Journal of Chromatographic Science, Vol.
27, January 1989
Determining Chlorine Concentrations in Air and
Water Samples for Scrubbing Studies Using
Ion Chromatography
William C. Askew a n d Stephen J. Morisani
D e p a r t m e n t of C h e m i c a l E n g i n e e r i n g , U n i v e r s i t y of S o u t h A l a b a m a , M o b i l e , A l a b a m a 3 6 6 8 8
Abstract
An ion chromatographic method is developed to measure
chlorine concentrations in air and water samples for
scrubbing studies in packed towers. The method uses a
sodium sulfite solution as a trapping agent for converting
chlorine to chloride ion in both air and water samples. The
method also features short analysis time and long shelf life
for collected samples awaiting analysis, but is subject to
chloride peak interference.
Introduction
Chlorine (Cl ) and chlorine dioxide (ClO ) are important
2 2
chemicals used in the bleaching operations of many paper mills.
Because of their hazardous nature, waste gas streams containing
C l and C l O must be treated before discharge to the atmosphere.
2 2
This treatment must provide a safe environment for workers,
consistent with government regulations. Reports of C l and C l O
scrubbing operations in industry indicate a need for continued
research in this area (1–4).
Recently, research was initiated at the University of South
Alabama to study the scrubbing of C l and C l O . Water scrub­
2 2
bing of C l air streams in packed towers to study the effectiveness
2 and air samples. A search for possible trapping agents showed
of different packings was the starting point for the research.
Feed gas compositions below 1000 ppm C l were used in this 2
study so results could be compared to published work. A s part
of this work, a method was needed to analyze air and water
samples for C l . Along with accuracy, precision and simplicity,
2 Eq. 4
it was desirable that the method be essentially the same for both
phases and more importantly that it allow samples to be taken
but not immediately analyzed. A long shelf life for samples
would allow a greater number of operating conditions to be
tested each day. A review of the literature indicated that no such
method was available (5,6).
The chemistry of chlorine dissolving in water is not simply
a case of physical absorption. U p o n dissolving in pure water,
molecular chlorine hydrolyzes quickly to establish equilibrium
with hydrochloric and hypochlorous acids (7,8):
In addition, hypochlorous acid can ionize into a hydrogen ion
42 Reproduction (photocopying) of editorial content of this journal is prohibited without publisher's permission.
and a hypochlorite ion to an extent dependent on the amount
of chlorine dissolved:
Eq. 2
As equation 1 indicates, the p H of a chlorine/water solution
at equilibrium is a measure of the total chlorine in solution that
is hydrolyzed in the absence of external p H control and of ap­
preciable H O C l ionization. For example, at p H of 3 and 25°C
– 4
( K = 3 . 9 4 4 × 1 0 ( 9 ) ) , more than 99% of the chlorine in solu­
1
tion is hydrolyzed, whereas at a p H of 1, only 4% of the chlorine
in solution is hydrolyzed. Ionization of H O C l in water at low
p H is not significant. Only 0.01% of the total H O C l in solution
– 8
is ionized when the p H is 3 ( K = 2 . 8 9 8 × 1 0
2 at 2 5 ° C ( 1 0 ) ) .
Moreover, for a chlorine/water solution with a p H of 6 at 25°C,
the percent H O C l in solution that is ionized increases only to
about 3%. In this work, the p H of chlorine/water samples to
be analyzed was usually below 3. Therefore, the percent of the
C l hydrolyzed in such samples might be significant, whereas
2
the percent of the H O C l ionized would be small.
Although a number of methods for determining chlorine were
2 2 under consideration, one using ion chromatography (IC) was
considered to have the greatest potential because chloride ions
-
( C l ) in solution are quite stable and are easily measured by
IC (11). In order to use I C , therefore, an appropriate trapping
–
agent for converting chlorine to CI was needed for both water
that a number of reducing agents could be used for converting
–
chlorine to CI (12). Examples of such agents are:
Eq. 3
Eq. 5
Other possible trapping agents are sulfur dioxide, sodium bi­
sulfite, sulfamic acid, and sodium hydroxide.
Experimental
Reagents
Reagent-grade chemicals were used in this work. Freshly
Eq. 1 distilled water was used for solution preparation and dilutions.
The HCl standards were prepared from 0.1 Ν HCl acculute
(Anachemia).
Journal of Chromatographic Science, Vol. 27, January 1989

