Reactive Polymers, 21 (1993) 53-64 53

Elsevier Science Publishers B.V., Amsterdam

Langmuir isotherm and its application

in ion-exchange reactions
Nasr Z. Misak

Nuclear Chemistry Department, Nuclear Research Centre, Atomic Energy Establishment,

Atomic Energy Post 13759, Cairo, Egypt

(Received July 13, 1992; accepted in revised form June 14, 1993)

Abstract

The simple Langmuir isotherm equation for adsorption of a single adsorbate on a

single-site surface is still frequently applied to ion-exchange reactions. When a single
straight line is not obtained by this equation, a multi-site surface is assumed and
additional terms of the equation are used for analysis. Ion exchange should be considered
as a competitive adsorption of two sorbates. Apart from the fact that the selectivity
coefficient or separation factor must be constant, other conditions of application of the
equation are frequently overlooked. This paper is intended to stress these conditions and
to point to the uncertainties in the quantities and conclusions derived from the Langmuir
plots of ion-exchange data.

Keywords: Langmuir isotherm; mass action law; single-site adsorption; multisite adsorption;
adsorption; ion exchange

Introduction plicit justification of its application. Unless

such a justification exists, the conclusions
The similarity and possibility of use of
drawn or the quantities calculated may
both Langmuir and mass action equations in
largely be wrong. It is intended here to show
the case of ion exchange has long been known
the scope and limits of the applicability of
[1-3]. It is readily conceivable that for ion
the equation. It is hoped to remove a lot of
exchange a Langmuir competitive adsorption
the existing confusion. Brief explanatory
model is involved. Thus, in the case of a
comments will also be given on some of the
single-site surface, the Langmuir simple
existing literature. In addition, for a general
equation for a single adsorbate is not ex-
comparative representation of the problem
pected applicable except under certain con-
of ion-exchange equilibria, a very brief ac-
ditions.
count of the approaches describing these
Actually, many papers use the simple
equilibria is included.
equation without giving any explicit or im-

0923-1137/93/$06.00 © 1993 - Elsevier Science Publishers B.V. All rights reserved

54
Discussion
Single-site homovalent exchange: equivalence
of Langmuir and mass action equations
The single-site Langmuir equation for ad-
sorption of a single component A is [4]:
QKACA
qA = 1 + KAC A
where qA is the amount of A sorbed ( m e q / g ) ,
CA is its equilibrium concentration ( m o l /
dm 3) in solution, Q is the maximum sorption
capacity, and K A is a constant related to
sorption energy (equilibrium constant, in the
Langmuir sense, of sorption of A). Usually,
eqn. 1 is put is the following linear form,
from which Q and K A can be obtained:
CA 1 CA
--+--
qA KAQ Q
Boyd et al. [1], considering a competitive
adsorption of two monovalent ions A and B,
give the following equation:
QKACA
q A = 1 + KAC A + K B C B
These authors declare that KACA + KBC B
>> 1 because an appreciable negative charge
cannot exist on the surface. Thus,
QKACA
qA = KACA h- K B C B
Eqn. 4 can be rearranged, taking into ac-
count that Q = qA -1-qa, resulting in:
KA qA/Q'CB qACB
K. . . . .
KB qB/Q'CA qBCA
K is obviously the selectivity coefficient of
the exchange reaction RB + A ~ R A + B,
where R represents the solid matrix. It can
easily be seen that eqns. 4 and 5 also apply
for homovalent exchange, i.e., when ions A
and B have the same charge.
From eqns. 4 and 5 (or from the following
general eqns. 16 and 17, assuming x = y), we
N.Z. Misak /React. Polym. 21 (1993) 53-64
get the following equation:
cA c. cA
--=--+-- (6)
qA KQ Q
As could be intuitively felt, a straight-line
Langmuir plot of CA/q A versus CA can be
obtained if C B is kept constant and if the
selectivity coefficient K remains constant.
(1) The latter requirement, which is a general
requirement in homovalent exchanges, means
that the activity coefficient ratios of the ions
in the solution and solid remain the same in
the experiments. In solution, this may be
achieved by the use of sufficiently dilute so-
lutions, involving no complexation or hydrol-
ysis (activity coefficients are almost equal to
1), or by the use of a constant ionic strength.
In the solid, the activity coefficient ratio may
very with exchanger composition, even for
(2) one type of site (homogeneous exchanger
with sites of the same binding energy). This
is the case, because the activity of one species
of ions may be affected by the other species
present on the surface [5,6]. It may, however,
be imagined that such an effect will be
(3) smaller when the surface site density is
smaller, i.e. when the exchange sites are
more widely separated from each other.
Assuming that C B in eqn. 6 is equal to
C O- C A, where Co = CA + CB, the following
equation results:
(4) K- 1 CO
q--2
As with eqn. 6, a straight line between
CA/q A and CA, from which K and Q can be
(5) obtained, results if C o and K remain con-
stant.
Single-site heterovalent exchange
Equivalence of the Langmuir and mass action
equations and plots using the selectivity coeffi-
cient
In the general case of exchange adsorption
of two cations A x + and B y + of different
N.Z. Misak / React. Polym. 21 (1993) 53-64 55

