International Standard

INTERNATIONAL ORGANIZATION FOR STANDARDIZATlONeME~YHAPO~HAR DPrAHM3Al&4R

0@
a4@!&
4 6059
l-l0 CTAHAAPTM3AlJlWORGANlSATlON INTERNATIONALE DE NORMALISATION

Water quality - Determination of the sum of calcium

and magnesium - EDTA titrimetric method
Qualit de l’eau - Dosage de la somme du calcium et du magnbsium - Mkthode titrimbtrique B I’EDTA

First edition - 1964-06-01

Gi UDC 643.3 : 643.24 : 646.41 : 646.46 Ref. No. IS0 6069-1964 (E)
3 Descriptors : water, quality, chemical analysis, determination of content, calcium, magnesium, volumetric analysis,
ii
6?
Price based on 4 pages
Foreword
IS0 (the International Organization for Standardization) is a worldwide federation of
national standards bodies (IS0 member bodies). The work of developing International
Standards is carried out through IS0 technical committees. Every member body
interested in a subject for which a technical committee has been authorized has the
right to be represented on that committee. International organizations, governmental
and non-governmental, in liaison with ISO, also take part in the work.

Draft International Standards adopted by the technical committees are circulated to

the member bodies for approval before their acceptance as International Standards by
the IS0 Council.

International Standard IS0 6059 was developed by Technical Committee ISO/TC 147,
Water quaky, and was circulated to the member bodies in January 1983.

It has been approved by the member bodies of the following countries:

Australia Hungary Poland

Austria India Romania
Belgium Iran South Africa, Rep. of
Brazil Iraq Spain
Canada Italy Sweden
China Japan Switzerland
Czechoslovakia Korea, Dem. P. Rep. of Thailand
Denmark Korea, Rep. of United Kingdom
Finland Netherlands USSR
France New Zealand
Germany, F. R. Norway

No member body expressed disapproval of the document.

0 International Organization for Standardization, 1994 l

Printed in Switzerland
INTERNATIONAL STANDARD IS0 6066-1664 (El

Water quality - Determination of the sum of calcium

and magnesium - EDTA titrimetric method

1 Scope and field of application 4 Reagents

This International Standard specifies a titrimetric method using During the analysis, use only reagents of recognized analytical
ethylenediaminetetraacetic acid (EDTA) for the determination grade and only distilled water or water of equivalent purity.
of the sum of the calcium and magnesium concentrations in
ground waters, surface waters and drinking waters. 4.1 Buffer solution.

The method is not intended for effluents and waters having a Dissolve 67,5 g of ammonium chloride (NH&I) in 570 ml of
high concentration of salts, such as sea waters. The lowest ammonia solution [25 % (m/m); em = 0,910 g/ml]. Then
concentration that can be determined is 0,05 mmol/l. add 5,0 g of the disodium magnesium salt of EDTA
(C,0H,2N208Na2Mg) and dilute to 1 006 ml with water.

Store the solution (shelf-life limited) in a polyethylene bottle.

2 References Dilute 10 ml of the solution to 100 ml with water. If this solution
fails to give a pH value of 10 f O,l, discard the original solu-
IS0 365/l, Laboratory glassware - Burettes - Part I: tion.
General requirements. 1)
4.2 EDTA, standard volumetric solution,
IS0 5667, Water quality - Sampling - c(NazEDTA) = 10 mmol/l.
Part 1: Guidance on the design of sampling programmes.
Part 2: Guidance on sampling techniques. 4.2.1 Preparation
Part 3: Guidance on the preservation and handling of
Dry a portion of the disodium salt of EDTA dihydrate
samples. 2)
(C10H14N20sNa2~2H20) at 60 OC for 2 h, dissolve 3,725 g of the
dry salt in water and dilute to 1 000 ml in a volumetric flask.

