New Methods for the Colorimetric Determination of Halogen Residuals. Part II.

Free and
Total Chlorine
Author(s): A. P. Black and G. P. Whittle
Source: Journal (American Water Works Association), Vol. 59, No. 5 (MAY 1967), pp. 607-
619
Published by: American Water Works Association
Stable URL: http://www.jstor.org/stable/41265215
Accessed: 27-04-2016 01:22 UTC

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 New Methods for the Colorimetrie Determination
oí Halogen Residuals. Part II. Free and
Total Chlorine

A paper submitted by A. P. Black, Project Director and Research

Prof. Emeritus, Univ. of Florida, Gainesville, Fla., and G. P. Whittle,
Assistant Prof., Dept. of Civil Engineering, Univ. of Alabama, Uni-
versity, Ala.

use of chlorine as a disinfectant Protection Against Pollution

for potable water supplies is one
of the greatest advances ever made in
preventive public health. However,
chlorine has some limitations. In par-
ticular, the almost universally accepted
o-tolodine test for chlorine residuals
is a subject of concern. The reac-
tion of chlorine with ammonia and
ammonium salts to form chloramines,
which are less effective disinfectants,
has long been recognized as a major
limitation in the application of chlo-
rine. Compounding this problem
has been the difficulty encountered in
the use of the o-tolidine test to distin-
guish between a free-chlorine and a
chloramine, or combined chlorine re-
sidual. Commonly called the "flash"
test, it is difficult to perform and the
results are not always interpreted cor-
rectly. Lowering of the sample tem-
perature to nearly 0°C and the arsenite
modification are procedures not easily
adaptable to general use. They are
most suited for carefully controlled lab-
oratory studies. The result has been
that, for the past 50 years or more, the
standard colorimetrie test employed in
this country for chlorine residuals us-
ing o-tolodine has been unsatisfactory
for the determination of free chlorine.
607
The importance of applying, main-
taining, and controlling a free-chlorine
residual in municipal water treatment
plants can readily be appreciated in
view of the ever-increasing pollution of
our water supplies, with the corre-
spondingly greater risk of serious wa-
terborne diseases. Morris г recently
suggested chlorination practices to pro-
vide and maintain residuals in the range
of 1-2 ppm of free Cl2 at a proper pH
for a sufficient contact time, for all wa-
ters that have been subjected to any
significant degree of contamination. Of
equal importance is the maintenance of
a free-chlorine residual in the almost
1,000,000 private and public swimming
pools in this country, as well as new
pools which are being built at a con-
stantly accelerating rate. The proper
disinfection of swimming pools is not a
simple matter. The chemical and bac-
tériologie standards to be met are
those promulgated by the UHPHS for
public drinking water supplies. In
many ways the disinfection of swim-
ming pool water is more difficult than
for municipal water supplies, as pool
water is subject to continuous reinfec-
tion from bathers, the atmosphere, and
the surrounding environment. In or-

