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The influence of temperature on the ion exchange properties of

phenolformaldehyde sorbents

Article  in  Russian Journal of Physical Chemistry · December 2009

DOI: 10.1134/S0036024409120218

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ISSN 00360244, Russian Journal of Physical Chemistry A, 2009, Vol. 83, No. 12, pp. 2122–2126. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © L.A. Shelkovnikova, O.T. Gavlina, V.A. Ivanov, V.I. Gorshkov, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 12, pp. 2325–2329.

PHYSICAL CHEMISTRY
OF SURFACE PHENOMENA

The Influence of Temperature on the Ion Exchange Properties

of Phenolformaldehyde Sorbents
L. A. Shelkovnikova, O. T. Gavlina, V. A. Ivanov, and V. I. Gorshkov†
Faculty of Chemistry, Moscow State University, Moscow, Russia
email: lubushka16@yandex.ru
Received September 24, 2008

Abstract—The influence of temperature on cation exchange on phenol groups of macroporous materials

based on phenolformaldehyde resins (PFRs) was studied for Amberlit XAD 761 with irregularly shaped grains
obtained by breaking up polycondensation resin blocks and FFS1.4/0.7 with spherical granules. An increase
in temperature caused some decrease in the sorption capacity of PFRs in the alkaline region, but almost did
not influence the selectivity of alkali metal ion exchange. The sorption capacity and selectivity of PFRs did
not change after multiple (dozens of cycles) transfer of phenol groups from the hydrogen to salt form and
back. Ion exchangers of this type can effectively be used for separating mixtures of alkali metal ions containing
cesium and rubidium.
DOI: 10.1134/S0036024409120218

INTRODUCTION groups were used to develop a method for extracting

The products of condensation of some phenols
with formaldehyde interact with alkalis and are capa
ble of sorbing many ions from solutions [1]. The con
clusion was, however, drawn that ion exchange on
phenol groups was impracticable because of their low
acidity and inefficiency in neutral and acid solutions.
For a long time, more convenient ion exchangers with
groups of other types (such as sulfoacid and carboxyl)
grafted to phenolformaldehyde resins (PFRs) have
been used [2, 3]. Later, they were replaced with more
stable and highcapacity ion exchangers based on sty
rene–divinylbenzene copolymers.
Nevertheless, such adsorbents as weakly basic
anion exchangers and sulfoacid cation exchangers
based on PFRs are still produced [3, 4]. Current inter
est in such materials is explained by their certain char
acteristics [4], namely, high adsorption properties with
respect to substances with large molecules and higher
density compared with polystyrene matrices, which
gives us certain advantages. A special feature of cation
exchangers based on PFRs is their higher selectivity
with respect to mixtures of alkali metal salts contain
ing rubidium and cesium compared with all the other
types of ion exchangers. The highest selectivity is
observed for exchange directly on phenol groups.
In spite of the commonly accepted view of a low
stability of these ionites, they were found to be suffi
ciently stable for using them as chromatographing
materials even with respect to alkaline media, and sev
eral procedures for separating alkali metal ion mix
tures containing rubidium and cesium ions were devel
oped with their use. In particular, macroporous PFRs
containing no exchange groups other than phenol
rubidium from concentrates of sea water processing
containing excess potassium ions [5–7]. In USA, phe
nolresorcin resin was used for selective extraction of
radioactive cesium from highactivity alkaline solu
tions [8, 9].
In this work, we studied the influence of tempera
ture on cation exchange on phenol groups of
macroporous sorbents based on PFRs, namely,
Amberlit XAD 761 with irregularly shaped grains
obtained by breaking up polycondensation resin
blocks and FFS1.4/0.7 with spherical granules; a
technology for producing them was developed in the
middle 1980s at the Niznii Tagil branch of NPO “Plas
tmassy.” The ion exchange properties of the latter
sample at room temperature were studied in detail in
[10, 11]. At this stage, it was important to include this
sample as an object of study to check its sorption prop
erties after prolonged use and storage and compare
them with the properties of other materials.
EXPERIMENTAL
The concentrations of alkalis were determined by
titration with a 0.1 M solution of potassium hydroxide,
and acids were determined by titration with a 0.1 M
solution of hydrochloric acid against methyl red as an
indicator. The concentrations of potassium ions in
individual solutions were determined by emission
flame photometry in a propaneair flame. Potassium,
rubidium, and cesium ions in mixed solutions were
analyzed by emission spectroscopy and mass spec
trometry with an inductively coupled plasma. Errors in
alkali metal concentrations determined by flame pho

