ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2018, Vol. 92, No. 2, pp. 265–270. © Pleiades Publishing, Ltd.

, 2018.
Original Russian Text © N.R. Meychik, S.I. Stepanov, Yu.I. Nikolaeva, 2018, published in Zhurnal Fizicheskoi Khimii, 2018, Vol. 92, No. 2, pp. 251–256.

CHEMICAL KINETICS
AND CATALYSIS

Calculating the Ionization Constant of Functional Groups

of Carboxyl Ion Exchangers
N. R. Meychika,*, S. I. Stepanovb, and Yu. I. Nikolaevaa
aDepartment of Chemistry, Moscow State University, Moscow, 119991 Russia
bMendeleev University of Chemical Technology, Moscow, 125047 Russia
*е-mail: meychik@mail.ru
Received March 1, 2017

Abstract—The potentiometric titration of a weakly basic carboxyl cation exchanger, obtained via alkaline
hydrolysis of an acrylonitrile copolymer with divinyl benzene (degree of crosslinking, 12%) in a wide range of
variation in a solution of рН (2–12) and NaCl (concentration 0.01, 0.1, 0.5, 1 М), is considered. The maxi-
mum ion-exchange capacity of the ion exchanger for Na+ is determined (10.10 ± 0.088 mmol/g of the dry
mass) and found to be independent of the solution’s ionic strength. It is established that in the investigated
range of NaCl concentrations and рН, the acid–base balance is adequately described by Gregor’s equation.
The parameters of this equation are calculated as a function of the NaCl concentration: рKа = 8.13 ± 0.04,
n = 1.50 ± 0.02 for 0.01 М; рKа = 6.56 ± 0.04, n = 2.60 ± 0.07 for 0.1 М; and рKа = 5.66 ± 0.6, n = 2.62 ±
0.06 for 0.5 and 1 М. It is shown that to describe the acid–base balance correctly within the proposed model
we must estimate the adequacy of the experimental and calculated values of the ion exchanger’s capacity at
each рН value according to the calculated parameters of Gregor’s equation.

Keywords: carboxyl cation exchanger, ionization constant, solution ionic strength

DOI: 10.1134/S0036024418010156

INTRODUCTION monofunctional carboxyl cation exchangers synthe-

Studies of the acid–base properties of ion exchang-
ers with different structures of functional groups is
important, since their results serve as confirmation of
the chemical structure of the functional groups of an
ion exchanger on the one hand; on the other, they
allow us to determine the рН interval in which these
groups are ionized and can participate in ion exchange
reactions.
Information on the acid–base balance in carboxyl-
containing ion exchangers is extremely limited [1, 2].
These processes have been studied by potentiometric
means, and Gregor’s equation was used to calculate
the ionization constant of functional groups.
In the literature, the potentiometric curves of the
titration of carboxyl ion exchangers are analyzed in
coordinates рН = f(V), where V is the titrant volume
[1], or рН = f(М), where М is the amount of the added
equivalents of acid or alkali per 1 g of the dry mass of
the cation exchanger [2]. The total content of func-
tional groups and their degree of ionization at each рН
value are determined from the position of the neutral-
ization jump [1, 2] and thus from the amount of added
titrant, which is expressed either in equivalent or vol-
ume units; the values of рKа and n parameters are then
calculated using Gregor’s equation. Experimental
titration curves were calculated in this manner for
sized via alkaline hydrolysis of copolymers of acrylo-
nitrile (TOKEM-200; degree of crosslinking, 6% [2])
and divinyl benzene (TOKEM-250, degree of cross-
linking, 12% [1]). The authors of these works estab-
lished that at ionic strength I = 0.1, the Gregor’s equa-
tion constants are рKа = 6.59, n = 1.29 М in TOKEM-
250. At I = 1.0, there are two ionization steps in
TOKEM-200: рKа1 = 5.08, n1 = 1.50 and рKа2 = 1.36,
n2 = 0.43. However, the authors of these studies failed
to answer two questions: (1) Do the obtained Gregor’s
equation constants describe the acid–base properties
of carboxyl cation exchanger throughout the region of
рН variation? (2) How do the acid–base properties of
carboxyl cation exchangers vary when the ionic
strength of the solution is changed?
The aims of this work were to determine experi-
mentally the ionization constants of carboxyl groups
of cation exchangers based on copolymers of acryloni-
trile, methyl methacrylate, and divinyl benzene
(degree of crosslinking, 12%) via potentiometry; to
determine the dependence of the degree of ionization
of functional groups on рН and the NaCl concentra-
tion; to assess the adequacy of calculated and experi-
mental potentiometric titration curves over a wide
interval of рН; and to comparatively evaluate ways of
calculating the ionization constants of monofunc-