Chlorine trapping
A suitable trapping agent for chlorine in air or water samples
–
must convert all of the chlorine to Cl for quantitative analysis
by I C . The agent must neither produce nor contain ions that
have long elution times nor produce peaks that interfere with
– –
the Cl peak. Although KI converts all of the chlorine to C l ,
–
it was rejected because the excess I had a peak elution time
of 18 min. Sodium thiosulfate was rejected also because the ex­
2 –
cess S O had a peak elution time of 21 min. Sulfamic acid
2 3
was unsuccessful because its elution time interfered with the
–
Cl peak. Sulfur dioxide was not tried because of the difficulty
in using a gaseous reagent. Sodium hydroxide was rejected be­
–
cause it produces more than Cl from its reaction with chlorine.
Sodium sulfite worked well as a trapping agent. Sulfite rapidly
were recorded. With these data, the moles of air sampled were
calculated, assuming the air to be an ideal gas saturated with
water vapor.
When not sampling air, the bottle portion of the impinger
was removed, and a tygon tube connected the impinger nozzle
to a caustic bubbler. This allowed a continuous flow of air
through the system to eliminate wall effects on the chlorine.
Prior to sampling, the air flow was momentarily stopped, the
tygon tube was removed from the nozzle, and the bottle portion
of the impinger containing 25 m L of trapping solution was
installed.
Water was sampled for chlorine in one of two ways. More
concentrated solutions were sampled by placing approximately
5 m L of trapping solution, typically 5 to 15 drops of 1 Μ N a S O 2 3

–
reduced chlorine quantitatively to Cl under either acidic or
basic conditions. The mechanism is probably p H dependent.
In this work, the p H varied from very acidic conditions when
trapping chlorine in water samples to basic conditions for air
samples bubbled through sulfite solutions. Standard oxidation-
reduction potentials indicated the likelihood that sulfite, besides
trapping agent in 5 m L of distilled water, in a 100–mL volumetric
flask. Five to ten grams of water sample were added by weight
and the flask was sealed. The used trapping solution was then
diluted to 100 m L for later analysis by I C . In weaker solutions,
usually the case in scrubbing operations, chlorine was trapped
by simply adding a few drops of 1 Μ N a S O trapping agent
2 3

–
reducing C l to C l , could reduce either H O C l under acidic
2 to a minimum 200–mL sample.
–
conditions or O C 1 " under basic conditions to Cl (13,14). In
addition to discussions of a general nature on chlorine and sulfite Analysis by IC
chemistry (15-17), other evidence indicating the ability of sulfite –
Trapped samples were analyzed for Cl on a Model 2000
to reduce chlorine through its hydrolysis products in acidic (18) i / S P ion chromatograph (Dionex) with a Model SP4200 com­
and basic (19) environments has been reported, although the puting integrator (Spectra-Physics) to record elution times and
mechanisms were not certain. The present work was consistent response areas. The column was an H P I C - A S 4 A anion separa­
with these findings. tor (Dionex) with an H P I C - A G 4 A guard column (Dionex).
–
Furthermore, the Cl produced by trapping with sodium Eluent (0.00075 Μ N a H C O , and 0.0022 Μ N a C O ) was 2 3

sulfite was easily measured by I C , and all ions had peak elution pumped through the column at 2 m L / m i n . The regenerant for
times of less than 6 min. The produced HCl was very stable. the ASF–1 suppressor cell (Dionex) was 0.025 Μ H S O at 2 2 4

