SLOVENSKI STANDARD

SIST ISO 6060:1996

01-junij-1996

.DNRYRVWYRGH'RORþDQMHNHPLMVNHSRWUHEHSRNLVLNX

Water quality -- Determination of the chemical oxygen demand

3-
) EW

a2
-0
.ai VI

7
96 17
eh E

19 c
.it R

0- e 03
Qualité de l'eau -- Détermination de la demande chimique en oxygène
ds P

06 / 3
ar RD

-6 st
so /si
t - i ds
nd DA

30 an :
8e /st rd
s r
/si da

Ta slovenski standard je istoveten z: ISO 6060:1989

4 1 g da
sta AN

c e l o an
ST

61 at st
47 i / c l l
4 - .a F u
a
eh
(
iT

4d e h

ICS:
- 9 .i t
0 f ds

13.060.50 3UHLVNDYDYRGHQDNHPLþQH Examination of water for

47 ar
nd

VQRYL chemical substances

sta /
s:/
tp
ht

SIST ISO 6060:1996 en

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
ht
tp
iT
s:/ eh
/ sta ST
nd (
47 ar sta AN
0 f ds
- 9 .i t nd DA
4d e h ar RD
4 - .a F u
47 i / c l l ds P
61 at st .it R
c e al o an eh E
4 1 g da
8e /st rd .ai VI
30 an : ) EW
/si da
t - i dss r
so /si
-6 st
06 / 3
0- e 03
19 c
96 17
7 -0
a2
3-
 ht
tp
iT
s:/ eh
/ sta ST

demand
nd (
47 ar sta AN
0 f ds
- 9 .i t nd DA
4d e h

Water quality
4 - .a F u ar RD
47 i / c l l ds P
61 at st .it R

-
c e al o an eh E
4 1 g da
8e /st rd .ai VI
STANDARD

30 an : ) EW
/si da
t - i dss r
so /si

Qua/it& de I’eau - Determination

-6 st
06 / 3
0- e 03
19 c
INTERNATIONAL

Determination

96 17
7-
0a
23
-
de la demande chimigue
of the chemical

en oxygene
oxygen

Reference number
IS0 6060: 1989(E)
Second edition
1989-l O-1 5
 IS0 6060:1989(E)

Foreword
IS0 (the International Organization for Standardization) is a worldwide
federation of national standards bodies (IS0 member bodies). The work
of preparing International Standards is normally carried out through IS0
technical committees. Each member body interested in a subject for
which a technical committee has been established has the right to be
represented on that committee. International organizations, govern-
mental and non-governmental, in liaison with ISO, also take part in the
work. IS0 collaborates closely with the International Electrotechnical
Commission (IEC) on all matters of electrotechnical standardization.

3-
) EW

a2
-0
.ai VI

Draft International Standards adopted by the technical committees are

7
96 17
teh RE

circulated to the member bodies for approval before their acceptance 19 c

0- e 03
as International Standards by the IS0 Council. They are approved in
s.i P

06 / 3
rd D

accordance with IS0 procedures requiring at least 75 % approval by the

-6 st
so /si
da AR

member bodies voting.

t - i ds
30 an :
8e st rd
s r
an D

/si da
4 1 g da
(st AN

International Standard IS0 6060 was prepared by Technical Committee

c e al o an
ST

ISO/TC 147, Water quality.

61 at st
/
47 i / c l l
4 - .a F u
eh

This second edition cancels and replaces the first edition

iT

(IS0 6060:1986). Technically the second edition is equivalent to the first

4d e h

edition, but the maximum permissible chloride content of the test portion
- 9 .i t
0 f ds

is now restricted to 1000 mg/l (first edition 2 000 mg/l).

47 ar
nd
sta /
s:/
tp
ht

8 IS0 1989
All rights reserved. No part of this publication may be reproduced or utilized in any form
or by any means, electronic or mechanical, including photocopying and microfilm, without
permission in writing from the publisher.
International Organization for Standardization
Case Postale 56 l CH-1211 Geneve 20 l Switzerland
Printed in Switzerland

ii
 IS0 6060:1989(E)

Introduction

The chemical oxygen demand, COD, of water as determined by this

dichromate method can be considered as an approximate measure of
the theoretical oxygen demand, i.e. the amount of oxygen consumed in
total chemical oxidation of the organic constituents to inorganic end
products (see also clause 10). The degree to which the test results ap-
proach the theoretical value depends primarily on how complete the
oxidation is. A great number of organic compounds are oxidized to an
extent of between 90 O/o and 100 %, and for waters where there com-