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 608 A. P. BLACK & G. P. WHITTLE Juur.AWWA
der to comply with the regulations of
the Conference of State Sanitary En-
gineers and the National Sanitation
Foundation requiring that a free-chlo-
rine residual of at least 0.4 ppm be
continuously maintained throughout a
pool water, it is essential that a rapid,
simple, and accurate colorimetrie test
be available to distinguish between free
and combined chlorine at normal pool
water temperatures.
The authors, cognizant of the need
to maintain a free-chlorine residual,
initiated this investigation to develop
a rapid, simple, accurate colorimetrie
test for free chlorine in the presence of
combined chlorine, without the serious
disadvantages inherent in the presently
accepted o-tolodine method.
Previous Methods
The limitations of o-tolodine were
recognized in a study by Adams and
Buswell 2 in 1933. They pointed out
that these include the development of
color by both free chlorine and chlor-
amines, oxidized manganese, Fe(III)
at concentrations greater than 0.3 ppm,
and nitrites at concentrations greater
than 0.1 ppm. In 1934, Tarvin, Todd,
and Buswell 3 attempted to find a re-
agent which eliminated some of the
difficulties experienced with o-tolodine.
A large number of different compounds
were evaluated as colorimetrie reagents
for chlorine but none was found to be
superior to o-tolodine.
The efforts of some later investiga-
tors to find a new reagent for chlorine
residuals have met with some suc-
cess. Palin 4 employed N,N-diethyl-p-
phenylene diamine (DPD) and re-
ported that a free-chlorine residual
may be determined by its instantaneous
reaction with this reagent to produce
a red color, whereas combined chlo-
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rine reacts at a slower rate, making
possible a differentiation between the
two types of chlorine residuals. One
disadvantage of this method is the in-
stability of DPD in solution form,
necessitating the use of dry powders or
tablets which require a waiting time
for complete solution in the water sam-
ple. Recently, Sollo and Larsen5
studied in detail the method originally
described by Taras6 involving the
bleaching effect of free chlorine on a
methyl orange solution and reported
significantly less interference from com-
bined chlorine than that obtained with
DPD. The methyl orange test, as
it depends upon bleaching rather than
color development, requires precise
measurement of the quantity of re-
agents added and is somewhat depen-
dent on temperature. Interested read-
ers are referred to a paper by Nichol-
son 7 which reviews all known methods
for determining free and combined
chlorine and two papers from the Wa-
ter Research Association of England,8
which provide similar information.
Experimental Method
In Part 1 9 of this series, a method
for the determination of iodine resid-
uals in water employing leuco crystal
violet, 4,4',4" methylidynetris (N,N-
dimethylaniline) as the indicator was
described. By this method a mixed
indicator solution is prepared consist-
ing of a dilute leuco crystal violet solu-
tion and a saturated mercury (II)
chloride solution. This mixed indi-
cator not only enhances color develop-
ment with aqueous iodine buffered at
pH 4 but also drastically retards color
development by any coexisting chlor-
amines.
In this investigation, the adaptation
of the previously developed iodine
method to the determination of a free
May 1967 COLORIMETRIC DETERMINATION 609
chlorine residual was studied. It was
found that at pH 4, the color produced
with chlorine had a distinct blue ap-
pearance compared to the normal crys-
tal violet color obtained with iodine.
In spite of this visual difference, the
color produced in the concentration
range of 0.1 mg/1-2 mg/1 of Cl2 was
found to possess а Л max of 592 т/л
with maximum absorbance at pH 4
identical to that found for crystal violet
solutions.
Preliminary studies indicated that
the color developed in dilute chlorine
solutions is probably the result of both
an oxidation process and a substitution
reaction producing a chlorinated indi-
cator species. This structural modifi-
cation resulting from chlorine substitu-
tion alters the absorption character-
istics of the final dye molecule to
produce the distinct blue color.
Quality of Indicator
The absorbance and to some degree
the color of the test solutions were
found to be somewhat dependent on the
quantity of indicator initially added.
However, employing an indicator so-
lution containing 3 g of leuco crystal
violet per liter, excellent reproducibil-
ity of absorbance values was obtained
with test solutions containing concen-
trations of 0.1-2 mg/1. The slight
change in color with increasing chlo-
rine concentrations was not accom-
panied by a change in Л max which
remained at 592 т/л over the entire
range of chlorine concentrations in-
vestigated.
The pH of the test sample should be
held in the range of 3.8-4.1, which is
normally provided by a strong acetic
acid-sodium acetate buffer. The ace-
tate buffer, however, prevents complete
solubility of the more concentrated in-
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dicator (3 g/1) solution in the test
sample. For natural waters employed
in this study, a mixed buffer consisting
of equal parts of acetate and citric buf-
fer systems was found to promote indi-
cator solubility while providing the
required pH control. For waters con-
taining large concentrations of dis-
solved solids which may affect the
solubility of the indicator, increasing
the proportion of the citric buffer sys-
tem will facilitate indicator solution,
provided good pH control is obtained.
Reagents
For the determination of free chlo-
rine, the following reagents are em-
ployed :
1. 4,4',4"-Methylidynetris (N,N-di-
methylaniline),* commonly designated
leuco crystal violet. Dissolve 3 g of
the above compound in approximately
500 ml of distilled water containing 7
ml of 70 per cent perchloric acid. Di-
lute to 1 liter with distilled water and
determine pH, which should be in the
range of 1.4 to 1.6. The initial solu-
tion of this compound in perchloric
acid should be carried out in darkness,
e.g., brown glass.
2. Mixed indicator solution. Mix
by volume, twelve parts of the above
solution of leuco crystal violet and one
part of a saturated aqueous solution of
mercury (II) chloride, HgCl2, and
store the mixture protected from
light.
3. Buffer solution, pH 4. Solution
(a) - mix by volume 35 parts 4 M
potassium hydroxide solution and 70
parts 2 M citric acid solution. Solu-
tion (b) - dissolve 161.2 g of acetic
acid and 49.5 g of sodium acetate, an-
* Eastman No. 3651, a product of Distil-
lation Products Industries, Eastman Organic
Chemicals Dept, Rochester, N.Y.
 610 A. P. BLACK & G. P. WHITTLE Jour. AW W Л