265
266 MEYCHIK et al.
tional carboxyl cation exchangers based on different
sets of experimental data.
EXPERIMENTAL
Carboxyl cation exchanger based on an acrylate
matrix was prepared via the radical suspension copo-
lymerization of acrylonitrile and methyl methacrylate
with divinyl benzene (12%) at OOO RZE-RKhTU,
according to the procedure described in [3]. Prior to
use, the cation exchanger was conditioned under
dynamic mode in a 3% NaOH–H2O–3% HCl–H2O
cycle. At the last stage, it was washed with water until
the absence of detectable Cl− ions in the column eluate.
Potentiometric titration was conducted in separate
batches [4]. Dry batches of conditioned cation
exchangers of 0.05 ± 0.001 g were placed in stoppered
flasks (volume, 50 mL) and poured with 20 mL of the
NaOH or HCl solutions of different concentrations
with constant ionic strength (I), adjusted by adding
the appropriate amount of sodium chloride (the back-
ground electrolyte). The range of variation in the acid
or alkali concentrations in the initial solutions was 0.1
or 0–10 mM, respectively, while that of the NaCl con-
centration was 0.01, 0.1, 0.5, and 1 М. After 48 h, the
samples were separated from the solution, рН was
determined in the latter using a Model 3320 pH meter
(Jenway, Great Britain), and the acid or alkali concen-
tration was found via titration with bromotymol blue
indicator. The acid or alkali concentration in the ini-
tial solutions was established in a similar manner. The
capacity of the cation exchanger at рНi was calculated
from the change in the Н+ or ОН– concentration in
the initial and equilibrium solutions:
(C o − C i )V
Si = , (1)
g
where Si is the capacity of the cation exchanger with
respect to NaOH at the corresponding equilibrium
рНi, in μmol/g of dry mass; Co and Ci are the initial
and the corresponding equilibrium NaOH concentra-
tion in the solution, mM; V is the solution volume,
mL; and g is the batch of the sample, g.
Experimental data at I = 1.0 were also presented in
the form of dependences рН = f(V), where V is the
titrant volume [1] and рН = f(М), where М is the
amount of added alkali equivalents [2], from which we
found in each case the neutralization point of the ion
exchanger and calculated the degree of dissociation
according to the method proposed by Saldadze in [5].
For each point of the potentiometric curve, the deter-
minations were made in 2–3 analytical repetitions.
The results were processed statistically using the Mic-
rosoft Excel and IBM SPSS Statistics programs.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
Calculating рKа from Dependences S = f(рН)
Potentiometric titration curves of the carboxyl cat-
ion exchanger represented by dependence Si = f(рНi)
are of a monosigmoid character and are characterized
by one inflection point in coordinates dSi = f(dpHi),
testifying to the monofunctionality of the studied cat-
ion exchangers (Fig. 1 shows an example of titration at
a NaCl concentration of 0.1 М). Regardless of the
concentration of the background electrolyte (СNaCl),
the capacity of the cation exchanger with respect to
Na+ reached its maximum level (Smax) at рН > 10:
10.10 ± 0.088 mM/g of dry mass. This value corre-
sponds to the total content of carboxyl groups in the
studied cation exchanger.
Using the experimentally obtained Smax and Si val-
ues, we determined the degree of dissociation of the
carboxyl group (αi) at corresponding рНi values
according to the formula
αi = Si/Smax, (2)
where Si is the ion exchange capacity of the carboxyl
groups with respect to Na+ at the corresponding equi-
librium рНi, and Smax is the total content of carboxyl
groups in the studied cation exchanger or the maxi-
ΔS/ΔpH
S
1
10 2
8 2
6
4 1
2
0 0
1 3 5 7 9 11 13
рН
Fig. 1. Potentiometric titration of the carboxyl cation
exchanger against a background of 0.1 М NaCl, presented
in the form of dependence S = f(pH), where S is the capac-
ity of the cation exchanger with respect to Na+ in mmol/g
of the dry mass of the ion exchanger. Points represent
experimental data; the solid line, the curve of potentio-
metric titration, calculated according to Eq. (4) with the
p K a' and n values established in this work at СNaCl = 0.1 М
(Table 1): (1) calculations according to Eq. (4) with the
p K a' and n values obtained in [1] for Tokem-250 cation
exchanger similar in structure at a solution ionic strength
of 0.1 М; (2) differential curve ΔS/ΔpH = f(pH), calcu-
lated according to the formula ΔSi/ΔpHi = (Si + 1 −
Si − 1)/(pHi + 1 − pHi − 1).
Vol. 92 No. 2 2018
 CALCULATING THE IONIZATION CONSTANT 267

