i v e chromatography negligibly
s u b s t a n c e s a r e usually i n t r o d u c e d , hence
t h e n we can w r i t e
XI
+ x2 =
small
quantities
of
(33)
or
(34)
hence
f(Kl
+ (KI
- 1)
[l +
1)
adsorption
(35)
X1
(91 -
_____----------
1)
X112
(36)
Kl
a.