2122
 THE INFLUENCE OF TEMPERATURE ON THE ION EXCHANGE PROPERTIES
tometry were taken to be 4%. Sorbents were prepared
for measurements by sequentially washing them in
columns with excess 0.5 M solutions of KOH, HCl,
and water. They were then isolated by filtration and
dried in air at room temperature until their weight
ceased to change.
The dependences of exchange capacity on solution
pH and alkali concentration were studied by potentio
metric titration at 295 and 343 K. Samples of each
material (0.5 g) in Hforms in glass flasks were poured
over with 0.1 M solutions of KOH and KCl taken in
various ratios; the total volume of solutions was 50 ml.
The flasks were periodically shaken for 24 days, and
liquid phase pH was measured. In all experiments, pH
almost did not change already after 12 days. After
equilibrium was established, liquid phase pH was mea
sured in each flask, the concentration of KOH in solu
tion was found by titration, and the amount of sorbed
potassium ions was determined. For this purpose, each
ionite sample was transferred into a column with a
porous glass filter, equilibrium solution was separated
using a waterjet pump for 2 min, and sorbed ions were
displaced with a 0.5 M solution of HCl and analyzed.
To study sorption from more concentrated solu
tions, solutions of KOH with given compositions
taken in a large excess were passed through ion
exchanger portions with known weights (in the airdry
state) in the H form. Ion exchange suspensions were
then unloaded into flasks and stirred for 0.5–2 days (it
was found earlier that the time of the attainment of
equilibrium did not exceed several hours at alkali con
centrations higher than 0.05 M [10]), and solution
compositions were determined. After the establish
ment of equilibrium, ion exchanger portions were
transferred into columns, equilibrium solutions were
removed using a waterjet pump, and sorbed K+ ions
were displaced with a 0.5 M solution of HCl and ana
lyzed.
Selectivity coefficients, which, for singly charged
alkali metal ions, coincided with ion exchange equi
librium coefficients,
yB xA
K = 
cB cA
 = 
, (1)
yA xB cA cB
where c i and ci are the concentrations of the compo
nents in the ionite and solution phases (gequiv/l) and
yi and xi are the equivalent fractions of exchanging ions
in the ionite and solution phases, respectively, were
determined (1) by the static method and (2) from fron
tal chromatography elution curves.
In the first method, a portion of the sorbent (~15 ml
of suspension) was brought to equilibrium with a solu
tion of a binary mixture of alkali metal hydroxides by
passing this solution taken in excess. Next, the equilib
rium solution was separated from the sorbent using a
waterjet pump, and sorbed ions were displaced from
the sorbent with a 0.5 M solution of HCl and analyzed.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
2123
qK, mgequiv/g
2
1 1
2
3
0
4 6 8 10 12
pH
Fig. 1. Dependences of the capacity of (1, 2) FFS 1.4/0.7
and (3) Amberlit XAD 761 sorbents on pH of equilibrium
solution at 295 K; (1) data from [11].
The selectivity coefficient was calculated according to
(1).
In the second method, a solution of a mixture of
alkali metal hydroxides was passed at a rate of 1–
2 ml/min through a glass column 0.8–1 cm in diame
ter filled with the ion exchanger under study in the H
form swollen in water. The filtrate was collected by
fractions and analyzed. Measurements were stopped
when the compositions of the outgoing and initial
solutions coincided. In performing reverse frontal
chromatography, a 0.1 M solution of HCl was passed
through a column with the ion exchanger brought to
equilibrium with a solution of a mixture of hydroxides
of the pair of ions under study (usually, as a result of
direct frontal chromatography). The selectivity coeffi
cient was then calculated by the equation [12]
K–1
 = −
1 + ( K – 1 )x 0
+ ∑ V c (x
i i 0 – x i )/Qx 0 ( 1 – x 0 ), (2)
where ci is the total concentration of exchanging ions
A and B in the ith sample (mgequiv/ml), Vi is the vol
ume of the ith sample (ml), x0 and xi are the equiva
lent fractions of more strongly sorbed ion A in the
initial solution and ith sample, Q is the total capacity
of the ion exchanger in the column (mgequiv), and