i i i i i i i i i >i
0.8

I °6

0.2

Ol^-

0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0

Free Chlorine- mg/l

Fig. 1. Standard Absorbance Curve for Free Chlorine

The cell is 1 cm, Л equals 592 w/x, and the pH of the samples is 4. The absorbance is
obtained on a 50 -ml sample treated with 1-ml buffer solution and 1-ml indicator
solution.

0.08 i

' 0.06

1 ^^ ^^°
о 0.04

| 0.02

2 4 6 8 10 12 14 16
Time-mm

Fig. 2. Reaction Bates of Mixed Indicator with Monochloramine as a Function of

Temperature

The solid lines represent samples containing 1 mg/l of Cl2 as NH2Cl and the broken
lines, 4 mg/l of Cl? as NH2Cl. The open circles and solid circles are for reaction
temperatures of 25° С and 35°C, respectively.

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May 1967 COLORIMETRIC DETERMINATION 611

hydrous, in distilled water and dilute To perform the analysis, measure 50

to 1 liter.
Final buffer solution. Mix equal
volumes of solution (a) with solution
(b).
All these reagents must be prepared
in ammonia-free distilled water.
Free-Chlorine Absorbance Curve
Free-chlorine solutions in the con-
centration range of 0.1-2. mg/1 of Cl2
ml of sample chlorine concentration
into a 100-ml volumetric flask. Add 1
ml of buffer solution, pH 4, and swirl
to mix. Add 1 ml of mixed indicator
solution by filling a pipet, placing the
tip against the glass inside the neck of
the volumetric flask, and allowing the
solution to flow down the glass surface
into the sample. Swirl to mix and de-
termine absorbance at 592 m^.

» I ' I 4- I I И
0.8

* 0.4

- - y^-
0 lcL¿

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

Chlorine, CI2-mg/l

Fig. 3. Total Chlorine Standard Absorbance Curve

The cell is 1 ml, A equals 592 mp, and the pH of the samples is 4. The open circles
represent samples containing free chlorine while the solid circles represent sam-
ples containing mono chlor amine.

are prepared by dilutions of a standard- A plot of absorbance values against

ized chlorine or hypochlorite solution,
using only ammonia-free distilled wa-
ter. Immediately prior to colorimetrie
analysis, each chlorine solution is ana-
lyzed for free chlorine by means of an
amperometric titrator.
chlorine concentrations is shown in
Fig. 1, and, as might be anticipated
from the chlorine substitution reaction,
Beer's law is not followed as the con-
centration of chlorine is increased.
Excellent reproducibility is obtained,

