Correction for Chloride Interference in the Chemical Oxygen Demand Test

Author(s): E. R. Burns and Craig Marshall

Source: Journal (Water Pollution Control Federation), Vol. 37, No. 12 (Dec., 1965), pp. 1716-
1721
Published by: Water Environment Federation
Stable URL: http://www.jstor.org/stable/25035442 .
Accessed: 04/09/2013 23:47

Your use of the JSTOR archive indicates your acceptance of the Terms & Conditions of Use, available at .
http://www.jstor.org/page/info/about/policies/terms.jsp

.
JSTOR is a not-for-profit service that helps scholars, researchers, and students discover, use, and build upon a wide range of
content in a trusted digital archive. We use information technology and tools to increase productivity and facilitate new forms
of scholarship. For more information about JSTOR, please contact support@jstor.org.

Water Environment Federation is collaborating with JSTOR to digitize, preserve and extend access to Journal
(Water Pollution Control Federation).

http://www.jstor.org

This content downloaded from 131.91.169.193 on Wed, 4 Sep 2013 23:47:48 PM

All use subject to JSTOR Terms and Conditions
 CORRECTIONFORCHLORIDE
IN THE CHEMICAL
INTERFERENCE
OXYGENDEMANDTEST
E. R. Burns and Craig Marshall

An improved procedure for chemical types of samples. The procedures

oxygen demand (COD) measurement which omit the addition of silver sul
has been used successfully for waste fate or allow a reduction in digestion
waters with saline concentrations as time for selected samples do not meet
high as 3 percent. Mercuric sulfate is the latter requirement. Such devia
added to complex the chloride, and tions are not recommended because
silver sulfate is the oxidation catalyst. wastes can be quite unpredictable and
The calculation requires both a sub comparative testing means little un
traction correction, which varies ex less a sufficiently rigorous universal
as the chloride concentra procedure is followed strictly.
ponentially
to Eecent and Jen
tion, and a multiplication correction papers by Cripps
compensate for oxidation interference. kins (2) and Dobbs andWilliams (3)
Test results on water containing only propose modifications for the standard
pure organic material and municipal COD procedure (1) to minimize the
effluents with no chloride addition are significant and uncertain corrections
on the same when appreciable amounts of chloride
compared with test results
samples to which known amounts of ion are present. Each has one or

chloride were added. more limitations which prevent its uni

The standard procedure for COD versal application.
1 is not entirely satisfactory for sam Dobbs and Williams (3) proposed
( )
amounts to eliminate the necessity for a chloride
ples containing appreciable
of chloride ion. The chloride ion oxi correction by a modification which
dation and the mutual effect of the would remove chloride ion from the
material and chloride ion on reaction by complexing it into a soluble
organic
one another are some of the complica undissociated compound. They sug
tions which had not been resolved gested that the addition of 1 g of
there was mercuric sulfate (A.E.), even in the
satisfactorily. Consequently,
need for a COD procedure to test chlo presence of 0.75 g of such an effective
which would catalyzing agent as silver sulfate,
ride-containing samples
be adequate to satisfy the requirements would quantitatively inhibit chloride
of both industry and official regulating ion oxidation by completely bonding
Such a procedure would the ion in a soluble mercuric chloride
agencies.
have to be as simple, accurate, and complex. Their work was confined to
as and applicable to all samples with chloride contents of 2,000
rapid possible,
mg/1 and less. At these concentrations,
E. B. Burns is Supervisor, Test Methods the suggestion appeared to be valid.
Laboratory, Standard Oil Company of Cali In our investigation, however, the rec
Calif. The late Craig
fornia, Richmond, ommended amount of added mercuric
Marshall was, at the time of this paper's
Test Meth sulfate was inadequate for higher
preparation, Analytical Chemist,
ods Laboratory, Standard Oil Company of chloride concentrations. Also, their as
California, Richmond, Calif. sumption that the COD of high-chlo^
1716

This content downloaded from 131.91.169.193 on Wed, 4 Sep 2013 23:47:48 PM

All use subject to JSTOR Terms and Conditions
Vol. 37, No. 12 CHLORIDE CORRECTION FOR COD 1717

ride samples can be measured success In both the standard and modified
fully by aliquoting did not work in procedures, 1 g of silver sulfate and
practice. Such aliquoted COD results 25 ml of 0.25 N potassium dichromate
increase markedly with dilution, some solution were used. Most test results
times by a factor of two or more for were single determinations and may be
dilutions of 10 to 1. As a consequence considered comparable to what might
the procedure is limited to wastes with be expected in routine testing.
low chloride concentrations, and in The best results for the modified
that range it may be adequate if the procedure were obtained by introduc
COD is not so high as to require that ing the sample into the flask first, then
an aliquot be used. adding the mercuric sulfate slowly over
Cripps and Jenkins (2) confirmed a period of two to three minutes while
that mercuric sulfate was an effective swirling the flask, followed by a five
chloride-ion suppressor, but not suffi minute waiting period during which
ciently quantitative to eliminate the the flask was swirled occasionally.
need for a correction. When silver The silver sulfate was added next.
sulfate was used to catalyze the oxida The flask was cooled in ice water, and
tion the correction was even greater. the 75 ml of sulfuric acid were added
The investigators apparently assumed slowly enough to prevent appreciable
the correction to be directly propor solution heating. The potassium di
tional to the chloride content, but our chromate solution was added last, and
work did not confirm this. However, the test finished as in the standard
Cripps and Jenkins developed a near procedure (1). While reasonable re
optimum mercuric-sulfate-to-chloride sults can be obtained in the higher
weight ratio of 10 to 1, which we also sodium chloride ranges by simply ad
used. ding the reagents to the flask, it is
Our work with the procedures of mandatory to follow the above mixing
these authors provided enough data to details for levels below 0.25 percent
conclude that a universally effective sodium chloride.
procedure and calculation would be
more complex than any previously de Chloride Oxidation

