Introduction

With the development of the ion-exchange technique, ion-

exchange resins have become more and more widely used; in
more than 80% of these case, resins are used in the treatment of
water. Ion-exchange technique is also an indispensable way to
obtain different grades of purified water. The quality of water is
important to ensure the safe and economical operation of large
capacity power generating sets at power plants. At present,
production sections needing purified water request that the
resins used not only have high mechanical strength and ion-
exchange rate, but also have large exchange capacity. So
analysts of factories must conduct the performance comparison
test for different kinds of ion-exchange resins before deciding
which kind of resin to choose for use.
The breakthrough exchange capacity (BEC), equilibrium
exchange capacity, and exchange rate of ion-exchange resins are
the main performance indices in the industry of water treatment.
So far, some researchers have conducted studies on the
determination of resin exchange performance,
13
but many users
have been adopting the manual methods
47
to determine the
exchange-resin performance. However, the methods
shortcomings are difficult operation, long testing time and large
consumption of resins and reagent. So it is necessary to develop
a simple, quick method for determining the performance of ion-
exchange resin.
For the above reasons, an automatic method for rapidly
determining the exchange performance of strongly basic anion-
exchange resin (SBAER) has been developed in this study
based on flow-injection spectrophotometry.
810
It is a pathfinder
in the aspects of theory and of rapid determination of ion-
exchange resin performance, and thus has important
significance.
Experimental
Theory
Figure 1(a) shows the schematic drawing of an ion exchange
resin column. When the chloride solution passes through the
column, the SBAER will remove chloride ion according to this
reaction:
Cl

+ ROH RCl + OH

(1)
where R represents the complex resin matrix.
In Fig. 1(a), Part I refers to resins which have finished the
above reaction (in the form of Cl); Part II refers to the resins
which are working. This part is called an exchange zone. With
the chloride solution continuously flowing through the column,
the exchange zone moves down. When the capacity of the
anion resin is exhausted (in the form of Cl), the chloride ions
will completely break through the resins.
Usually, one can monitor the conductivity of outwater of the
anion-exchange tower to indirectly monitor the break through
point, but when the content of sodium ion in the outflow water
from prior cation-exchange tower of water treatment system
increases unexpectedly (e.g. cation-exchange tower exhaustion),
831 ANALYTICAL SCIENCES MAY 2004, VOL. 20
2004 The Japan Society for Analytical Chemistry
Determination of Anion-Exchange Resin Performance Based on
Facile Chloride-Ion Monitoring by FIA-Spectrophotometry
with Applications to Water Treatment Operation
Yong-Sheng LI*

and Yi-Ling DONG**

*School of Chemical Engineering of Sichuan University, No. 24 Southern Section 1, 1st Ringroad,
Chengdu City, Sichuan Province 610065, China
**Peninsula Water Treatment Ltd., No. 381 Central Plaza, Huaihai Zhong-road, Shanghai 20020, China
Based on a flow-injection spectrophotometry, an automatic analytical method for determination of ppb-level chloride-ion
has been established. By use of this method, a novel FIA method for the determination of SBAER performance has also
been developed. In this paper, the effects of concentration, dosage, and flow rate of the regenerant on BEC of SBAER
were first investigated dynamically by the FIA method. In addition, the flow rate of the sample water and the temperature
of the ion exchange resin were also examined. The optimum conditions were obtained: the volume of the regenerant
(sodium hydroxide) was 50 mL (0.15 g resin), and its concentration was 3% (w/v); the volumetric flow rates of the
regenerant and the sample water were 0.5 ml/min (4.3 m/h) and 1.5 ml/min (13 m/h), respectively. The exchanging
temperature was 25 5C. The method is characterized by the use of a micro resin-column, shorter testing cycle, easy
operation, and high reproducibility. The proposed method is approximately 30 times more efficient than the manual
method, and it can be used for the exchange performance comparison of various SBAER.
(Received March 31, 2003; Accepted November 19, 2003)

To whom correspondence should be addressed.