Table 1. Effect of the background electrolyte’s concentration (СNaCl, М) upon the potentiometric titration of carboxyl-
containing cation exchanger on the values of the apparent ionization constant ( p K a' ) and constant n
СNaCl 0.01 0.1 0.5 1
p K a' 8.13 ± 0.04 6.56 ± 0.04 5.70 ± 0.02 5.62 ± 0.09
n 1.50 ± 0.02 2.60 ± 0.07 2.67 ± 0.09 2.58 ± 0.04
r 0.978 0.991 0.999 0.989
Calculations of p K a' and n were performed in accordance with Eq. (3); r is the correlation coefficient of dependence pHi = f(log(αi/(1 – αi))).

Table 2. Estimates of the correspondence between the experimental and calculated data on the potentiometric titration of
carboxyl cation exchanger at different NaCl concentrations in the solution (СNaCl, М); А and B are the parameters of regres-
sion equation (5)
СNaCl 0.01 0.1 0.5 1
А 1.004 ± 0.03 0.990 ± 0.016 1.04 ± 0.04 0.996 ± 0.004
В 0.0310 ± 0.180 0.024 ± 0.101 0.089 ± 0.273 0.004 ± 0.252
r 0.988 0.997 0.988 0.981

mum ion-exchange capacity of the carboxyl groups
with respect to Na+.
To calculate the ionization constants of the car-
boxyl group ( pK a' ) at each concentration of the back-
ground electrolyte, we used the equation proposed by
Gregor for describing the potentiometric titration of
polyelectrolytes based on the Henderson–Hasselbach
equation [6]:
pHi = p K a' + nlog(αi/(1 – αi)),
where pK a' is the apparent ionization constant, since
the value for weakly basic cation exchangers depends
on the concentration of ions in the solution [7]; αi is
the degree of dissociation of the group at correspond-
ing рНi; n is a constant that depends on the structure
of the polymer matrix and the nature of the counterion
[7], and is associated with the change in the electro-
static free energy of the macromolecule upon its neu-
tralization [6].
Calculations showed that regardless of the concen-
tration of the background electrolyte, the experimen-
tal curves with high correlation coefficients were lin-
earized in the coordinates of Eq. (3), in accordance
with which the pK a' and n values were calculated
(Table 1). For each NaCl concentration with the
obtained pK a' and n values (Table 1), the ion
exchanger’s capacity at the corresponding рНi were
calculated according to the equation
max
cal
Si = S
1 + 10 (рК а − рНi )/ n
' obtained potentiometric curves, we found neutraliza-
where S ical is the calculated ion exchange capacity of
carboxyl groups at рНi, mmol/g of dry mass; Smax is
the maximum ion exchanger capacity, mmol/g of dry
mass; p K a' and n are parameters of Eq. (3) (Table 1);
and the calculated potentiometric titration curves are
plotted (Fig. 1 shows an example at a solution ionic
strength of 0.1 М). The correspondence between the
calculated and experimental cation exchanger capaci-
ties was estimated via regression analysis according to
the equation
S ical = АS iexp + В, (5)
(3)
where S ical и S iexp are calculated according to Eq. (4)
and experimental ion exchanger capacities with
respect to sodium ions at the corresponding рНi val-