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612 A. P. BLACK & G. P. WHITTLE Jour. AW WA
however, and chlorine residuals within
±0.02 mg/1 of the amperometric titra-
tion results may be rapidly determined.
Chlorine-Ammonia Compounds
As demonstrated previously by the
method for iodine residuals,9 the pres-
Fig. 4. Comparison of Colorimetrie and
Amperometric Titration Results for the
Determination of Free and Total Chlorine
The samples initially contained 0.1 mg/l
of NHS added as NHACl and were main-
tained at 24°C and pH 6.5. The reaction
time was 4 hr. The upper graph is for
free chlorine and the lower for total chlo-
rine. In both graphs, the square points
are for amperometric titration results and
the solid circular points for colorimetrie
results.
enee of mercury (II) chlorine in the
sample effectively retards formation of
color by chlorine-ammonia compounds
for a sufficient interval, to permit an
accurate determination of free chlo-
rine. The rate of color development
by monochloramines as a function of
time and temperature and the corre-
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sponding error introduced into a test
for free chlorine are shown in Fig. 2.
For absorbance readings, a square cell
providing a 3-cm light path was em-
ployed to increase sensitivity. This
figure shows that, if a sample is read
within 3 min after the addition of the
Fig. 5. Comparison of Colorimetrie and
Amperometric Titration Results for the
Determination of Free and Total Chlorine
The samples initially contained 0.1 mg/l
of NHS added as NH4Cl and were main-
tained at 24°C and pH 6.5. The reaction
time was 16 hr. The upper graph is for
free chlorine and the lower for total chlo-
rine. In both graphs, the square points
are for amperometric titration results and
the solid circular points for colorimetrie
results.
mixed indicator, an error no greater
than 0.02 mg/l of Cl2 results, with
combined-chlorine concentrations as
high as 4 mg/l of Cl2 and reaction tem-
peratures as high as 35 °C.
Only the rate of color development
by monochloramine was investigated,
May 1967 COLORIMETRIC DETERMINATION 613

as efforts to prepare significant concen- shown by the reactions,

trations of di- and tri-chloramines at
normal pH values for swimming pool
water or potable water were unsuccess-
ful, except with very high concentra-
tions of chlorine. Data to be presented
in a following section on breakpoint
I- + CI2 + H2O = HIO + 2C1- + H+ (1)
I" + NH2C1 + H2O
= HIO + Cl" + NH3. (2)
Accordingly, a method for the deter-
mination of total chlorine was de-
veloped. It involved the addition of

TABLE 1

Comparison of Colorimetrie Method with Amper ometric Titration for the Determination of
Chlorine Residuals. Sample Temperature of 24° С Samples Initially Contained
0.1 tng/l of NHZ, added as NHACl

Amperometric Titration - mg/1 of CI2 Colorimetrie Results - mg/1 of Cl2

Sample "* Dí¿; *nd

"* Cl«r is *= ££=; <äfc «к. № as? «га
pounds

Reaction Time - 4 hr

1 0.2 0.01 0.16 0.00 0.16 0.17 0.00 0.18 0.18

2 0.4 0.03 0.33 0.00 0.33 0.36 0.01 0.35 0.36
3 0.6 0.01 0.38 0.04 0.42 0.43 0.01 0.39 0.40
4 0.8 0.01 0.13 0.06 0.19 0.20 0.00 0.17 0.17
4 1.0 0.12 0.03 0.01 0.04 0.16 0.13 0.03 0.16
6 1.2 0.24 0.05 0.04 0.09 0.33 0.21 0.10 0.31
7 1.4 0.40 0.11 0.05 0.16 0.56 0.42 0.15 0.57
8 1.6 0.59 0.10 0.05 0.15 0.74 0.55 0.20 0.75
9 1.8 0.70 0.13 0.04 0.17 0.87 0.72 0.16 0.88
10 2.0 0.95 0.13 0.05 0.18 1.13 0.89 0.21 1.10