E-mail: lysgxf@mail.jl.cn

http://www.paper.edu.cn
it will result in mistaken information of exhaustion of the anion-
exchange towers exchange capicity. In fact, at this time, the
exchange capicity of anion-exchange tower has not been
exhausted.
At power plants, chloride ions are the main cause of various
metal corrosions. Its content also must be monitored and
controlled strictly. Therefore, we selected the method of
monitoring the chloride concentration in the outflow water.
The chloride is determined according to the reactions below:
Hg(SCN)2 + 2Cl

HgCl2 + 2SCN

(2)
3SCN

+ Fe
3+
Fe(SCN)3 (red complex) (3)
The absorbance of Fe(SCN)3 is proportional to the concentration
of chloride. So the concentration of chloride will be obtained as
soon as the absorbance of Fe(SCN)3 is measured at 465 nm.
11
Through detecting the chloride in the outflow water, we can
obtain the outflow curve
12
that is shown in Fig. 1(b). At the
beginning stage of the operation (from point a to point b), the
concentration of chloride in the outflow water is low, because
the chloride ions in the water are exchanged sufficiently with
hydroxide ions on the resins when the sample water flows
through the resins. At the point of b, chloride ions break
through the resins in the minicolumn, so the curve rises sharply.
Point b is called the breakthrough point. If the ion-exchange
operation continues for some time, the resins in the column will
be completely exhausted. Thus, the concentration of chloride
ions detected in the outflow water will be equal to that detected
in the inflow water.
The value of breakthrough exchange capacity (BEC) of anion-
exchange resins should be calculated by the following equation:
E=Q/m=
a
b
CdV (C0 Cx)V= (C0 Cx)qt (4)
1

m
1

m
where E refers to the breakthrough exchange capacity (mmol/g);
m, Q, C, and V refer to the weight of resins in the column (g),
the amount of ions absorbed by the exchange column (mmol),
the differential concentration of chloride ions between the
inflow water and the outflow water of the column (mmol/L),
and the volume of water flowing through the column (L),
respectively. C0 and Cx refer to the concentration of Cl

in the
inflow water and in the outflow water (mmol/L); t and q refer to
operating time of the column (min) and volumetric flow rate of
the sample water (L/min), respectively.
Equation (4) shows that the breakthrough exchange capacity
is proportional to the volume of the sample water flowing
through the column as soon as the weight of resins remains
constant. It will be used to calculate the exchange capacity in
the later results and discussion.
Apparatus
A FIA-T1-721 Type flow-injection spectrophotometer with a
flow cell (light path: 20 mm) made in the Instrumental Factory
at Northeast China Institute of Electric Power Engineering
13
and
a FIA-3100 Type flow-injection analyzer made in Wantuo
Company (Beijing, China) were used. A XWT-100 Type
recorder made in Dahua Meter Factory (Shanghai, China) was
also used.
Preparations of reagent and sample solutions
All chemicals (bought from the Chemical Reagent Company
of Beijing) used in the experiment were of analytical-reagent
grade except that the sodium hydroxide, which was first-rate-
reagent grade. Ultra purified water whose conductivity is
0.0556 s/cm was used for the preparation of these solutions.
Chloride stock solution of 1000.0 mg/L. A 1.6485-g volume of
sodium chloride heated for 2 h at 105C was weighed, dissolved
in water and diluted exactly to 1000 mL. Working standard
solutions (20 mg/L Cl

) were prepared by appropriate dilution.