veloped. As a consequence we de 1 illustrates

Figure typical pure sys
veloped a more comprehensive pro tem chloride corrections in terms of
cedure, accumulated data, and fitted COD units for variations in both so
a calculation to it. dium chloride content and mercuric
sulfate-to-chloride weight ratios. The
Experimental standard procedure (1) that includes
the use of one gram of silver sulfate
Apparatus and Procedure
was used to establish the corrections.
The apparatus consisted of a 300 Known amounts of sodium chloride
ml round-bottom flask with 24/40 and mercuric sulfate were added and
ground-glass neck, a Friedrichs con 50 ml of water replaced the usual like
denser, and a heating mantle. The size sample. The standard calculation
standard procedure (1) was used for (1) was used to determine the COD
chloride-free solutions of pure chemi value of each mixture without, of
cals and municipal effluents to which course, regard for a chloride correc
no sodium chloride was added. The tion.

procedure was modified for such solu An inspection of Figure 1 indicates

tions and effluents containing added that weight-ratio levels other than 10
sodium chloride by including mercuric to 1 could be used. However, the 10:1
sulfate to equal 10 times the weight of ratio was favored because it provides
chloride ion present. reasonable corrections which are not

This content downloaded from 131.91.169.193 on Wed, 4 Sep 2013 23:47:48 PM

All use subject to JSTOR Terms and Conditions
1718 JOURNAL WPCF December 1965

5 10 15
WEIGHT RATIO OF MERCURICSULFATE TO CHLORIDE

FIGURE 1.?COD due to chloride in the presence of varying amounts

of HgSO* and NaCl.

markedly reduced by increasing the sulfate-to-chloride weight ratio of

amount of mercuric sulfate. Our 10:1.
curve for 2 percent sodium chloride
parallels but is not identical with Incomplete Oxidation
that of Cripps and Jenkins (2). This 2 corrections were
When the Figure
indicates that similar correction curves
included in the calculation for COD
must be established by each laboratory values of either acetic acid or phthalic
for its own equipment and reagents. in solutions so
anhydride containing
Figure 2 is a working correction dium chloride, the results were about
curve plotted from the data in Fig 83 percent of theoretical values over
ure 1, for chloride contents as high rather wide concentrations of chloride
as 3 percent with a constant mercuric ion. This suggested that there is a

This content downloaded from 131.91.169.193 on Wed, 4 Sep 2013 23:47:48 PM

All use subject to JSTOR Terms and Conditions
Vol. 37, No. 12 CHLORIDE CORRECTION FOR COD 1719

.10 -25
PERCENTSODIUM
CHLORIDE

FIGURE 2.?COD due to various amounts of sodium chloride and a constant mercuric
sulfate to chloride weight ratio of 10 to 1.

constant oxidation interference related where :

to the mutual presence of organic ma A = ml for blank
Fe(NH4)2(S04)2
terial and chloride ion which can be B = ml for
Fe(NH4)2(S04)2 sample
for by including a multi C = of Fe(NH4)2(S04)2
compensated normality
of When D = chloride correction
plication factor 1.20. this (from Figure
factor is made a part of the calcula 2)
tion its reads: for the usual 50-ml samples. This
equation becomes
COD, mg/1 COD, mg/1

BUA-B)CXSm-SOD\
[ ml sample j
.{<A-B)?X8'000-?>}X1.20
TABLE I.?Effect of Variable Amounts of Salt on COD Measurements of Pure Chemicals

COD
(mg/1)

Amount
NaCl Added Recovered
Compound
<%) (mg)
Theoretical
Standard Proposed
Calculation Calculation

0.0 Acetic acid 10.9 232.4 226 97

0.3 Acetic acid 10.9 232.4 221 95
0.6 Acetic acid 10.9 232.4 218 94
1.5 Acetic acid 10.9 232.4 230 99
2.4 Acetic acid 10.9 232.4 226 97

0.0 Phthalic anhydride 10.0 324.0 319 98

0.3 Phthalic anhydride 10.0 324.0 320 99
0.6 Phthalic anhydride 10.0 324.0 320 99
1.5 Phthalic anhydride 10.0 324.0 321 99
2.4 Phthalic anhydride 10.0 324.0 323 99