Although sodium bisulfite was not tried as a trapping agent,
it would probably work similarly to N a S O . A l l chlorine trap­
2 3
ping solutions were freshly prepared from 1 Μ N a S O trapping
agent to provide excess reagent for the stoichiometric conver­
sion of chlorine to H C l .
Sampling
m L / m i n . The conductivity cell was operated at 100ΜSfor a 1–V
signal to the computing integrator. The integrator attenuation
2 3 was 1024 m V for full scale deflection, and the peak threshold
value was 2000. A stable base line was obtained within 1 h of
startup of the equipment. The sample size was 50 μL injected
by glass syringe.
The N a S O reagent used in preparing trapping solutions con-
2 3

A i r was sampled for chlorine by passing 1 L through a midget

impinger containing 25 m L of trapping solution, as shown in
Figure 1. A l l air samples were taken from sources above at­
mospheric pressure, which provided the approximately 15 i n .
of H O pressure (gauge) needed to drive the air sampling system.
2

A typical trapping solution for air sampling was 6 drops of 1

Μ N a S O trapping agent added to 25 m L of distilled water
2 3

giving a N a S O concentration of about 0.012 Μ and a p H of

2 3

about 8.7 in the midget impinger. Sample volume was controlled

by displacing 1 L of water from an intermediate vessel, initially
filled to overflowing, into an empty 1–L volumetric flask. When
air flow in the sampling system was stopped, the vacuum breaker
on the intermediate vessel eliminated suction on the water in
that vessel, which prevented overfilling the 1–L flask. A single
impinger was sufficient because a second impinger with trapping
solution in series showed no chlorine breakthrough upon analy­
sis. The rate of air sampling, controlled by a Teflon stopcock
upstream of the impinger, ranged from 70 to 250 m L / m i n with
no difference in the results.
The used trapping solution in the impinger was then carefully
washed with distilled water into a 100–mL volumetric flask. The
sample was then diluted to 100 m L for later analysis by I C . A l l
surfaces upstream of the impinger were either glass or Teflon.
The ambient temperature and pressure and the resulting water
Figure 1. Gas sampling apparatus.
head pressure on the air contained in the intermediate vessel

43
 Journal of Chromatographic Science, Vol. 27, January 1989

tained an unknown impurity that appeared on chromatograms
–
at the F elution time. This counteracted the water dip, which
had about the same elution time. A sample strength of about
0.003 Μ N a S O resulted in an impurity peak size that effec­
2 3
tively nullified the water dip and gave a straight base line from
–
injection to the Cl peak. A l l samples, including standards,
were dosed as needed with N a S O to a concentration of 0.003
2 3
Μ to eliminate the water dip and give consistent base lines on
all chromatograms.
Ten HCl standards were prepared over the concentration
range 18.23 to 1.823 m g / L . This range was selected because,
–
on an equivalent Cl basis, it matched Cl concentrations ex­
Gas samples were collected on a volume basis, and the chlorine
mole fraction was calculated by converting the trapped mass
–
of Cl into equivalent moles of chlorine and dividing by the
–
moles of gas sampled. The trapped mass of Cl was the pro­
–
duct of the measured Cl concentration of the diluted trapped
sample multiplied by its volume.
For water samples collected on a weight basis, the trapped
–
mass of Cl was determined as it was for air samples. This
–
trapped mass of Cl was then divided by the sample volume
taking the density of the solution as 1 g / m L to give chlorine
concentration. When the chlorine in water samples was trapped
–
by adding a few drops of 1 Μ N a S O to a minimum 200–mL 2 3