Reaction Time - 16 hr

1 0.2 0.00 0.17 0.00 0.17 0.17 0.00 0.14 0.14

2 0.4 0.01 0.33 0.00 0.33 0.33 0.00 0.34 0.34
3 0.6 0.01 0.37 0.02 0.39 0.40 0.00 0.41 0.41
4 0.8 0.01 0.11 0.00 0.11 0.12 0.01 0.09 0.10
5 1.0 0.01 0.04 0.00 0.04 0.05 0.01 0.02 0.03
6 1.2 0.13 0.06 0.00 0.06 0.19 0.11 0.06 0.17
5 1.4 0.33 0.08 0.04 0.12 0.45 0.35 0.13 0.48
8 1.6 0.45 0.08 0.05 0.12 0.57 0.40 0.16 0.56
9 1.8 0.70 0.10 0.04 0.14 0.84 0.68 0.14 0.82
10 2.0 0.93 0.11 0.04 0.15 1.08 0.90 0.16 1.06

chlorination indicate that di- and tri-
chloramines do not interfere with the
determination of free chlorine in the
concentration range studied.
Determination of Total Chlorine
At pH 4, both free chlorine and
combined chlorine - that is, chlorine-
ammonia compounds - oxidize the io-
dide ion to hypoiodous acid (HIO) as
potassium iodide to the sample, fol-
lowed by the colorimetrie determina-
tion of the iodine residual produced.
The iodine determined or, more con-
veniently, the absorbance of the color
produced in the test solution, is re-
lated to the concentration of total chlo-
rine initially present. The reagents
required and the test procedure are
given below.

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614 A. P. BLACK & G. P. WHITTLE Jour. AW W A

1. Acetate buffer, pH 4: dissolve thoroughly and read absorbance of the

161.2 g of glacial acetic acid and 49.5
g of sodium acetate, anhydrous, in dis-
tilled water and dilute to 1 liter.
2. Total-chlorine buffer: dissolve 3
g of potassium iodide in 1 liter of the
acetate buffer, pH 4. Store in brown
solution at 592 m//,.
Following this procedure, a standard
absorbance curve for total chlorine,
shown in Fig. 2, was prepared, em-
ploying sample solutions containing
known concentrations of free chlorine

Fig. 6. Proposed Mechanisms of Oxidation of Leuco Crystal Violet by Hypoidodous

Acid and Hypochlorous Acid

In (a), hypoiodous acid reacts through a hydride transfer to produce crystal violet.
In (b), hypochlorous acid, in addition to a hydride transfer, also reacts by a chloride
substitution producing a new species, chlorinated crystal violet.

glass or opaque bottle and keep tightly or monochloramine. At concentrations

closed when not in use.
3. Mixed-indicator solution: pre-
pare as previously described under
method for determination of free chlo-
rine.
The procedure is as follows : mea-
sure 50 ml of sample into a 100-ml
volumetric flask. Add 0.5 ml of the
total-chlorine buffer and swirl to mix.
Allow a reaction time of at least 10
sec, followed by the addition of 0.5 ml
of the mixed indicator solution. Mix
of total chlorine greater than 0.3 mg/1
of Cl2, absorbance values for both free
chlorine and monochloramine fall on
the same line. Below this total-chlo-
rine concentration, the absorbance
values obtained with solutions of mono-
chloramine were slightly less than
those for free chlorine.
It is suggested that at these very
low concentrations of reactants, a state
of equilibrium is approached in the
redox reaction involving monochlor-

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May 1967 COLORIMETRIC DETERMINATION 615

amine and the I" ion. In this case, less
than a stoichiometric quantity of H IO
is produced, resulting in lower absorb-
ance values. In any event, the error
introduced is small and by reference
to the dotted line in Fig. 2, precise
results may be obtained for samples
tions as high as 50 mg/1 of I" did not
interfere when the mixed indicator was
employed. The concentration of 20
mg/1 of I" will theoretically allow
the determination of a total-chlorine
residual up to 10 mg/1, but the extreme
sensitivity of the method prohibits an

Fig. 7. Comparison of Absorbance Curves Obtained With Different Procedures for Indi-
cator Addition