832 ANALYTICAL SCIENCES MAY 2004, VOL. 20
outflow water
Part III
R-OH type resin
Exchange zone
Part II
Cl

+ R-OH R-Cl +OH

R-Cl and R-OH type resins

Part I
R-Cl type resin
sample water
(inflow water)
( a )
T
h
e

c
o
n
c
e
n
t
r
a
t
i
o
n

o
f

C
l

i
n

t
h
e

o
u
t
f
l
o
w

w
a
t
e
r
breakthrough point
a
c
d
e
time
b
(b)
C0
Cx
fiber
Breakthrough
capacity
Equilibrium exchange capacity
Fig. 1 Schematic drawing of ion exchange process in an ion exchange resin column. (a) The ion exchange
process in the column; (b) variation curve of concentration of chloride in outflow water from the column. C0,
concentration of Cl

ion in the inlet water; Cx, concentration of Cl

ion in the outlet water; b point,

breakthrough point; c point, the end point (completely exhausted point of the resin column).
http://www.paper.edu.cn
Chromogenic reagent. The solution was prepared by dissolving
0.626 g of mercuric thiocyanate and 30.3 g of ferric nitrate in
water, with 3.4 mL of concentrated nitric acid and 150 mL of
alcohol (95%) added later, and then diluted exactly to 1000 mL
with water.
Sodium hydroxide solution of 3.0% (w/v). A 30.95-g volume of
sodium hydroxide was weighed, dissolved in water, and then
diluted exactly to 1000 mL.
Preparation of ion-exchange mini column
Preliminary treatment of resin.
14
201x7 Type resins (equivalent
to Amberlite IRA-400 Type resins (US) and Diaion SA-10A
Type resins (JAP)) were weighed out to 0.15 g, immersed in the
saturated sodium chloride solution for 12 h, and then immersed
in 5% of hydrochloric acid and 3% of sodium hydroxide for 4
8 h, respectively. Finally, the resins were rinsed with ultra-
purified water for 20 min.
Filling of the ion-exchange column. The size of the ion-
exchange mini column was 3.0 mm inner diameter and 42 mm
long. The treated resins were filled in the column, and two ends
of the column were sealed with nylon net of 100 screen mesh to
prevent the resins from flowing outside. In addition, some little
fiber threads were put in the two ends of the column to prevent
loosing or cracking of the resins caused by expansion and
contraction. Then the column was connected in the flow
manifold with a polytetrafluoroethylene tube (1.0 mm i.d.), as
shown in Fig. 3.
FIA manifold and analysis procedures
Determination of chloride ion by FIA. First, rapid
determination of ppb-level Cl

was researched by FIA manifold,

as shown in Fig. 2. Effects on the sensitivity of wavelength,
temperature, length of reaction coils, pump speed, sampling
volume, and concentration of the chromogenic reagent were
investigated, and the optimum conditions of determining
chloride ions were obtained.
15
Namely, the wavelength is 465
nm; the flow rate is 2.78 ml/min; the length of reaction coils is
300 cm (0.5 mm i.d.); and the sampling volume is 400 L. The
chromogenic reagent is the mixing solution of 0.063% (w/v)
mercuric thiocyanate, 3.03% (w/v) iron(III) nitrate, 15% (v/v)
alcohol and 0.472% (w/v) nitric acid.
The procedures are as follows: when the injection valve is
switched to the loading position, the sample solution containing
chloride is filled into the sample loop. Then the valve is
switched to the injection position and the sample plug is
injected into the carrier, and goes into the reaction coil (RC)
after merging with the chromogenic reagent. The absorbance of
the red product (Fe(SCN)3) is measured at 465 nm while it is
flowing through the flow cell. And the concentration of
chloride is obtained by the peak height.
The methods detection limit
16
is 20 g/L, recoveries of
adding standard sample are between 100% and 105%, the
relative standard deviation is 0.89% for twelve determinations
of 1.0 mg/L chloride solution, the sampling rate is up to 60
120 samples/h. The method has been applied successfully to
the determination of chloride ion in the boiled water at power
plants, in natural water, tap water and so on.
15
In the study, by using the method, we have monitored chloride
ion in the outflow water of the minicolumn to research the
performance of the anion-exchange resin.
Determination of exchange performance of anion-exchange
resins by FIA. Figure 3 shows a FIA manifold used for the
determination of ion-exchange resin performance. There is a 2-
channel synchronous injection valve (including V1 and V2) in it.
The procedures are as follows: first, under the optimum
conditions mentioned above, a series of chloride standard
solutions as the sample was determined, and the calibration
curves were obtained as shown in Fig. 4. Second, the standard
solution of 20 mg/L Cl