charge, Boyd et al. [1] give the following Using eqns. 9 and 10, it can be proved that
equations for the Langmuir approach: the last two terms in the denominator of eqn.
13 are equal to f a + f J l - - f A - - f B . This
QKAC~
(8) quantity should be much higher than 1, oth-
qA = K A C ~ + K B C ~ erwise a considerable negative charge would
As eqn. 8 is generally not valid, which will be present on the surface [1]. Eqn. 13 thus
be seen later, it seems instructive to give in becomes
some detail the sequence of equations for f l / x = ( lt~l/xl/x'][lC1/x~t'l/xrr(x"-'A
-~'A ]\'~A '~A JA 1)/x
the Langmuir approach in this case. k" ~ k'( 1 y ) / x ~ ( 1 - y ) / x f ( y - l ) / x ) - I
The surface reactions can be put as "~ B"~ B ' " A ~A JA
(14)
xS + A ~ + ~- SxA
Using fA l/x, dividing by fA(y 1)/x and rear-
and ranging, we get
yS + B Y + ~-~-
- SyB f~(/XKBC B
1- - fA- lgy/xl~y/x (15)
KA and KB are equal to: "~A "-'A
y
fA Assuming that KA/K ux = K and fa = qA/Q,
KA= CA(1 _fA_fB)X (9) we get
(qA/Q)YC~
f. K= (qB/Q)~C~ (16)
KB= CB(1 _fA_fB)y (10)
K is the equilibrium quotient or selectively
where fA and fB are the fractions of surface coefficient of the exchange reaction
covered by A and B, respectively; fA = qA/Q
XSyB+yA ~+ ~ y S , A + x B y+
and fB = qB/Q"
From eqns. 9 and 10 the following equa- From eqn. 15 and assuming fA = qA/Q, we
tion can be derived: get the equation
Qy/Xk'y/xg~y/x
K Al / X r"~A1 I x//'~~ Bl / y (""B
' , 1/y : f l / x / f l B / Y "'-A ""A
qA = [-)(y-x)/xk,-y/xl.-,y/x
~,~ "~'A " A -'1-KBCBq(Ay - x ) / x
Hence
fa = fx/yl( ¢" / l g y / x ( - ' y / x
(17)
JA "~ B'-" B / ' ~ A "-'A (11)
From eqn. 17 it is readily seen that even if
From eqn. 9 we have C B is constant, the simple Langmuir equa-
f~/~=K1A/*C1/~(1 --fA --fB) (12) tion cannot describe the adsorption of A,
i.e., the variation of qA with C A. For ho-
Transferring the value of fB from eqn. 11 to movalent exchange (y = x ) , eqn. 17 becomes
eqn. 12, we get eqn. 4 given by Boyd et al. [1] for the ex-
change of monovalent ions.
fl/x = *XAlC'l/x['~l/x[l""A/[*--fA fy/XKBCBK~/,C~/]X A simplified Langmuir equation for the
case of heterovalent exchange can be ob-
= (K1A/xC~/X)( 1+ "'Ak'l/x("l/xf(x-x'A JA 1)/x
tained as follows. From eqn. 15 and assum-
ing f A = qn/Q, we have
+KBCBK(AI-Y)/xc(~-yl/xf(AI-y)/x) -1 (1 qA/Q) ~/y = (qA/Q)" C~/YK{3/y
- (18)
(13) KAC A
56 N.Z. Misak / React. Polym. 21 (1993) 53-64