3-
) EW
pounds predominate, such as municipal effluents, the COD value is a

a2
realistic measure of the theoretical oxygen demand. For other waters

-0
.ai VI

7
which contain large quantities of certain substances that are difficult to
96 17
eh E

19 c
.it R

oxidize under the conditions of the test (see clause IO), the COD value
0- e 03
ds P

is a poor measure of the theoretical oxygen demand. This may be the

06 / 3
ar RD

-6 st
so /si

case for some industrial effluents.

t - i ds
nd DA

30 an :
8e /st rd
s r
/si da

The significance of a COD value thus depends on the composition of the

4 1 g da
sta AN

c e l o an

water studied. This should be borne in mind when judging results ob-
ST

61 at st

tained by the method specified in this International Standard.

47 i / c l l
4 - .a F u
a
eh
(
iT

4d e h
- 9 .i t
0 f ds
47 ar
nd
sta /
s:/
tp
ht

...
III
ht
tp
iT
s:/ eh
/ sta ST
nd (
47 ar sta AN
0 f ds
- 9 .i t nd DA
4d e h ar RD
4 - .a F u
47 i / c l l ds P
61 at st
a
c e l o an
.it R

This page intentionally

4 1 g da eh E
8e /st rd .ai VI
30 an : ) EW
/si da
t - i ds s r
so /si

left blank
-6 st
06 / 3
0- e 03
19 c
96 17
7 -0
a2
3-
INTERNATIONAL STANDARD IS0 6060:1989(E)

Water quality - Determination of the chemical oxygen

demand

1 Scope 2 Normative references

The following standards contain provisions which,

through reference in this text, constitute provisions
of this International Standard. At the time of publi-

3-
) EW
This International Standard specifies a method for cation, the editions indicated were valid. All stand-

a2
-0
ards are subject to revision, and parties to
.ai VI

the determination of the chemical oxygen demand,

7
96 17
eh E

COD, of water. agreements based on this International

19 c Standard
.it R

0- e 03
are encouraged to investigate the possibility of ap-
ds P

06 / 3

It is applicable to water with a COD value of between

ar RD

plying the most recent editions of the standards in-

-6 st
so /si

30 mg/l and 700 mg/l. The chloride content must not dicated below. Members of IEC and IS0 maintain
t - i ds
nd DA

30 an :
8e /st rd
s r

exceed 1000 mg/l. A water sample which is in ac- registers of currently valid International Standards.
/si da
4 1 g da
sta AN

cordance with these conditions is used directly for

c e al o an
ST

61 at st

analysis. IS0 385.1:1984, Laboratory glassware - Burettes -

47 i / c l l
4 - .a F u
eh

Part I: General requirements.

(

If the COD value exceeds 700 mg/l, the water sam-

iT

ple is diluted. For greatest accuracy it is preferable

4d e h

IS0 57903979, Inorganic chemical products for in-

- 9 .i t

that the COD value of the sample is in the range of

dustrial use - General method for determination of
0 f ds

300 mg/l to 600 mg/l.

47 ar

chloride content - Mercurimetric method.

nd
sta

Under the given reaction conditions, organic com-

/
s:/

pounds are extensively oxidized. Excluded are com- 3 Definition

tp
ht

pounds with certain structural elements (e.g.

pyridine nucleus, quaternary nitrogen compounds). For the purposes of this International Standard, the
Volatile hydrophobic substances may evaporate and following definition applies.
thus escape the oxidation. Inorganic compounds
being oxidized under the reaction conditions are, for chemical oxygen demand (COD): The mass concen-
example: tration of oxygen equivalent to the amount of
dichromate consumed by dissolved and suspended
- bromide ions, iodide ions; matter when a water sample is treated with that
oxidant under defined conditions.
- certain sulfur compounds;

- nitrite ions; and 4 Principle

9
- certain metal compounds. Reflux in the presence of mercury(ll) sulfate of a test
portion with a known amount of potassium
On the other hand, certain compounds may react as dichromate and silver catalyst in strong sulfuric acid
oxidizing agents under the reaction conditions. De- for a fixed period of time, during which part of the
pending on the use of the test results, these cir- dichromate is reduced by the oxidizable material
cumstances shall be kept in mind. present. Titration of the remainder of the dichromate
with ammonium iron sulfate. Calculation of the
For interferences, particularly from chlorides, see
COD value from the amount of dichromate reduced.
clause 10.
1 mole of dichromate (Cr*O;-) is equivalent to
I,5 moles of oxygen (0,).