–
pected in trapped samples. Seven successive analyses of an in­ sample, the chlorine concentration was equal to the Cl con­
dividual standard gave area responses with a coefficient of varia­ centration corrected for dilution.
–
tion (RSD) of 0.4%. This value was well within the chromato­ The column gave excellent separation of Cl from other
graph manufacturer's operational limit of an R S D value of 3% anions. Chromatograms of trapped chlorine solutions clearly
– 2 – 2 – 2 –
(20). Table I gives the instrument calibration data. Only two showed C l , excess S O , and produced S O . The S O
3 4 3

2 –
measurements of each standard were made because all R S D to S O conversion could not be correlated quantitatively
4

2 – 2 –
values of standards were within 3 % . Although area response because S O slowly forms S O
3 in water in the absence of
4

to standards could vary up to 2% over an 8–h period, samples
and standards were usually analyzed within 10 min of each
other. A typical chromatogram is shown in Figure 2.
The standard concentration vs. area curve for the calibration
data in Table I deviates slightly from linearity at the low end
of the concentration range. This was possibly the result of a
large peak threshold value eliminating a larger percentage of
a smaller peak.
chlorine. Analysis of trapped samples repeated three weeks after
an initial analysis gave identical results showing at least a three-
week shelf life for trapped samples.
Testing the method
The I C method for analyzing chlorine in gas samples was
tested by using it to measure the composition of a certified
C l / N gas mixture of 530 ppm ±2% (cylinder pressure was
2 2

Trapped samples (unknowns) were analyzed for Cl by –

2000 psig) purchased from Linde. To verify the method for
proper dilution with 0.003 Μ N a S O so that the Cl concen­
2 3
–
determining chlorine in water samples, a comparison was made
tration was within the range of the calibration data while keeping
–
the Cl peak as large as possible, but still on the recorder
–
scale. A standard was then analyzed that gave a Cl peak area
as close in size as possible to the unknown. With the known
– –
standard concentration on a Cl basis, the Cl concentration
(mg/L) of the unknown was calculated using a straight line slope
for the standard concentration vs. area curve at this point and
the responses of the standard and the unknown. The slope was
based on the two standards closest in concentration to the
unknown.

Table I. Data for Standard Curve for Chloride Analysis

Cl Peak areas –

(integirator counts χ 10 ) –6

HClConcn Standard
(mg/L) Sample Mean deviation

18.23 529.204 529.123 0.114

529.042
16.41 473.190 473.594 0.571
473.998
14.58 413.939 414.886 1.339
415.833
12.76 358.704 360.083 1.950
361.462
10.94 303.384 303.452 0.095
303.519
9.115 249.378 248.708 0.948
248.037
7.292 197.115 196.992 0.173
196.870
5.469 143.143 142.990 0.217
142.836
3.646 94.399 94.572 0.244
94.745
1.823 47.861 46.888 1.376
Figure 2. Typical chromatogram of a trapped air or water sample.
45.915