If the approximation (1 - q A / Q ) x/y = 1 - Eqn. 23 shows that a straight-line relation-

( x / y ' q A / Q ) is made, we get the following ship between CA/qA and C A cannot be ob-
expression: tained, as in the case of homovalent ex-
QKACA change, by keeping C o constant instead of
C a. However, such a straight line may be
qA = ( x / y ) K A C A + C~/YK~/y (19)
obtained if C A << C 0.
As the selectivity coefficient K equals
K Ay / K B,
x
eqn. 19 becomes Plots using the separation factor
Considering eqns. 9 and 10 and assuming
QK1/YCA
bA = f A / C A and b B = f B / C B it is easy to see
qA = ( x / y ) K 1 / Y C A _t_C~/y (20) that bA/b B, which is the separation factor a,
can be defined as follows
If y = 1 and x = 2, 3 , . . . , eqn. 19 becomes
similar in form to, but not identical with eqn. fACB
8 given by Boyd et al. [1] for the general bA/b B = a = - - (24)
CAfB
case. Obviously, eqn. 8 does not represent
the general case of heterovalent exchange. Also, it can readily be seen that
y x x y x
Eqn. 20 is similar in form to eqn. 4 for K A / K B = ff, " C B / C ~ "fB (25)
homovalent exchange and can give rise to a
From eqns. 24 and 25 we get:
simple Langmuir plot similar to that given by
eqn. 6. Thus, from eqn. 19 we have
KA/K B (26)
(x/y)CA KU'CU'
CA/qA = "1- (21)
Q QKA From eqn. 15 we have
Similarly, eqn. 20 gives rise to the following (1 --fA) x
analogous equation: = - - (27)

(x/y)CA c /y From eqns. 26 and 27 we get:

CA/qA +- - (22)
Q QK
CB
Considering the above approximation
leading to eqns. 19 and 20, it can be readily f~, = a-x. CI
calculated that the error in the quantity (1 - Rearrangement results in
q A / Q ) x/y on approximation is less then ca.
1 --fA CB
10% for x / y values < 1 (A is the ion of
lower charge) and q A / Q values < ca. 0.65 _+ fA "CA
0.70. For x / y > 1, such an error ( < 10%) is Assuming fA = q A / Q and rearranging, we
observed up to q a / Q values of 0.45, 0.35, obtain
0.25, 0.15 and 0.10 for x / y values 4/3, 3/2,
2, 3 and 4, respectively. The error is smaller
,QCA
when the value of q A / Q is smaller. qA = a C A + CB (28)
If the total concentration C o ( m e q / c m 3) is Eqn. 28 is similar to eqn. 4 for homovalent
kept constant, we get the following equation exchange and can be put in a form similar to
by assuming C B = (C o --XCA)/y: the corresponding eqn. 6:
(x/y)C A (Co-xCA) x/y C A C B
CA/qA = Q + y X/YQK (23) CA/qA = ---Q + aQ (29)
N.Z. Misak /React. Polym. 21 (1993) 53-64 57