sign “plus” corresponds to direct and “minus” to
reverse frontal separation. Maximum errors in K were
of 10–14%.
RESULTS AND DISCUSSION
The data of potentiometric titration of ionites FFS
1.4/0.7 and Amberlit XAD 761 are shown in Figs. 1, 2.
We found that the dependences of sorption of KOH by
Vol. 83 No. 12 2009
2124 SHELKOVNIKOVA et al.
qK, mgequiv/g
1
2 6
1 2
0 0.02 0.04 0.06
cКОН, M
Fig. 2. Dependences of the capacity of FFS 1.4/0.7 sorbent
on the concentration of KOH at (1) 295 and (2) 343 K.
the FFS 1.4/0.7 sorbent on pH at 295 K closely coin
cided with the titration curve of this sorbent obtained
in [10]. It should be borne in mind that this sorbent
was used to study ion exchange separation methods
described in part in [5, 7]; that is, the material under
went multiple (dozens) successive treatments with
acid and alkaline solutions. The dependence for the
Amberlit XAD 761 sample also closely corresponded
to the dependences for FFS 1.4/0.7. Titration curves
showed that both sorbents, Amberlit XAD 761 and
FFS 1.4/0.7, did not contain substantial amounts of
functional groups other than phenol groups, because
alkali metal ions were sorbed by them at pH > 8 only.
A fairly sharp increase in sorption capacity contin
ues as pH increases above 12 (рК of phenol groups in
unsubstituted phenol is 9.98) (Fig. 1) and as the con
centration of alkali grows (Fig. 2). This can be related
to both variable pK of phenol groups in sorbents (the
presence of groups with рК > 10) and substantial
molecular sorption of the electrolyte. The transition of
phenol ion exchangers from the H form (in acid or
neutral solutions) into the form of alkali metal ions (in
alkaline solutions) is accompanied by a substantial
increase in ion exchanger swellability and a contrast
change in color of resin grains from sand yellow to
black.
The sorption capacities of FFS 1.4/0.7 and Amber
lit XAD 761 also substantially increase as the concen
tration of alkali in solution increases above 0.1 M
(Fig. 3). It was shown in [5, 7] that, in this region,
almost all PFR phenol groups were ionized, and an
increase in sorption capacity was caused by molecular
sorption of the electrolyte. This molecular sorption
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
qK, mgequiv/g
4
1
2
3
4
0 0.2 0.4 0.6 0.8
cКОН, M
Fig. 3. Dependences of the capacity of (1, 2) Amberlit
XAD 761 and (3, 4) FFS 1.4/0.7 sorbents on the concen
tration of KOH at (1, 3) 295 and (2, 4) 343 K.
can be related to either Donnan electrolyte distribu
tion in resin gel regions or the presence of the liquid
phase similar to the external solution in ionite
macropores. An increase in temperature somewhat
decreases the sorption capacity of PFRs in the alkaline
region (Figs. 2, 3). This can be caused by the influence
of temperature on phenol group рК values, the disso
ciation constant of water, and superequivalent electro
lyte sorption. The sorption capacity decreases by
approximately the same value in the region of alkali
concentrations higher than 0.1 M, which is evidence
of the predominance of the last factor. A decrease in
superequivalent sorption as the temperature increases
is likely related to a decrease in the swellability of ion
exchangers.
The selectivity of ion exchangers was studied for
the Cs+, Rb+, and K+ ions and binary solutions of
hydroxides with the total concentration ~0.1 M and a
1 : 1 ratio between ions. The selection of these ions was
caused by their closeness to each other in properties.
In addition, they accompanied each other in many
objects of interest for practice, such as natural
hydromineral raw materials.
The results of chromatographic experiments
(Figs. 4, 5) showed that Amberlit XAD 761 sorbent
possessed equally good dynamic ion exchange proper
ties (sharp ion exchange fronts were formed on it) and
equally high selectivity with respect to mixtures Cs+–
Rb+ and Rb+–K+ as the FFS 1.4/0.7 sorbent studied
earlier. The experimental selectivity coefficients at
293 K for these two samples were close to each other
(table). The selectivity coefficients at two tempera
tures on Amberlit XAD 761 were also close. In experi
Vol. 83 No. 12 2009
 THE INFLUENCE OF TEMPERATURE ON THE ION EXCHANGE PROPERTIES 2125