is used as sample water. The sample

water continuously flows through the minicolumn and enters
into the loading loop of the valve (V1). After the valve is
switched to the injection position automatically, the sample
water flows through V2 to waste. At the same time, the sample
plug in the loop is injected into the carrier and goes to the
reaction coils (RC) and reacts with the reagent to form a
complex (Fe(SCN)3). The following procedures are the same as
above.
When the exchange capacity of the resins in the column has
been exhausted (in the form of Cl), a running cycle of the
column is finished. Consequently, a set of response peaks were
obtained. Connecting these peak heights, we get an outline of
outflow water of the column. Through this outline and
calibration curves in Fig. 4, we can get information about
chloride concentration, the breakthrough exchange capacity,
equilibrium exchange capacity and resin exchange rate.
During the whole experiment, the flow rate of the sample
water, injection time, switch over of valve position etc. are
controlled automatically by the computer.
Besides, after the exchange capacity of the resins in the
column has been exhausted, the column is regenerated with
sodium hydroxide solution, and then rinsed with ultra-purified
water for 10 min.
Under the optimum conditions, according to the analytical
procedures as mentioned above, we measured the exchange
833 ANALYTICAL SCIENCES MAY 2004, VOL. 20
Fig. 2 Manifold for the determination of ppb-level chloride ions
with FIA method. P, peristaltic pump; C, carrier stream; R,
chromogenic reagent; RC, reaction coil; D, spectrophotometer; V, 3-
channel synchronous/asynchronous injection valve; W, waste.
Fig. 3 FIA manifold for the performance determination of ion-
exchange resins. P1, P2, peristaltic pump; C, carrier stream (purified
water); IE, ion-exchange column; RC, reaction coil; D,
spectrophotometer; V1 and V2, 2-channel synchronous injection
valve; W, waste.
http://www.paper.edu.cn
performance of SBAER (the resins used were made in JY
Manufactory). The results obtained are given in Fig. 5. It is
found that the change tendency of the curve obtained by FIA
corresponds with that of the theoretical curve in Fig. 1(b).
In addition, such procedures were repeated twice under the
same experimental conditions. The two curves are almost
overlapping, which indicates that the method has high
reproducibility.
Results and Discussion
Effect of regenerant dosage on breakthrough exchange capacity
In the later experiments, exchange performance of anion-
exchange resins were investigated by the FIA manifold in Fig.
3. The regenerant dosage is an important factor affecting the
regeneration efficiency of resin; thus, the effect of the volume
of the regenerant on the breakthrough exchange capacity was
investigated first. In the test, 2% (w/v) of sodium hydroxide
solution was used as a regenerant, and the volumetric flow rates
of both regenerant and sample water were 1.2 ml/min.
The volume of the regenerant was controlled in the range of
15 140 mL. The effect of volume of the regenerant on the
resins breakthrough exchange capacity was examined through
changing the regeneration time. The experimental results are
given in Fig. 6. They show that the exchange capacity increases
with the increase of the regenerant volume, but the degree of
increase begins to decrease when the volume is over 50 mL.
Because it is not economical to increase the breakthrough
exchange capacity by increasing the volume of regenerant,
under the premise of ensuring the quality of outflow water to
meet expectations, the volume of the regenerant should be
chosen according to the economical principle. In this
experiment, it was selected as 50 mL (0.15 g resin).
Effect of regenerant concentration
The volume of sodium hydroxide was fixed at 50 mL, and
other experimental conditions were as mentioned above. The
effect of the regenerant concentration on the breakthrough
exchange capacity of resins was examined in the range from 0.5
to 10% (w/v). The results obtained are shown in Fig. 7. The
exchange capacity increases initially, and then decreases as the
concentration of the regenerant increases. There are two
reasons to explain this phenomenon: first, the mole volume of
OH