Store the EDTA solution in a polyethylene bottle and check the

3 Principle concentration at regular intervals.
Complexometric titration of calcium and magnesium with an
4.2.2 Standardization
aqueous solution of the disodium salt of EDTA at a pH value of
10. Mordant black 11, which forms a claret or violet colour in Standardize the solution (4.2.1) against the calcium standard
the presence of calcium and magnesium ions, is used as the in- reference solution (4.3) by the procedure described in clause 7.
dicator.
Use 20,O ml of the calcium standard reference solution (4.3)
In the titration, the EDTA, reacts first with the free calcium and and dilute to 50 ml.
magnesium ions in solution, and then, at the equivalence point,
with those calcium and magnesium ions which are combined 4.2.3 Calculation of the concentration
with the indicator, liberating the indicator and causing the col-
our to change from claret or violet to blue. The concentration of the EDTA solution, cl, expressed in
millimoles per litre, is given by the equation
The results are given in amount of substance concentration
units. If the calcium content has been determined separately, c =--
c3 Vl
1
the mass concentration of magnesium can be computed. v,

1) At present at the stage of draft. (Partial revision of ISO/R 395-1964.)

2) At present at the stage of draft.
IS0 6059-1984 (El

where 7 Procedure

cz is the concentration, expressed in millimoles per litre, of

the calcium standard reference solution (4.3) ; 7.1 Preparation of the test portion

VI is the volume, in millilitres, of the calcium standard The samples do not require pretreatment except that samples
reference solution; containing gross amounts of particulate matter should be
filtered through a 0,45 pm pore size filter as soon as possible
V, is the volume, in millilitres, of the EDTA solution used after collection. If filtration is carried out there is a risk of
for the standardization. removing some calcium and magnesium.

Dilute test portions having a total calcium and magnesium con-

tent exceeding 3,6 mmol/l until they are below that concentra-
4.3 Calcium, standard reference solution, tion and record the dilution factor F.
c(CaC0-J = 10 mmol/l.
If the test portions have been acidified for preservation,
Dry a sample of pure calcium carbonate for 2 h at 150 “C, and neutralize them with the calculated amounts of 2 mol/l sodium
allow to cool to room temperature in a desiccator. hydroxide solution. In the calculation of results, take into
account any dilution of the sample, or test portion, by acid or
Place 1,001 g in a 500 ml conical flask, and moisten it with alkali.
water. Add dropwise 4 mol/l hydrochloric acid until all the
carbonate has dissolved. Avoid adding excess acid. Add 200 ml
of water and boil for a few minutes to expel carbon dioxide. 7.2 Determination
Cool to room temperature and add a few drops of methyl red
indicator solution. Add 3 mol/l ammonia solution until the solu- 7.2.1 By means of a pipette, transfer 50,O ml of the test solu-
tion turns orange. Transfer the solution quantitatively to a tion to a 250 ml conical flask. Add 4 ml of the buffersolution
1 066 ml one-mark volumetric flask and make up to the mark (4.1) and 3 drops of mordant black 11 indicator (4.4): The
with water. colour of solution should now turn to claret or violet and its pH
value should be IO,0 f 0,l.
1 ml of the solution contains 0,460 8 mg (0,Ol mmol) of
calcium. Titrate immediately, adding the EDTA solution (4.2) from a
burette (clause 5) under continuous stirring. Titrate rather
NOTE - Commercially available solutions may be used. rapidly at the beginning and slowly towards the end of the titra-
tion. Add the EDTA solution when the colour of the solution
starts to change from claret or violet to blue. The end-point is
4.4 Mordant black 11, indicator. reached when the last red shade has disappeared. The colour
should not change any more on addition of another drop of
Dissolve 0,5 g of mordant black 11, the sodium salt of EDTA solution.
[l-(l-hydroxy-2-naphthylazo)-6-nitro-2-naphthol-4-sulfonic
acid1 (C2cH12N307SNa), in 100 ml of triethanolamine 7.2.2 Titrate an additional test portion in the following
[(HOCHzCH,)sNI. Up to 25 ml ethanol may be added instead of manner.
triethanolamine to reduce the viscositv of the solution.
Transfer 50,O ml of the test solution to a flask. Add an amount
NOTE - To facilitate the detection of the end-point, the indicator may of EDTA solution that is 0,5 ml less than that consumed in the
be modified by the addition of 0.17 g methanil salt (4-anilido- first titration (7.2.1). Add 4 ml of the buffer solution (4.1) and
azobenzene-sulfonic acid sodium salt). The colour will now change 3 drops of the mordant black 11 indicator (4.4). Add EDTA
from red to pale grey or green. dropwise until the end-point is reached.