The cell is 1 cm, ' equals 592 тц, and the pH of the sample is 4. The open circles
represent addition of indicator solution down surface of sample flask while the solid
squares represent direct addition of indicator solution to sample.

containing essentially all chlorine in accurate absorbance reading at this

the combined form. The incorpora-
tion of potassium iodide in the pH 4
buffer solution afforded a convenient
one-step sample treatment for this de-
termination. This solution has been
found to be stable for months if reason-
ably protected from exposure to light
and air. The quantity of potassium
iodide added is adjusted to produce a
concentration of approximately 20 mg/1
of I" in the sample. This concentration
of I" is not critical, however, as pre-
vious studies showed that concentra-
high concentration without suitable
dilution procedures.
The difference between the free-
and total-chlorine determination repre-
sents the combined chlorine present,
and it may be accurately determined
in the following manner.
Breakpoint Chlorination
Results of the proposed colorimetrie
method were compared with those ob-
tained by amperometric titration on
water samples containing an initial am-

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616 A. P. BLACK & G. P. WHITTLE Jour.AWWA
monium ion concentration and treated
with increasing quantities of a chlorine
solution. A series of water samples
containing SO mg/1 of alkalinity, added
as sodium bicarbonate, and 100 mg/1
of total hardness, added as calcium
chloride, were treated with an am-
monium chloride solution to contain
0.1 mg/1 of NH3. Increasing incre-
ments of a standardized chlorine solu-
tion were added providing an initial
concentration range of 0.2-2 mg/1 of
Cl2 in the sample series. The reaction
pH was near 6.5, and after standing
for 4 hr, the samples were analyzed by
amperometric titration for free chlo-
TABLE 2
F ree- Chlorine Déterminations on Samples
at Various Temperatures
Sample Amperometric Colorimetrie
Temperature Titration Result
°C free. Clr-mg/l free Cl^-mg/l
8°C 0.42 0.45
8°C 0.76 0.78
15°C 0.22 0.21
15°C 0.50 0.52
25 °C 0.48 0.49
25°C 0.85 0.82
32°C 0.58 0.57
35°C 0.57 0.57
35°C 1.34 1.32
rine, monochloramine, and di- and tri-
chloramines and colorimetrically for
free and total chlorine. The analyses
were repeated after allowing the sam-
ples to stand for a total of 16 hr. The
results are tabulated in Table 1 and
shown in Figs. 4 and 5. Excellent
agreement was obtained between color-
imetrie and amperometric titration re-
sults, and the data presented in Table 1
indicate that di- and tri-chloramines do
not interfere in the determination of
free chlorine in th concentrations ob-
tained. In addition, a comparison of
the two methods shows that both di-
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and tri-chloramines are included in the
colorimetrie method for total chlorine.
Interferences
The interference from combined
chlorine has been shown to be very
slight with relatively high concentra-
tions of chloramines at elevated tem-
peratures, provided the determination
is completed within a reasonable time.
The interference from iron and ni-
trate ions up to 20 mg/1 is negligible
for the determination of both free and
combined chlorine. Colorimetrie tests
performed on both natural and syn-
thetic waters indicate no interference
from alkalinity values up to 150 mg/1
and total hardness values up to 300
mg/1. No interference was found with
chloride ion concentrations up to 600
mg/1. Chloride ion concentrations
above this value result in slightly lower
absorbance values.
The nitrite ion produces a color at
a very slow rate but the interference
in both the free- and total-chlorine
tests is negligible when the concentra-
tion of NO2" is less than 2 mg/1.
The oxidized forms of manganese
were found to interfere as even very
low concentrations of these species pro-
duced a rapid color development with
the indicator. Although not investi-
gated in this study, it is believed that
a suitable arsenite modification may be
employed to compensate for this inter-
ference.
Many colorimetrie tests performed
on natural surface and ground waters,
as well as swimming pool waters, indi-
cate that constituents normally present
in water do not interfere in the de-
termination of free chlorine.
Influence of Temperature
The colorimetrie test for free chlo-
rine is, to a remarkable degree, unaf-
May 1967 COLORIMETRIC DETERMINATION 617