1
IS0 6060:1989(E)

If the test portion contains more than 1000 mg/l of 800 ml of water. Add, with caution, 100 ml of sulfuric
chlorides, a modified procedure must be applied? acid (p = I,84 g/ml). Allow to cool and dissolve
11,768 g of potassium dichromate, dried at 105 “C
for 2 h, in the solution. Transfer the solution
5 Reagents and materials quantitatively to a volumetric flask and dilute to
1000 ml.
WARNING - This method involves the handling and
boiling of strong solutions of sulfuric acid and The solution is stable for at least I month.
dichromate. Protective clothing, gloves and full face
protection are necessary. In the event of spillage NOTE 2 If so desired, the dichromate solution may be
immediate washing with copious volumes of clean prepared without the mercury salt. In this case, add 0,4 g
water is the simplest and most effective remedy. of mercury(ll) sulfate to the test portion before the addi-
tion of the dichromate solution (5.3) in 8.1 and mix thor-
Addition of concentrated sulfuric acid to water must oughly.
always be carried out with care and with gentle
swirling of the contents of the flask. 5.4 Ammonium iron sulfate, standard volumetric
Care is required when preparing and handling sol- solution, c[(NH,),Fe(SO,),.6H,O] z 0,12 mol/l.
utions containing silver sulfate and mercuric sulfate Dissolve 47,0 g of ammonium iron sulfate
as these substances are toxic. hexahydrate in water. Add 20 ml of sulfuric acid
Used reagents contain mercury, silver and chro- (P = I,84 g/ml). Cool and dilute with water to
mium salts. Used reagents shall be treated for dis- 1000 ml.

3-
) EW

a2
posal according to national or local regulations (see This solution shall be standardized daily as follows:

-0
.ai VI

also IS0 5790, 1979, annex B).

7
96 17
eh E

Dilute IO,0 ml of potassium

19 c dichromate solution
.it R

0- e 03
During the analysis, use only reagents of recognized
ds P

(5.3) to about 100 ml with sulfuric acid (5.1). Titrate

06 / 3
ar RD

-6 st

analytical grade and only distilled water or water of this solution with the ammonium iron sulfate to
so /si
t - i ds

equivalent purity.
nd DA

be standardized, using 2 or 3 drops of ferroin (5.6)

30 an :
8e /st rd
s r
/si da

as indicator.
4 1 g da
sta AN

c e al o an

NOTE 1 The quality of the water is of great importance

ST

61 at st

for the precision of the results. Check the quality of the The concentration, c, expressed in moles per litre,
47 i / c l l
4 - .a F u

water by running blanks (described in 8.2) and similar

eh

of the ammonium iron sulfate is given by the ex-

(

parallel tests without any boiling, but otherwise exactly

iT

pression.
as stated. Note the consumption of ammonium iron
4d e h

IO,0 x 0,040 x 6 -- 2,4

- 9 .i t

sulfate solution (5.4) in both cases. A difference of more

-
0 f ds

than 0,5 ml indicates poor water quality. For determi- V V

47 ar

nation of COD values below 100 mg/l the difference shall

nd
sta

not exceed 0,2 ml. The quality of distilled water can often where V is the volume, in millilitres, of ammonium
/
s:/

be improved by redistilling it from an acidified solution of iron sulfate consumed.

tp

potassium dichromate or potassium permanganate, using

ht

all-glass distillation equipment.

5.5 Potassium hydrogenphthalate, standard refer-
5.1 Sulfuric acid, c (H,SOJ = 4 mol/l. ence solution, c(KC,H,O,) = 2,0824 mmol/l.
Add to about 500 ml of water, 220 ml of sulfuric acid Dissolve 0,425 1 g of potassium hydrogenphthalate,
(P = I,84 g/ml) in portions and with caution. Allow dried at 105 OC, in water and dilute to 1000 ml.
to cool and dilute to 1000 ml.
The solution has a theoretical COD value of
5.2 Silver sulfate - sulfuric acid. 500 mg/l.

Add 10 g of silver sulfate (Ag,SO,) to 35 ml of water. This solution is stable for at least 1 week if stored
Add in portions 965 ml of sulfuric acid at approximately 4 “C.
(P = I,84 g/ml). Allow 1 or 2 days for dissolution.
The dissolution is enhanced by stirring. 5.6 Ferroin, indicator solution.