is larger than that of Cl

, so when the concentration of OH

834 ANALYTICAL SCIENCES MAY 2004, VOL. 20

Fig. 4 Calibration curves of chloride ions at higher and lower concentrations obtained with flow injection
spectrophotometry. Experimental conditions are as follows: pump speed, 60 rpm; diameter of the pump tubing, 0.89
mm; sampling volume, 400 L; wave length, 480 nm; legnth of reaction coil, 300 cm; reaction temperature, 25C;
coloring reagent, 0.063% (w/v) mercuric thiocyanate + 3.03% (w/v) iron(III) nitrate + 15% (v/v) alcohol + 0.472%
(w/v) nitric acid.
Fig. 5 Effluent curve of the anion-exchange resins (IER)
determined by FIA spectrophotometry. Flow rate of the sample
water, 1.5 ml/min; area of abde, breakthrough capacity; area of
abcde, equilibrium exchange capacity; area of bcgf, the resins
exchange zone.
Fig. 6 Effect of the regenerant dosage on the exchange capacity.
http://www.paper.edu.cn
is too high, the Cl

will be absorbed prior to OH

. Secondly,
there is an electrical double layer at the resin solution interface.
In the concentrated solution, the electrical double layer is
contracted, so the resins are regenerated with difficulty. The
greatest exchange capacity was achieved when the
concentration of sodium hydroxide was 3%. Therefore, the
concentration was selected as 3% (w/v) in this experiment.
Effect of flow rate of regeneration solution
The volumetric flow rate of regenerant exerts an influence on
the regeneration efficiency, so its effect on the exchange
capacity was also investigated in the range of 0.5 6.5 ml/min.
The experimental conditions were as in the section above. The
results obtained are shown in Fig. 8. The breakthrough
exchange capacity is inversely proportional to the volumetric
flow rate of the regenerant, which means that the contacting
time between the regenerant and resins is shortened when the
flow rate increases. In this experiment, the volumetric flow rate
was selected as 0.5 ml/min (4.3 m/h).
Effect of flow rate of sample water
The experimental conditions were as in the section above,
except that the volumetric flow rate was 0.5 ml/min. Effect of
volumetric flow rate of the sample water (20 mg/L chloride
solution) on the resin capacity was examined in the range from
0.5 to 4.3 ml/min. The experimental results are shown in Fig. 9.
The figure illustrates that the resin capacity remains nearly
constant in the range of low flow rate of the sample water, and
then decreases with the increase of the flow rate. When the
flow rate is at 4.3 ml/min, the quality of outflow water becomes
worse. Because the higher the rate of flow and the wider the
resin exchange zone, the more chloride ions will break through
the resins before exchanging with hydroxide ions once the
width of the exchange zone is more than the length of the mini
column. Based on the idea of both reducing the exchange time
and increasing the exchange capacity, the volumetric flow rate
of the sample water was selected as 1.5 ml/min (13 m/h).
Effect of temperature
Temperature is usually one of the most important influencing
factors in chemical reactions, so in this experiment the effect of
temperature on the resin performance was examined. The
experimental conditions were as in the section above, except
that the volumetric flow rate of the sample water was 1.5
ml/min. The mini column was put in the automatic thermostat
bath of a FIA-T1 Type flow-injection analyzer. The
835 ANALYTICAL SCIENCES MAY 2004, VOL. 20
Fig. 7 Effect of concentration of the regenerant on the exchange
capacity.
Fig. 9 Effect of volumetric flow rate of the sample water on the
exchange capacity.
Fig. 8 Effect of volumetric flow rate of the regenerant on the
exchange capacity.
Fig. 10 Effect of temperature of the exchange resins on the
exchange capacity.
http://www.paper.edu.cn
temperature of the resins was controlled by changing the water
bath temperature in the range from 20C to 80C, while at the