ues, respectively; and А and B are regression coeffi-
cients.
Calculations showed that the experimental and cal-
culated Si values were in complete agreement in the
рН regions of 2–12, as was indicated by the values of
the А and B coefficients (А → 1, B → 0, which is within
the error of the titration method) and the values of the
correlation coefficients (Table 2, Fig. 1).
Calculating рKа from Dependences V = f(рН)
and M = f(рН)
The potentiometric titration curves (I = 1.0) of car-
boxyl cation exchanger represented by the depen-
dences Vi = f(рНi) and Mi = f(рНi) have the same
character (Fig. 2). At рН ≥ 12, an increase in the
amount of added NaOH does not change the form of
the curve, indicating the complete neutralization of
, (4) carboxyl groups under these conditions. From the
tion points Mmax and Vmax corresponding to the total
concentration of carboxyl groups in the ion exchanger:
12 meq NaOH for Mi = f(рНi) and 3.5 mL NaOH for
Vi = f(рНi), respectively.

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 92 No. 2 2018

268 MEYCHIK et al.

M V pH
11
36 1
8 2
9

18
4
7

0
0 5 10 15
рН −0.5
Fig. 2. Curves of the potentiometric titration of carboxyl
cation exchanger at a solution ionic strength of 1М, pre-
sented in the form of dependences Vi = f(pHi) and M =
f(pH), where V and M are the amounts of added alkali at
the corresponding equilibrium рН, expressed in mL or
meq/g of the ion exchanger, respectively.
Using the obtained Mmax and Vmax values, we deter-
mined the degree of dissociation of the carboxyl group
(αi) at the corresponding рНi values according to for-
mulas:
αi =Mi/Mmax, (6)
αi = Vi/Vmax, (7)
10
where Mi and Vi are the amounts of added alkali,
expressed in meq/g of the ion exchanger or mL,
respectively, at equilibrium рНi; Mmax and Vmax are the
amounts of added alkali necessary for the complete
neutralization of carboxyl groups, expressed in meq/g
of the ion exchanger or mL, respectively.
Using the calculated αi values (Eqs. (6) and (7))
and the corresponding рНi, the dependences we plot-
ted in the coordinates of Eq. (3), and the рKа and n
values were determined according to the least squares
method (Fig. 3). These dependences are linear, since
the correlation coefficients are greater than 0.99. The
potentiometric curves were calculated using the deter-
mined рKа, n, and Smax values (Fig. 4).
0 0.5 1.0
log(α/(1 − α))
Fig. 3. Anamorphoses of the potentiometric curves of the
titration of carboxyl cation exchanger at a solution ionic
strength of 1 М in the coordinates of Gregor’s equation.
The degree of ionization (α) was calculated from depen-
dences (1) V = f(pH) and (2) M = f(pH) in accordance with
Eqs. (6) and (7), where V and M are the amounts of the
added alkali at the corresponding equilibrium рН,
expressed in mL or meq/g of ion exchanger, respectively.
Dots represent experimental data; dotted lines, the lines of
the trend: (1) рН = 5.46 log(α/(1 − α)) + 6.75, r = 0.996
and (2) рН = 4.51 log(α/(1 − α)) + 6.13, r = 0.996.
S
1
2
3
8
6
4
2