This content downloaded from 131.91.169.193 on Wed, 4 Sep 2013 23:47:48 PM

All use subject to JSTOR Terms and Conditions
 JOURNAL WPCF
1720 December 1965

TABLE II.?Effect of Variable Amounts of Salt on COD Measurements of Municipal Effluents

COD
(mg/1) Deviation from
NaCl Identification
Sample Average
(%) (%)
Standard Calculation Proposed Calculation

0.0 Municipal effluent-I 175

0.5 Municipal effluent-I 178
2.0 Municipal effluent-I 173
3.0 Municipal effluent-I 175

0.0 Municipal effluent-II 417

0.5 Municipal effluent-II 425
2.0 Municipal effluent-II 409
3.0 Municipal effluent-II 422

for aliquoted samples. (Note that for Probably the most severe evaluation
aliquots, D is derived from the sodium is that of aliquoted samples with
chloride concentration calculated to a substantial chloride concentrations,
dilution of 50 ml.) particularly those with high dilution
factors. This is evident from consid
Results and Discussion eration of Figure 2, which shows that
the rate of decrease of the correction
Table I shows that the revised pro
is generally much less than that of
cedure and calculation are very ef
the sodium chloride concentration. As
fective for acetic acid and phthalic
a consequence, the amount of the ef
anhydride determinations over a wide
fective correction may increase by an
range of sodium chloride concentra
order of magnitude approaching one
tions.
for a 10:1 dilution. Despite the mag
A more severe evaluation of the
nitude of the correction, aliquoting of
modified procedure and revised calcu
municipal effluent samples did not
lation was made on typical municipal
change the level of test results, as
effluents. The samples were tested as
shown in Table III.
received and with various amounts of
sodium chloride added. Table II shows
Conclusions
the correction to be effective for so
dium chloride concentrations as high The revised procedure for chloride
as three percent. containing samples provides the neces

TABLE IH.?Effect of Diluting Saline Municipal Effluents

COD
(mg/1)
Aliquot Sample Identification
(ml) Uncorrected
Standard Proposed
Calculation
Calculation

5 Municipal effluent-III 906 403

10 Municipal effluent-III 636 391
25 Municipal effluent-III 484 417
50 Municipal effluent-III 444 446

5 Municipal effluent-IV 846 355

10 Municipal effluent-IV 553 298
25 Municipal effluent-IV 394 312
50 Municipal effluent-IV 355 342

This content downloaded from 131.91.169.193 on Wed, 4 Sep 2013 23:47:48 PM

All use subject to JSTOR Terms and Conditions
Vol. 37, No. 12 CHLORIDE CORRECTION FOR COD 1721

References
sary control over the testing operation
"
to supply data for an improved calcu 1. Standard Methods for the Examination
of Water and Waste Water." 11th
lation which will insure the most ac
Ed. Amer. Pub. Health Assn., New
curate COD measurements presently York (1960).
possible. 2. Cripps, J. M., and Jenkins, D., "A COD
Method Suitable for the Analysis of
Acknowledgment Highly Saline Waters.'' This Jour
nal, 36, 10, 1240 (Oct. 1964).
The authors wish to express appreci 3. Dobbs, R. A., and Williams, R. T., "Elimi
ation to R. C. Vollmar for his helpful nation of Chloride Interference in the

suggestions and for reviewing the Chemical Oxygen Demand Test."

Anal. Chem., 35, 1064 (1963).
manuscript.

MEETINGS OF INTEREST

1966
Jan. 5 Sixteenth Annual Sanitary Engineering Conference, Uni
versity of Kansas, Lawrence. Dana A. Leibengood, Univer
sity Extension Building, University of Kansas, Lawrence,
Kans. 66045.

Feb. 8 Eighth Sanitary Engineering Conference, Urbana, 111. Prof.

John H. Austin, 203 Civil Engineering Hall, Univ. of Illinois,
Urbana, 111. 61803 ; C. W. Klassen, Chief Sanitary Engineer,
Dept. Public Health, Springfield, 111.; or R. C. Wickland,
Div. of Univ. Extension, Univ. of Illinois, Urbana.

Feb. 20-24 Technical Association of The Pulp and Paper Industry, 51st
Annual Meeting, New York Hilton Hotel, New York, N. Y.
TAPPI, 360 Lexington Ave., New York, N. Y. 10017.

Apr. 4-5 National Conference on Solid Waste Management, Davis

Campus, University of California, Davis, Calif. Professor
Samuel A. Hart, Department of Agricultural Engineering,
University of California, Davis, Calif. 95616.
Apr. 4-7 Special Lecture Series on Advances in Water Quality Im
provement, University of Texas, Austin. Special Lecture
Series, Engineering Laboratories Bldg. 305, University of
Texas, Austin, Tex. 78712.

May 31-June 3 19th Water International Days of CEBEDEAU, Palais des

Congr?s, Liege, Belgium. CEBEDEAU, 2, rue, A. St?vart,
Liege, Belgium.

This content downloaded from 131.91.169.193 on Wed, 4 Sep 2013 23:47:48 PM

All use subject to JSTOR Terms and Conditions