fected by the temperature of the sam-
ple, as accurate determinations may be
obtained, without any special precau-
tions, over a sample temperature range
of 8°C-35°C. This is demonstrated
by the data shown in Table 2 in which
colorimetrie results are compared with
amperometric titration values over a
wide sample temperature range.
It was shown previously in Part I 9
of this series that for the determination
of total chlorine (the determination of
iodine released by chlorine) the effect
of temperature up to 40° С is negligible.
August when pool water temperatures
were between 28°C-32°C. The color-
imetrie results are compared with am-
perometric titration results on the same
sample as shown in Table 3. To in-
sure that a free-chlorine residual would
be present, all pool waters with the
exception of No. 7 were treated heavily
with hypochlorite or gaseous chlorine
prior to these spot determinations.
A similar study was carried out in a
water treatment plant and the results
obtained with the new colorimetrie test,
amperometric titration, and the o-toli-

TABLE 3

Spot Determination of Free- Chlorine Residuals in Eight Pools by New Colorimetrie Test

Amperometric Titration
Poni Water Free Cl2 by
TWMn S N TemP- New Test
TWMn S N °C mg/l Free Cl2 Combined Cl2 Tot. CI2
mg/l mg/l tng/l

1 30 0.01 0.02 0.13 0.15

2 31 0.28 0.27 0.03 0.30
3 30 0.18 0.20 0.18 0.38
4 32 0.31 0.32 0.10 0.42
5 28 0.17 0.15 0.07 0.22
6 31 0.20 0.18 1.20 1.38
7 30 0.06 0.05 3.00 3.05
8 30 0.35 0.38 2.10 2.48

Although the reaction rate between
combined chlorine and the indicator
increases with an increase in tempera-
ture (Fig. 2), free chlorine may be
accurately determined at relatively high
dine test are compared in Table 4. The
new colorimetrie test was performed
rather rapidly by a person who had
only a few minutes instruction in its
use.

sample temperatures, provided the de-
termination is carried out in a reason-
able time.
Field Tests
A test kit for determining free chlo-
rine with appropriate color standards
was assembled and employed in a spot
determination of free chlorine in eight
typical swimming pool waters. These
tests were performed in the month of
Both these field studies confirm the
laboratory findings that free chlorine
may be accurately determined in the
presence of combined chlorine at rela-
tively high water temperatures.
Discussion
In Part I of this series, the indicator,
leuco crystal violet, has been shown to
undergo a normal oxidation reaction to
its highly colored form, crystal violet,