RESULTS AND DISCUSSION
Raising the concentration of the background elec-
trolyte from 0.1 to 0.5 M lowers the pK a' value of the
carboxyl groups of the ion exchanger by 0.86 units of
рН; i.e., their acid properties are enhanced, but the
pK a' value is not in the 0.5–1 M range of NaCl con-
centrations (Table 1). For weakly crosslinked (degree
of crosslinking, 1–4%) carboxyl ion exchangers, it is
known that the pK a' value depends on the concentra-
tion of the background electrolyte, and at 1 М the con-
centration of the latter is approximately equal to the
0 2 4 6 8 10 12
рН
Fig. 4. Calculated curves (Eq. (4)) of the potentiometric
titration of carboxyl cation exchanger; S = f(pH) at a solu-
tion ionic strength of 1 М (where S is the capacity of the
cation exchanger with respect to Na+ in mmole/g of the
dry mass of the cation exchanger): (1) calculations with the
p K a' and n values presented in Table 1 (dots represent
experimental data); (2, 3) calculations with the p K a' and n
values (Fig. 3) from dependences M = f(pH) and V =
f(pH), where M and V are the amounts of the added alkali
at the corresponding equilibrium рН, expressed in meq/g
of the ion exchanger or mL, respectively.

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 92 No. 2 2018

 CALCULATING THE IONIZATION CONSTANT
pK a' of the linear polyacid [6, 8]. Compared to weakly
crosslinked ion exchangers, the change in the pK a' val-
ues along with the concentration of the background is
smaller in the studied cation exchanger, and the
obtained pK a' value of 5.62 in 1 М NaCl (Table 1) is
greater than the value of this factor for polyacrylic acid
(4.8 [7]).
Parameter n (Eq. (3)) does not depend on the con-
centration of the background electrolyte in the range
of 0.1–1 M NaCl (Table 1). It is 2.62 ± 0.05, but falls
along with СNaCl by ~1.8 times, from 0.1 to 0.01 М.
According to current concepts, n is a constant that
depends on the structure of the polymer matrix and
the nature of the counterion [7], and is associated with
the change in the electrostatic free energy of a macro-
molecule upon its neutralization. In our experiment,
the first two variables remained constant. We may
assume that the changes in parameter n were associ-
ated with different trends in the change of the free
energy of a macromolecule upon its neutralization in
solutions with СNaCl = 0.01 and СNaCl ≥ 0.1 М. In the
first case, it fell; in the second, it grew [6].
A comparative analysis of the ways of calculating
рKа and n according to Eq. (3) shows that these values
differ as a function of the set of experimental data
(Fig. 3, Table 1). The agreement between the calcu-
lated and experimental values of the cation
exchanger’s capacity can serve as a criterion for using
one calculation procedure or another. The presented
data (Fig. 1) show that the values of the ion exchanger
capacity calculated according to Eq. (4) with рKа and
n values from dependence S = f(рН) correspond to the
experimental data (Figs. 1, 4, Table 2) with an accu-
racy sufficient for practical purposes throughout the
interval of рН variation, while рKа, and n found from
dependences V = f(рН) and M = f(рН) do not provide
such agreement (Fig. 4). We may therefore conclude
that without experimental determination of the values
of (1) the total content of carboxyl groups in the ion
exchanger and (2) the ion exchanger capacity at a spe-
cific рН value, it is impossible to obtain a correct
description of the acid–base balance with the partici-
pation of carboxyl ion exchangers. The results also
indicate it is impossible to assess the processes of the
acid–base balance only on the basis of the high values
of the correlation coefficients of dependences рН =
f(α/(1 – α)) (Fig. 3), as was noted in [1, 2]. We must
estimate the correspondence between the experimen-
tal and calculated values of the ion exchanger’s capac-
ity at each рН value in accordance with the calculated
parameters of Gregor’s equation.
The pK a' value of 6.56 in 0.1 М NaCl obtained in