44
Journal of Chromatographic Science, Vol. 27, January 1989
between the method of this work and a standard iodometric
method (wet test) (21) by using both procedures to measure the
concentration of chlorine/water solutions. The iodometric
method was chosen over others because it is a well-established
procedure for determining chlorine over a wide range of con­
centrations and it requires only standard laboratory equipment
(6,22).
The comparison of the water analysis method with the wet
test was made at four different chlorine/water concentrations.
Test chlorine/water solutions were prepared by bubbling both
pure chlorine from a standard 150-pound cylinder and the cer­
tified C l / N mixture mentioned above through distilled water
2 2
in an equilibrium cell at 20°C and at 30°C. In each case, water
samples were taken at equilibrium. Preliminary experiments in­
dicated that bubbling pure chlorine through water at 600 m L / m i n
for approximately 45 min would produce a saturated solution;
however, to insure equilibrium in the cell, pure chlorine was
bubbled for two hours before sampling. Equilibrium was con­
firmed when hourly I C analysis of water samples from the cell,
made after two hours of bubbling, showed no change in com­
position. When bubbling with the certified C l / N mixture, the
2 2
liquid was assumed to be saturated with chlorine when hourly
analysis of the exit gas of the cell by our I C method was un­
changed. For this case, analysis of the exit gas showed no change
in composition after bubbling for approximately 4 h at 600
m L / m i n . In either case, once equilibrium between gas and liquid
had been reached, water samples were taken in duplicate for
analysis, one by I C and the other by wet test.
The wet test for chlorine is based on the formation of iodine
from the reaction of iodide ion with chlorine:
Eq. 6
The iodine is then reduced by sodium thiosulfate with starch
as an indicator:
Eq. 7
The C l concentration is given by:
2
Eq. 8
The procedure follows:
1. Ten milliliters of 2% by weight K I , 2 m L of glacial acetic
acid, and approximately 1 m L of a standard 1% starch
solution were added to a 100-mL volumetric flask which
was tightly capped and tared.
2. A chlorine/water sample was introduced into the flask,
which was immediately capped and weighed. Sample sizes
varied from 10 to 15 g.
3. The sample was then titrated using either 0.1 or 0.005 Ν
N a S O depending on the expected chlorine concentration.
2 2 3
For the comparison involving the water analysis, all chlorine/
water solutions were prepared with freshly made distilled water
stored in a nonmetal system. For wet test analyses, chlorine/
water solutions made with pure chlorine were titrated with 0.1
Ν N a S O , whereas 0.005 Ν N a S O was used for titration
2 2 3 2 2 3
of much weaker solutions made with the certified C l / N mix­ 2 2
ture. Stock 0.1 Ν N a S O was diluted to make 0.005 Ν N a S O .
2 2 3 2 2 3
The strength of the N a S O was checked by a standard method
2 2 3 measure the chlorine added to the scrubbing water in the packed
using titration with potassium iodate (23). The entire process
from loading the flask to completing the titration took approx­
imately 30 min for three samples analyzed by wet test.
Results and Discussion
The I C method of analysis for C l in air was tested on the
2
certified C l / N mixture of 530 ppm ±2%. Analyses for five
2 2
samples taken directly from the cylinder spanning five days gave
an average composition of 538 ppm C l with a standard devia­
2
tion of 11 ppm C l . 2
Agreement between the wet test and the I C method for the
analysis of chlorine in distilled water was also very good, as
shown in Table II. Trials 1, 2, and 3, representing measurements
made on three different days, showed a percent difference be­
tween the two methods of less than 1%. In addition, standard
deviations of concentrations determined by wet test and I C for
the same trials were, respectively, 0.6 and 1.4 m g / L . O f the re­
maining three trials for different operating conditions, only Trial
4 showed a larger difference between the methods than was ex­
pected. The difference found for Trial 4, more than 4%, was
probably because the equilibrium cell had not been adequately
flushed between Trials 3 and 4, which were made sequentially
on the same day. A s a result, the distilled water charged to the
equilibrium cell for Trial 4 probably became contaminated with
–
a small amount of Cl remaining in the cell from the previous
trial. This would cause the Trial 4 analysis by IC to be larger
than that by the wet test. The chlorine concentration range
covered for these samples was 160 to 7000 m g / L .
As part of the comparison of the water analysis method with
the wet test, the exit gas of the equilibrium cell was analyzed
by the I C method to determine equilibrium when bubbling with
the certified C l / N mixture. This was approximately one year
2 2
after the original analysis of the certified C l / N mixture, and
2 2
cylinder pressure at this time was about 1400 psig. Eight analyses
were made of the exit gas (i.e., the certified gas mixture after
having been bubbled through the cell for equilibrium conditions
at 20°C and 30°C). One analysis of a sample taken directly from
the supply cylinder of the certified gas mixture also was made.
These nine analyses spanning three days gave an average com­
position of 512 ppm chlorine with a standard deviation of 3
ppm C l . The analysis of the sample taken directly from the
2
cylinder was 511 ppm. The higher precision of these analyses
compared to the original analysis of the certified mixture was
probably due to better purging of the gas sampling apparatus
before sampling. The small change in chlorine concentration
from 538 to 512 ppm is easily possible, because C l / N mix­ 2 2
tures stored in steel cylinders are known to change concentra­
tion by adsorption or desorption of chlorine as cylinder pressure
changes. The 512 ppm C l concentration is included as operating
2
information in Table II.
The IC method of this work was also used on a pilot 4-in.
packed tower that scrubbed chlorine from air with city water
at 30°C. Analysis of air samples taken from the scrubber covered
a concentration range of 50 to 800 ppm. Additional H C I stand­
ards more dilute than those given in Table I were used when
analyzing air samples as low as 50 ppm, because the resulting
–
trapped samples gave Cl concentrations below the range
shown in Table I. For water samples taken from the scrubber,
the concentration varied from 8 to 65 m g / L . The city water
–
already contained some chlorine as well as Cl from other
sources; therefore, the chlorine concentration could not be deter­
mined by the I C method. The method was used, however, to
tower. This application of the I C method was satisfactory
because chlorine input-output balances for 10 trials were on
average within 3%, with a maximum difference of only 5°7o.
45
 Journal of Chromatographic Science, Vol. 27, January 1989