or the corresponding eqn. 7: Hinshelwood [7] gave the following Langmuir

expression for multi-site adsorption of one
CA/qA = - ~ 1 -- --~y + --ayQ (30) adsorbate A
K1Q1CA K2QzCA
Eqns. 29 and 30 show that if a is constant, qA = + + ... (32)
1 + K1C A 1 + K2C A
keeping C B or C o constant gives, as in the
case of homovalent ion exchange, a straight- Each term in eqn. 32 is the single-site
line relationship between CA//qA and C A. Langmuir expression given by eqn. 1. Eqn. 31
From the straight line, o~ and Q can be becomes similar to eqn. 32 if C B is constant.
determined. F r o m eqn. 25 we have If C B in eqn. 31 is equal to C 0 - C A, it is
easy to see that each term in this equation
x[qA/O_l " x will be replaced by a term of a similar form,
1 namely Q K C A / [ C A ( K - 1) + CII]-
Therefore, ~ may fortuitously happen to Heterovalent exchange
remain u n c h a n g e d or little changed over the Eqn. 20 can be extended, similar to the
exchanger composition involved, at the time case of homovalent exchange, to give the
when K is continuously changing. Obviously, following equation which is analogous to
a, in contradistinction to K, cannot be con- eqn. 31:
sidered as a constant related to the adsorp-
qA = qlA -{- Q 2 A "[- • • •
tion energy of the sites occupied. Therefore,
in heterovalent exchange where the Lang- Q IK~/ YCA
muir equation is obeyed, one must find out (x/y)K~/YCA + C~/y
w h e t h e r this is due to the constant K or c~
before considering values for Q. Q2K~/YCA
+ (x/y)K' /YCA + C /Y + ' " (33)
Multi-site Langmuir equations It must, however, be noted that, as previ-
ously mentioned, this equation may be used
Homovalent exchange for x/y values < 1. For x/y values > 1, the
Starting from eqn. 4 or 5 (or from eqn. 16 term for each site applied for site occupan-
or 17, assuming x = y), i.e., from either the cies of about 45% at x/y = 4 / 3 and 10% at
Langmuir or mass action equations for sin- x/y = 4.0.
gle-site adsorption, the following multi-site On the other hand, eqn. 28 in which the
adsorption equation can be obtained: separation factor is used can be extended to
qA=QIA +q2A + ' ' ' give the following equation whose terms ap-
K1Q1CA KzQzCA ply for any site occupancy:
- + + ... (31)
K1C A + C B K 2C A + C B
qA = qlA -k- qZA + "" •
alQ1CA o~2QzCA
In this equation, the numbers 1, 2 . . . refer to - + +... (34)
oL1C A -{- C B o ~ 2 C A ~- C B
the different sites, Q = Q1 + Q2 + . . . , Q1 =
qlA + qlB, Q2 = q2A + q2B, K1 corresponds to Analogous to single-site adsorption, eqn.
the following reaction (similar equations rep- 34 is similar to eqn. 31 for homovalent ex-
resents K 2 , . . . ): change. Assuming C B in eqn. 34 equals Co/y
q l A / Q I " CI~ --XCA/Y , it is easy to see that each term in
K1= this equation will be replaced by the similar
qIB/Q1 "CA term olQCA/{CA[a -- ( x / y ) ] + C(>/y}.
58 N.Z. Misak/ React. Polym. 21 (1993) 53-64

For the analysis of composite isotherms Explanatory remarks and comments

represented by eqns. 31, 33 and 34, we refer
to the method given by Loganathan and Bu- The first condition of applying the simple
rau [7]. In this method it is assumed that at (single-site single-adsorbate) Langmuir equa-
certain (high) C A values and sufficiently dif- tion to ion exchange on a single-site surface
ferent values of K a, K 2, etc., or al, a2, etc., is that the selectivity coefficient or separa-
the first term (or terms) can be assumed tion factor remains unchanged or little
equal to Q1 (or Q1 + Q2, etc.). In the case of changed over the exchange composition in-
two sites, eqn. 31 for example, can be put in volved. The second condition for homovalent
the form: exchange and for heterovalent exchange, in-
volving an almost constant separation factor,
KeQ2CA is that the concentration of one of the ions
qA = Q1 q- (35)
KzC A + C B or of the total solution is constant. Unlike
the selectivity coefficient, the separation fac-
Rearrangement results in tor obtained from the Langmuir plot cannot
CA CB be regarded as a constant depending on site
CA/qA = + adsorption energy.
Q1 + Q2 K2(Q1 + Q2) In the case of heterovalent exchange in-
volving a constant selectivity coefficient, the
QICB
(36) second condition is the constancy of the con-
qAK2(Q1 + O2) centration of one of the ions. The constancy
of the total solution concentration is not a
CA CB(qA Q1)
satisfactory condition. Also, the straight-line
-