this work (Table 1) was close to the one given in [1],
which was determined from the dependence V = f(рН)
for cation exchanger TOKEM-250, which is similar in
structure and degree of crosslinking ( pK a' = 6.59;
0.1 М NaNO3, n = 1.29), but the n values of Eq. (3)
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
269
differ by more than 200%. Calculations using the val-
ues of the Gregor’s equation parameters given in [1]
show that the data do not reflect real processes of the
acid–base balance with the participation of carboxyl
cation exchangers (Fig. 1).
Calculating the parameters of the acid–base bal-
ance of TOKEM 200 carboxyl cation exchanger from
the dependence M = f(рН) without assessing the
agreement between the calculated and experimental
data led the author of [2] to conclude that in 1 М NaCl
this ion exchanger exhibits the properties of a dibasic
polymeric acid having two types of carboxyl groups
with pK a' (1) < 2 and pK a' (2) ~ 5.0. The results of the
present work show clearly that carboxyl cation
exchangers are monofunctional and do not contain
the second ionogenic group with pK a' < 2 (Fig. 4). In
the acid region (рН 1–2), carboxyl groups are incom-
pletely deprotonated, since at these рН values the cat-
ion exchanger capacity with respect to Na+ varies from
0.1 to 0.35 mmol/g of dry mass, due not to the two-
basicity of the ion exchanger but to the change in the
electrostatic free energy of the macromolecule upon
the protonation of carboxyl groups in 1 М NaCl solu-
tion. This is confirmed by the results from the poten-
tiometric titration of carboxyl cation exchanger in
NaCl solutions with concentrations of 0.01 and 0.1 М.
The calculations using the data of Table 1 and Eq. (4)
show that in 0.01 and 0.1 М NaCl at рН 1 and 2, the
carboxyl groups are almost completely protonated,
since the cation exchanger’s capacity with respect to
Na+ is 0.000208 and 0.000521 and 0.0795 and
0.134 mmol/g, respectively.
CONCLUSIONS
A comparative assessment of the calculated ioniza-
tion constants of our carboxyl cation exchanger over
the potentiometric titration curves presented in differ-
ent coordinates showed we must estimate the agree-
ment between the experimental and calculated values
of the ion exchanger capacity at each рН value in
accordance with the calculated pK a' , and n values.
New data on the patterns of the acid–base balance
that occurring with the participation of crosslinked
macroporous carboxyl cation exchangers were
obtained. As with their linear analogs, the pK a' value of
the carboxyl groups for these polymers depends on the
concentration of the salt in the medium, but it is
higher than for homopolymer carboxylic acids.
Parameter n in the Henderson–Hasselbach equation
modified by Gregor is determined not only by the ion
exchanger’s degree of crosslinking and the nature of
the ion filling the sorbent, but also by the concentra-
tion of the electrolyte in which the potentiometric
titration of carboxyl cation exchangers is conducted.
Some believe the ionization constant depends on the
degree of ion sorbent filling [1]. However, our data
show that at a fixed value of a solution’s ionic strength,
Vol. 92 No. 2 2018
270 MEYCHIK et al.

the pK a' value of carboxyl groups remains constant,
since the obtained values of the constants of Gregor’s
equation describe the acid–base properties of the car-
boxyl cation exchanger throughout the investigated
рН interval under these conditions.
ACKNOWLEDGMENTS
This work was performed under the auspices of
the Chair of Plant Physiology, Moscow State Uni-
versity, project no. АААА-А16-116021660106-0. It
was supported by the RF Ministry of Education and
Science, agreement no. 14.579.21.0099, project
no. RFMEF15791X0099.
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4. Yu. A. Leikin, N. R. Meichik, and V. K. Solov’ev,
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Translated by L. Mosina

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 92 No. 2 2018