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618 A. P. black & G. P. whittle Jour. A WW A
in the presence of an iodine residual.
Kinetic data indicate that this reaction
proceeds exclusively through HIO,
possibly through a hydride transfer, as
shown in Fig. 6 (a). There is evi-
dence that leuco crystal violet, in the
presence of free chlorine, undergoes a
chlorine substitution reaction in addi-
tion to the normal oxidation step. A
possible reaction path and product are
presented in Fig. 6 (b). Hypochlor-
ous acid is shown as the reactive spe-
cies, as aqueous chlorine buffered at
pH 4 is predominantly in this form.
The absorbance data show that the
values obtained with free chlorine
TABLE 4
Comparison of Methods for Chlorine Residuals
on Waters From Treatment Plant
AlTitřaUoenrÍC New Test o-Tolidine Test
Free Cl2f Total Cl2, Free Cl2, ^f)1 Tot. Cl2,
mg/l mg/l mg/l &ffi rng/l
0.73 2.79 0.70 0.02 2.8
0.70 2.44 0.75 0.02 2.5
0.90 2.99 0.85 0.06 2.9
0.80 2.86 0.85 0.00 1.9
0.15 2.49 0.20 0.00 1.9
0.02 2.09 0.00 0.00 1.9
(Fig. 1) are approximately one-half
those theoretically expected (Fig. 3),
and for this reason the reaction of two
moles of HOC1 to produce one mol of
colored product is shown in Fig. 6
(b). However, di- and tri-chloro re-
action products may also be produced
as the relative decrease in absorbance
values with increasing chlorine concen-
trations indicate that larger proportions
of the chlorine residual are consumed
in substitution rather than oxidation.
As a result of the substitution reac-
tion, the final colored product is in-
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fluenced by the ratio of free Cl2 to
indicator at the beginning of the re-
action. The addition of the indicator
solution down the sides of the sample
flask prevents agitation of the sample
solution, so that the entire quantity of
indicator solution is added before ap-
preciable reaction takes place. This
permits a high initial concentration of
indicator to be present and, on mixing,
produces solutions of the highest ab-
sorbance. A comparison of the ab-
sorbance curves obtained by two differ-
ent methods of indicator addition is
shown in Fig. 7. The dotted line rep-
resents the direct addition of the indi-
cator solution to the sample, and the
solid line denotes the addition of indi-
cator solution down the surface of the
flask (Fig. 1). The difference in ab-
sorbance values between the two ad-
dition procedures increases as the con-
centration of chlorine increases. This
is probably as a result of the increases
in the chlorine substitution reaction
and its greater dependence on mixing
conditions. Regardless of the method
employed, excellent reproducibility of
results is obtained as to both color and
absorbance, provided the same indica-
tor addition procedure is followed for
each sample.
Summary
A method for the determination of
free chlorine employing leuco crystal
violet as the indicator has been shown
to give accurate and reproducible re-
sults with minimal interference from
combined chlorine at relatively high
water temperatures. The method is
very rapid, involving only a matter of
seconds to develop the test color, and
the stability of the developed color al-
lows ample time for accurate color
May 1967 COLORIMETRIC DETERMINATION 619
matching with standards. The effect
of sample temperature on the accuracy
of the method is negligible over a wide
range and constituents normally pres-
ent in water do not interfere. The
oxidized forms of manganese produce
the only serious interference found,
and in the case of the relatively few
waters presenting this problem, it is
believed that it can be solved by using
a suitable arsenite modification.
Application of the test method in
field studies involving swimming pool
and treatment plant waters gave results
in close agreement with those obtained
by amperometric titration. All re-
agents are easily prepared and show
exceptional stability in solution form.
The test method is most satisfactorily
employed with free-chlorine concentra-
tions of 2 mg/1 or less, but may be ex-
tended greater than this concentration
by suitable dilution methods.
A very sensitive method for total
chlorine has been presented and when
used in conjunction with the free-chlo-
rine test, will permit the determination
of a combined chlorine residual by dif-
ference.
As of publication date, there are at
least six manufacturers * in the process
of preparing test kits based on these
methods for the determination of free
and total chlorine, and it is anticipated
that these kits will be available by early
1967.
*Hach Chem. Co., P.O. Box 907, Ames,
Iowa 50011; Industrial Specialties, 7122
7122 Gerald Ave., Van Nuys, Calif. 91406;
The LaMotte Chem. Prod. Co., Chestertown,
Md. 21620; Salisbury Industries, Inc., 130
County Courthouse Road, Garden City Park,
N.Y. 11040; W. A. Taylor & Co., 7300
York Rd., Baltimore 21204; and one in Eng-
land, Tintometer Ltd., Waterloo Road,
Salisbury, Wiltshire, England.
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Acknowledgments
Appreciation for valuable help in the
application of these test methods is
expressed to Dr. R. N. Kinman, now
Assistant Chief, Demonstration Grants
Activity, FWPCA, Dept. of Interior,
Washington, D.C.
The project was supported in part
by the Special Purpose Training
Grant SP-6-63 from the Division of
Community Health Services, USPHS,
and in part by Demonstration Grant
WPD- 19-04-66 from the Division
of Research and Training Grants,
FWPCA, Dept. of Interior, Washing-
ton, D.C.
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