+ (37)
Q1 + Q2 K2qA(Q1 + Q2)
If it can be considered that qA >> Q1 (at high
C A and qA), we get the following equation
representing a straight line (given that C a is
constant) from which Q1 + Q2 (total capacity
for this case of two sites) and K 2 can be
calculated:
CA C8
CA/qA = + (38)
Q1 + 02 K2(Q1 + 02)
If qA does not happen to be much higher
than Q1, eqn. 38 does not apply. In this case,
Loganathan and Burau [7] indicate that a
two-variable multiple linear regression analy-
ses can be used to fit the experimental data
to the simplified expression
1 the other ion.
CAIq A = k 1 + CAk 2 + %--k 3 (39)
~A
where C A is one variable and 1 / C A is the
other.
Langmuir plot does not apply over the whole
exchanger composition. The plot for the ion
of smaller charge is more favourable as it
gives a straight line up to relatively high
(65-70%) occupancies by this ion. For the
ion of higher charge, the occupancy at which
the straight-line relationship is no more
obeyed is lower when the ratio of this charge
to the charge of the other ion is higher.
When this ratio equals 4, the occupancy is
about 10%.
In the case of a multi-site surface, an
equation of additional terms of the simple
equation applies under the same conditions
given above. For heterovalent exchange, the
equation using the selectivity coefficient may
be used for the ion of smaller charge, but not
for that of a charge more than double that of
The simple Langmuir equation has been
used in many works [1-3,7-18] to describe
ion-exchange data. However, the above-men-
tioned conditions for the applicability of the
N.Z. Misak / React. Polym. 21 (1993) 53-64
equation were frequently not observed. The
work with hydrous oxides was perhaps more
fortunate in this respect. This work generally
involved a constant pH, i . e . constant concen-
tration of one of the ions (H +) involved in
the exchange. Besides, as expected, it was
often found that the equation was obeyed at
low cation concentrations on the surface [8-
12,14-16] where the ratio of activity coeffi-
cients for the surface species can be claimed
to be 1 [19]. U n d e r other conditions, the
Freundlich isotherm was found to apply
[14,20-25].
Concentrating on some exemplary and
rather recent works in the literature, we find
that Konya and co-workers [17,18] applied
the simple Langmuir equation (eqn. 2) for a
single adsorbate to the exchange adsorption
of Zn(II) on Ca(II)-bentonite. They deduced
from the composite isotherms obtained the
presence of at least three types of site in the
solid. However, eqn. 2 or 32, composed of
additional terms of eqn. 2, is not expected to
apply under the conditions given where the
individual concentrations of Zn and Ca and
their total concentration changed along each
isotherm. Besides, the selectivity coefficient,
calculated by the authors from the law of
mass action, decreases considerably with the
increase of the amount of Zn in bentonite to
about 60% of the maximum loading [18].
Afterwards, it changes a little with loading
because the surface activity coefficient ratio
of Zn and Ca remains almost unchanged. No
isotherm data are given in this favourable
region of having an almost constant selectiv-
ity coefficient. Therefore, the deduction
made by the authors about site types may be
wrong.
Konya and co-workers [17,18] give amounts
for the sites that increase with increasing
temperature. Though this may be due to a
rather overlapping nature of site energies, it
can also be due to a large uncertainty arising
from the non-observance of the conditions of
applicability of the Langmuir equation. Be-
59
sides, the number of different sites seems to
be calculated by the approximate equation
given by Loganathan and Burau [7], who
assumed, as in eqn. 38, that at higher con-
centration qA >> Q~" Assuming different
types of site, the data show that the number
of sites in the second type is not much higher
than that in the first type. Hence, the ap-
proximation involved is a drastic one. The
ion-exchange isotherms indicate that the
Z n - C a exchange in bentonite is endother-
mic. Thus, the parameter given by the au-
thors (equivalent to 1 / K A in eqn. 2) should
have decreased with the increase of tempera-
ture. The results of the authors, however,
frequently show a reverse trend. This may
partly be due to the adopted increase of the
number of exchange sites with the increase
of temperature.
Loganathan and Burau [7] applied the sin-
gle-adsorbate Langmuir equation to the
sorption of Ca, Zn and Co by manganese
dioxide. These authors worked at a constant
pH. For Ca(II) where the exchange involved
only H + in the oxide, a good straight line
was apparently obtained up to ca. 40% of
the total capacity. This is in conformity with
what we have mentioned for a divalent ion
replacing a monovalent one. The selectivity
coefficient calculated by us for this exchange
from the data given was found to be equal to
ca. 0.26, 0.30, 0.32 and 0.40 × 10 4 at cal-