5.3 Potassium dichromate, standard reference sol- Dissolve 0,7 g of iron sulfate heptahydrate
ution, c(K,Cr,O,) = 0,040 mol/l, containing mercury (FeSO,*7H,O) or 1 g of ammonium iron sulfate
salt. hexahydrate, [(NH,),Fe(SO&6HZO] in water. Add
I,50 g of 1 ,lO-phenanthroline monohydrate C2H,N,s
Dissolve 80 g of mercury(ll) sulfate (HgSO,) in H,O and shake until dissolved. Dilute to 100 ml.

1) Modified procedures for samples exceeding 1000 mg/l chloride content are currently being studied by
ISO/TC 147/SC2. A procedure for low level COD, below 30 mg/l, is also under study.

2
 IS0 6060:1989(E)

This solution is stable for several months if stored solution (5.3). Add a few boiling aids (6.4) to the test
in the dark. It is commercially available. portion (always IO ml) and mix well.
Slowly add 15 ml of silver sulfate-sulfuric acid (5.2)
6 Apparatus and immediately attach the flask to the condenser.
Usual laboratory equipment, and Bring the reaction mixture to boiling within IO min
and continue boiling for another 110 min.
6.1 Reflux apparatus, consisting of a 250 ml re-
action flask or tube with ground glass neck con- The temperature of the reaction mixture should be
nected to a condenser so that there may be no 148 “C +- 3°C.
significant loss of volatile material.
Cool the flask immediately in cold water to about
The co ndenser ma y be cooled by cold water or a 60 “C and rinse the condenser with a small volume
stream of cold air. of water. Remove the condenser and dilute the re-
action mixture to about 75 ml and cool it to room
Clean new apparatus by running a blank as de- temperature.
scribed in 8.2. Clean apparatus that is in use for
COD determinations by rinsing with distilled water Titrate the excess dichromate with ammonium
after each titration. Do not use any detergents. iron sulfate (5.4) using 1 or 2 drops of ferroin
(5.6) as indicator.
6.2 Heating mantle, hotplate or other heating NOTES
device, capable of bringing the sample to boiling

3-
) EW
within IO min. Ensure that the device works without 3 The reaction mixture has to boil gently without any

a2
-0
causing local overheating to solutions being heated. bumping. Bumping indicates local overheating of the sol-
.ai VI

7
96 17
ution, which may lead to false results. Bumping may be
eh E

19 c
.it R

0- e 03
caused by intense heating or by inefficient anti-bumping
6.3 Precision burette, of capacity IO ml, graduated
ds P

granules.
06 / 3
ar RD

-6 st

in divisions of 0,02 ml, and complying with IS0 385-l.

so /si
t - i ds
nd DA

4 Although the quantity of ferroin added is not critical,

30 an :
8e /st rd
s r
/si da

6.4 Boiling aids. Roughened glass beads, of diam- it should be kept as constant as possible. Take as the
4 1 g da
sta AN

c e al o an

eter 2 mm to 3 mm, or other boiling aids, cleaned end-point the first sharp colour change from blue-green
ST

61 at st

by the procedure described in 6.1. to reddish brown, even though the blue-green colour may
47 i / c l l
4 - .a F u

reappear after some minutes.

eh
(
iT

NOTE ON THE PREPARATION OF GLASSWARE

4d e h
- 9 .i t

The glassware used shall be scrupulously clean and

0 f ds
47 ar

shall be protected from dust. It shall be reserved 8.2 Blank test

nd

solely for COD tests.

sta /

Carry out two blank tests in parallel with each set

s:/
tp

7 Sampling and samples of determinations by the procedure given in 8.1, but

ht

replacing the test portion with IO,0 ml of water. See

Laboratory samples shall be collected preferably in also the note to clause 5.
glass bottles, although polyethylene bottles are also
suitable. Analyse the samples as soon as possible
and not later than 5 days after sampling. If the sam-
ples have to be stored prior to analysis, add IO ml 8.3 Check test
of sulfuric acid (5.1) per litre of sample. Keep them
at 0 “C to 5 “C. Shake the storage bottles and make For each set of determinations check the technique
sure that their contents are well homogenized when and the purity of the reagents by analysing IO,0 ml
withdrawing a test portion for analysis. of the standard solution (5.5) by the same procedure
as given for the test portion.
8 Procedure The theoretical oxygen demand of this solution is
500 mg/l; the experimental procedure is satisfactory
8.1 Determination if the result of the check test is at least 96 O/o of this
value.
Transfer IO,0 ml of the sample (diluted if required)
to the reaction flask (see 6.1) and add A blank test should be carried out, as indicated
5,00 ml +- 0,Ol ml of the potassium dichromate in 8.2.