same time, the sample solution was heated to the same
temperature as the column. The results obtained are shown as
in Fig. 10.
Results show that the exchange capacity increases as the
temperature rises in the range of 20 60C, and decreases as the
temperature rises in the range of 60 80C. It was found that
when the temperature was at 80C, the quality of outflow water
became worse, the resin beads cracked and their color became
deep. In the actual operation, the temperature should be kept in
the range of 20 40C, because the physical degradation of resin
will take place if the temperature is too high. Thus, in this
experiment, the temperature was selected as room temperature,
25 5C.
Conclusion
Based on flow-injection spectrophotometric analytical
technique, a method for determining the exchange performance
of SBAER has been developed. Factors affecting the
breakthrough exchange capacity of the resins were also
investigated, and the optimum conditions were obtained. The
wavelength is 465 nm; the flow rate of chromogenic reagent is
2.78 ml/min; and the length of the reaction coil is 300 cm (0.5
mm i.d.); the sampling volume is 400 L; the chromogenic
reagent consists of 0.063% (w/v) mercuric thiocyanate, 3.03%
(w/v) iron(III) nitrate, 15% (v/v) alcohol and 0.472% (w/v)
nitric acid; the length of the ion-exchange minicolumn is 42 mm
and the width is 3.0 mm. The amount of resins used is 0.15 g;
the volume of the regenerant (sodium hydroxide) is 50 mL per
0.15 g resin, and its concentration is 3% (w/v). The volumetric
flow rates of the regenerant and the sample water are 0.5 ml/min
(4.3 m/h) and 1.5 ml/min (13 m/h), respectively. The
exchanging temperature is 25 5C.
This automatic method is characterized by the use of an ion-
exchange minicolumn, easy operation, high reproducibility, and
rapid determination. Finishing the determination requires only
6 8 h by this method, in contrast to the duration of one week
needed by the manual method.
4,5
So the method is
approximately 30 times more efficient than the manual method,
and it can be used to compare the exchange performance of
various SBAER and to do theoretical research satisfactorily.
In addition, some factors (such as the length and, the width of
the column) affecting the breakthrough exchange capacity of
resin were not examined in this experiment, so the value of
breakthrough capacity is lower than that obtained by other
methods. Thus, this method will be studied further.
References
1. F. R. Jiang, Liaoning Chemical Industry, 1997, 26, 239.
2. Q. Zuo, S. F. Ran, J. Tang, and C. Y. Zhu, Ion Exchange
and Adsorption, 1995, 11, 314.
3. B. S. Wang, Y. M. Liu, Y. G. Zhang, W. L. Li, and B. L.
He, Ion Exchange and Adsorption, 1995, 11, 407.
4. ASTM D 3087-91, Standard test method for operating
performance of anion-exchange materials for strong acid
removal, 1998.
5. GB 5760-86, Determination for exchange capacity of
anion exchange resins, 1986.
6. GB 8144-1987, Determination for exchange capacity of
cation exchange resins, 1987.
7. GB 11992-1989, Strong basic anion exchange resins in
chloride formDetermination of exchange capacity,
1989.
8. Y.-S. Li and W.-C. Cheng, Flow Injection Analysis
(Chinese), 1987, Beijing University Publishing House,
No. 1320947.
9. Y.-S. Li and Y. Narusawa, Bunseki Kagaku, 1992, 41, 463.
10. Y.-S. Li and Z.-J. Wang, Laboratory Robotics and
Automation, 1995, 7, 229.
11. Y. Utsumi, Nikka, 1952, 73, 835.
12. X.-J. Shi, Treatment of water in power plants, 1993,
Water Conservancy and Electric Power Publishing House,
152.
13. Y.-S. Li and W.-C. Cheng, Fenxi Yiqi, 1986, 3, 46.
14. J.-X. Yao, X.-W. Xu, and Y.-Y. Li, Industrial Boiler
Water Treatment and Analysis of Water Quality, 1987,
China Labor Publishing House, 188.
15. Y.-S. Li and Y.-L. Dong, North China Electric Power,
2003, 266, 18.
16. Z. Liu, Instrumental Analysis, 2001, Chemical Industry
Publishing House, 228.
836 ANALYTICAL SCIENCES MAY 2004, VOL. 20
http://www.paper.edu.cn