cium occupancies of ca. 26, 37, 42 and 53%,
respectively. Thus, K is almost constant up
to about 40% occupancy. Hence, the results
are well founded.
In the case of Zn(II) adsorption, these
authors gave a two-site isotherm explained
by exchange with H + sites and structural
Mn(II) sites (higher energy) in the oxide.
Along the high concentration part of thc
isotherm, where the exchange might have
involved mainly H +, the concentration of H *
was kept constant (constant pH). Since the
overall capacity mainly involves this ex-
change, such capacity, calculated from the
60
high-concentration part on the basis of an
exact equation (similar to eqn. 39), may
probably involve only a relatively small error.
With Co(II), the sorption involves, in addi-
tion, structural Mn(III) sites (highest energy)
in the oxide. The capacity due to these and
the Mn(II) sites is relatively high. It is there-
fore possible that the calculated overall ca-
pacity of the oxide for Co(II) involves a rela-
tively large error, though the pH is kept
constant. For Z n ( I I ) / M n ( I I ) and Co(II)/
Mn(II), Mn(III) isotherms constructed from
the amount of manganese released, the ca-
pacities given due to exchange with struc-
tural manganese ions are probably in large
error, because the manganese concentration
in solution changed all the time. This is
probably the reason for the considerable dif-
ferences found between these capacities and
those calculated from the overall isotherms.
When the simple Langmuir equation is
applied to the sorption of metal cations on
hydrous oxides and H ÷ (pH) and anion con-
centrations are not maintained constant, the
capacity or sorption heat values obtained [13]
can be highly unreliable. The applicability of
the equation in such cases is only a fortuitous
misleading event. Cation sorption from acid
solutions on hydrous oxides may be affected
by the anions present because these anions
are sorbed from such solutions. Anion sorp-
tion depends on acidity and anion concentra-
tion, and it may affect cation sorption even if
the cations and anions are sorbed on differ-
ent sites [26]. Determination of cation sorp-
tion on hydrous oxides at constant pH is
necessary not only to satisfy a condition for
the applicability of the equation but also to
work at a constant electrostatic interaction at
the surface [27].
Models and approaches describing ion-ex-
change equilibria
Many models or approaches have been
suggested for describing ion-exchange equi-
N.Z. Misak/ React. Polym. 21 (1993) 53-64
libria and were claimed to fit certain ion-ex-
change data. Models, throwing light on the
interactions involved in ion exchange, can be
useful in predicting ion-exchange equilibria
(selectivity patterns) and changes in selectiv-
ity coefficient or selectivity in the same ex-
changer or from one exchanger to another.
An excellent account of most of the ap-
proaches is given in the excellent book of
Helfferich [3]. Because of its relevance to the
present work, a very brief account of the
most important approaches is given below.
Many of the approaches given are based on
the law of mass action which is equivalent to
the Langmuir equation. However, except
where rigorous thermodynamics are used, site
heterogeneity is ignored.
The model adopted by many authers for
ion-exchange resins [3] and by Bukata and
Marinsky [28] for open zeolites is the osmotic
(swelling) pressure model. In this model, the
water and cations in the exchanger are con-
sidered as a concentrated electrolyte solu-
tion. The molal selectivity coefficient K '
(molal concentrations are used for the solid
phase in contrast to the previously men-
tioned selectivity coefficient K where equiv-
alent fractions are used) is given by:
--x
In K ' = In ~ + In y~" + YUA)
(40)
where y is the molal activity coefficient (the
bar refers to the solid phase), ~ the osmotic
pressure, and u the partial molar volume.
Bukata and Marinsky [28] have found that
eqn. 40 applies to Linde A zeolite and that in
certain cases [29] it applies where electro-
static models like those of Pauley and Eisen-
man (to be discussed later) fail. Considering
solvated ions (volume u') and the system
behaving ideally except for solvation, Gregor
and co-workers [30-32] reduce eqn. 40 to
77"
In K ' = - - ( x v ' B - y v ) ~ ) (41)
RT
N.Z. Misak / React. Polym. 21 (1993) 53-64
Eqn. 41 explains the experimentally ob-
tained general preference of strong-acid
resins to the alkali ion of the smaller hy-
drated radius and the decrease of the affinity
of the resin to an ion as the exchange pro-
gresses. However, affinity reversals or cross-
overs in the In K ' - l o a d i n g curves of these
resins, obtained with the change of the de-
gree of crosslinking, are not predicted by this
equation [33]. Also, Gregor et al. [34] found
that the swelling pressure model does not
apply to many ion exchangers in strong-base
resins, and he was obliged to invoke the