Table II. Comparison of IC and Wet Test Analysis of 2. J.L. Morrison. Recovery scrubber for waste chlorine gas. Tappi
Chlorine/Water Samples from Equilibrium Cell 51(12): 124A–25A (1968).
Cell Cl con centratioms 3. G.Y. Pan, J.F. DeGraw, and J.J. Renard. Tappi Proceedings, 1982
2

Pulping Conference, pp. 365–70.

Cell Liquid, mg/L b

4. I.F. Rees. Bleach plant scrubber for chlorine and chlorine dioxide.
temperature
Trial Gas a
Wet test IC Difference 6 Appita 34(6): 471–74 (1981).
(°C)
5. A laboratory investigation of an iodometric method for determining
1 30 pure 5467 5480 0.24 chlorine and chlorine dioxide in pulp and paper industry workplace
2 30 pure 5390 5407 0.32 atmospheres. NCASI Technical Bulletin 409. September 1983.
30 pure 5481 5429 –0.95 6. G.C. White. Handbook of Chlorination, 2nd ed. Van Nostrand
3

4 30 512 ppm 159 166 4.40 Reinhold, New York, 1986, pp. 214–55.
5 20 pure 7072 6904 –2.38 7. G.C. White. Handbook of Chlorination, 2nd ed. Van Nostrand
CD

20 512 ppm 169 171 1.18

a This column indicates the gas bubbled through the equilibrium cell. Pure C l gas 2
contained 0.5% inerts.
b Each reported chlorine concentration for the water in the equilibrium cell, as analyzed
by the method indicated, is the average value for three samples except for Trials
1 and 6, which had one and two samples, respectively,
c Based on the wet test.
Further testing of the method at other air and water concen­
trations was felt to be unnecessary because of the good results
obtained in the comparison studies and in the scrubber material
balance calculations.
The chlorine trapping method of this work for air and water
analysis could easily be extended to higher chlorine concentra­
tions by using a stronger trapping solution followed by greater
dilution of the trapped samples. Lower chlorine concentrations
in air and water samples could be determined simply by using
more sensitive range settings on the chromatograph and larger
sample volumes. A l s o , it should be possible to modify the gas
sampling apparatus to accommodate unpressurized gas samples.
Acknowledgment
This work was done under Grant ARI–108 of the Alabama
Research Institute whose support is most gratefully acknow­
ledged.
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1. L.M. Bungey. Bleach plant atmosphere improved at CFP by scrub­ Manuscript received December 29, 1987;
bing off-gases. Pulp & Paper 55(7): 106–11 (1981). revision received July 25, 1988.

46