c, M

0.08
1
2
0.06 3
4

0.04

0.02

0 400 800 1200

V, ml

Fig. 4. Frontal chromatography elution curves of a mixture of 0.046 M CsOH and 0.056 M RbOH on Amberlit XAD 761 at
(1, 2) 293 and (3, 4) 343 K; (1, 3) Rb+ and (2, 4) Cs+; sorbent bed height 76 cm.

ments with frontal separation, zones (eluate fractions)
formed on fairly small Amberlit XAD 761 layers. The
solution in these zones was substantially enriched in
one of the components of the mixture subjected to
separation.
According to the elution curves shown in Fig. 4, an
increase in temperature shifts sorption fronts to the
left, which is also evidence of a decrease in sorption
capacity as the temperature increases.
Traditionally, low thermal and chemical stability
of phenolformaldehyde resins in oxidative and alka
line media are considered their shortcomings [2].
Noticeable solution of phenolformaldehyde resin in
alkaline solutions was mentioned already in [1]. The
authors of [13] also faced substantial destruction of
the resin obtained by block polycondensation of
phenol with formaldehyde in studies of the ion
exchange properties of the resin in alkaline solu
tions. Low chemical stability of bifunctional sul
fophenol, carboxyphenol, and phosphorophenol
ion exchangers in alkaline solutions was also men
tioned in the literature [2].
In this work, we checked the capacity and selec
tivity of the FFS 1.4/0.7 ion exchanger after per
forming a long series of works on creating a counter
flow ion exchange method for separating a mixture
of potassium and rubidium ions described in [5, 7].
Its characteristics (sorption capacity and selectiv
ity) were found to remain unchanged after multiple
(dozens of cycles) transfer of PFR from the hydro
gen to salt form and back. The capacity of Amberlit
XAD 761 also remained unchanged in the course of
this study.
It follows that the sorbents on the basis of
macroporous PFRs that we used were much stabler
than expected. This stability can be related to their
macroporous structure. Macroporous structure
makes ion exchangers more stable with respect to
aggressive chemical reagents compared with gel
structures; this is known for ion exchangers based
on styrenedivinylbenzene matrices [14]. The results
obtained for phenol ion exchangers correlate with
these data. The role of porosity of polymeric mate
rials and its influence on their chemical and thermal
stability might be considered in terms of the special
properties of nanomaterials, which is currently a
priority topic.
The importance of phenoltype ion exchangers is
not limited to their historical role in the discovery of
the principles of the creation of ion exchange resins.
Thanks to certain unique physicochemical properties,
they remain of importance for solving certain practical
problems. These unique properties include high selec
tivity with respect to mixtures of alkali metals contain
ing cesium and rubidium ions. Ion exchangers of this
type can very effectively be used for separating mix
tures of alkali metal ions, which are very difficult to
Selectivity coefficients for exchange of alkali metal ions
˜˜ Rb ˜˜ Cs
Sorbent T, К K K K K
FFS 1.4/0.7 293 К 1.5–1.7 2.2–2.6
Amberlit XAD 761 293 К 1.5–1.6 2.1–2.5
343 К 1.6 2.0

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 83 No. 12 2009

2126 SHELKOVNIKOVA et al.

c, M ACKNOWLEDGMENTS
(а) The authors thank V.A. Demidov and I.V. Bakhtin,
workers of the Moscow Office of Rohm&Haas Com
1
pany, for the samples of sorbents.
2
0.04 3
4
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