concept of cluster ion-pair formation.
Harris and Rice [35,36] gave a somewhat
different model in which they assumed that
in the resin the ions are present as free and
bound (ion-paired with the fixed groups) ions.
The model predicts the experimentally ob-
tained increase of selectivity with the in-
crease of crosslinking, the decrease of the
equivalent fraction of the preferred ion, and
the dilution of the external solution. How-
ever, it is not in conformity with other exper-
imental facts [3,33]. Thus, it predicts an in-
crease of selectivity with increase of capacity
and it does not predict affinity reversals.
Pauley [37] suggested a simple electro-
static model in which all the counter ions are
assumed to be present in the exchanger at
the distance of their closest approach to the
fixed ionic groups. According to this model,
the thermodynamic equilibrium constant K~
for uni-univalent exchange is given by
-AG O Ne2 ( 1 1 ) (42)
In K ~ - R---T-- RTD- a°a a°
where N is Avogadro's number, e is the
electronic charge, D is the dielectric con-
stant, and a ° is the distance of closest ap-
proach. In accordance with experimental re-
sults, eqn. 42 leads to the preference of the
counter ion with a smaller a ° and to a linear
change of In K a with 1 / a °. However, the
61
model fails in many systems, as will be shown
below with Eisenman's model [38] which is a
development of Pauley's model [37].
Eisenman [38], working on ion exchange in
glasses and assuming that the counter ions
are bound unhydrated to the exchange sites
and that no change occurs in the entropy of
the exchanger, obtained the following equa-
tion:
_ AG o
In K~,- = (~-G e - A G h ) / R T (43)
RT
where A G h is the difference in the hydration
energies of the counter ions and ~--Ge is the
difference in their coulombic electrostatic in-
teraction energies with the exchange sites.
Eisenman's model application was consid-
ered for zeolites [39], organic resins [33] and
hydrous oxides [40-43]. Though useful pre-
dictions and conclusions could be obtained,
the model was found to apply only qualita-
tively in most cases and not to apply at all in
certain cases. Reasons for this are the ex-
changer entropy changes, which seem to be
mainly connected with ion hydration inside
the solid, non-coulombic interaction forces in
counter ion binding, and the heterogeneity of
ion-exchange sites [39-43]. The latter factor,
which is usually ignored in models, may lead
to a very complex variation of selectivity with
the ionic composition of the exchanger [5].
The most important approach applicable
to many ion exchangers in zeolites is that of
Kielland [3,44]. Kielland, considering the
heteroionic form of the exchanger as a solid
solution of the two-component ionic forms,
gives the solid phase activity coefficients of
the A and B components as
In fA = C~2 and In fB = CX2 (44)
where X is the equivalent fraction of the
component and C is the Kielland empirical
62
constant. K is then related to K a by the
equation
In K ( o r l n Kc) = l n K , - C ( 1 - 2XA)
"/A
+ In-- (45)
YB
From eqn. 45 In K (or In K c, where K c is
a corrected selectivity c o e f f i c i e n t equal to
K . YB/'/A) is a linear function of X A and K a
is equal to K or K c at X A-- 0.5. This was
the case with many zeolites [3] but, as we
m e n t i o n e d above, the situation may become
very complex with multi-site exchangers. Eqn.
45 does not apply to organic resins and,
hence, the Kielland equation was not suc-
cessful with these exchangers [3]. Kielland's
equation has been theoretically proved by
Barrer et al. [45], using a statistical thermo-
dynamic approach. The latter approach has
been used by other authors [3,46-50] who
gave equations based on Jenny's model [51]
for ion exchange on colloidal aluminosili-
cates. These equations have apparently not
been tested enough. The simpler of these
equations [46,47] gives a constant selectivity
coefficient (ideal ion exchange), for homova-
lent exchange which is rarely the case.
Finally, we may mention the thermody-
namic t r e a t m e n t of ion-exchange data, where
activities are used instead of concentrations
in the law of mass action, and no models or
assumptions are suggested. The most rigor-
ous treatment is that of Gaines and Thomas
[52] who took into consideration electrolyte
sorption and changes in solvent content. Ne-
glecting these factors, which is frequently the
case, this and previous [3,53-56] treatments
give the following equation for Ka:
In K a = ( Y - X ) + f011n K c d X A (46)
For homovalent exchange, eqn. 46 shows that
K a is a kind of average of the values of K c
over the whole composition of the exchanger.
This average, which can very frequently be
N.Z. Misak / React. Polym. 21 (1993) 53-64
taken as the value of K c at 50% loading, can
be used for comparing selectivity in the same
exchanger and in different exchangers
[13,57-59].
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