7.2.3 If the consumption of EDTA solution is less than 4,5 ml,

titrate using a larger test portion, and increase the volume of
5 Apparatus the buffer solution (4.1) in proportion.

Ordinary laboratory apparatus, and : If the consumption of EDTA solution exceeds 20 ml, titrate
using a smaller test portion. Add water so that the starting
Burette, 25 ml capacity, graduated in divisions of 0,05 ml, volume is 50 ml.
conforming to the requirements of IS0 385/l, class A, or
equivalent equipment.
8 Expression of results
The sum of the calcium and magnesium contents, cCa + r.,,,s,
6 Sampling and samples expressed in millimoles per litre, is given by the equation

The samples should be taken in accordance with the relevant Cl h

CCa + Mg = -
parts of IS0 5667. VO

2
 IS0 6069-1964 (El

where either because they are titrated as calcium and magnesium, or

because they obscure the colour change at the end-point.
cl is the concentration, expressed in miilimoles per litre, of Orthophosphate and carbonate ions may precipitate calcium at
the EDTA solution; the pH of the titration. Also some organic matter may interfere
Ve is the volume, in millilitres, of the test portion (normally with the determination.
50 ml);
The interference from iron ions at concentrations of 10 mg/l or
Va is the volume, in millilitres, of EDTA used in the titra- less can be masked by the addition of 250 mg of sodium
tion (see 7.2.2). cyanide to the test portion. Cyanide also minimizes interference
from zinc, copper and cobalt. Ensure that the solution is
If a diluted test portion has been used, modify the calculation
alkaline before adding sodium cyanide.
accordingly, using the dilution factor F.

For calculation of hardness, see the annex. If the interferences cannot be eliminated, use an atomic absorp-
tion method. A suitable method will form the subject of a future
International Standard.

9 Precision
11 Test report
The repeatability of the procedure is f 0,04 mmol/l,. cor-
responding to approximately 2 drops of the EDTA solution.
The test report shall include the following information :
a) a reference to this International Standard;
10 Interferences bj complete identification of the sample;

WARNING - Sodium cyanide is a poison. Take the cl the result, expressed in millimoles per litre, to the
necessary precautions when handling and disposing of nearest 0,02 mmol/l;
the chemical. Solutions containing sodium cyanide must d) the preparation of the test portion (if any);
not be acidified.
e) any deviation from the procedure specified in this Inter-
The metal ions of aluminium, barium, lead, iron, cobalt, cop- national Standard or any other circumstances that may have
per, manganese, tin and zinc interfere with the determination, affected the results.

Bibliography

Ill AMERICAN PUBLIC HEALTH ASSOCIATION, AMERICAN WATERWORKS ASSOCIATION, WATER POLLUTION CONTROL FEDERATION, JOINT
EDITORIAL BOARD. Standard Methods for the Examination of Water and Wastewater, 15th ed., Denver, Colorado, USA,
1980, p. 185.

PI SCHWARZENBACH, G. and FLASCHKA, H. Complexometric Titrations, 2nd ed., New York, Barnes & Noble, 1959.
IS0 6059-1984 (E)

Annex

Concepts of hardness of water

(This annex does not form part of the Standard.)

A.0 Introduction
Hardness of water is an old concept used to describe the content of calcium and magnesium in waters. There are different kinds of
hardness (total hardness, carbonate hardness and others) and various countries have adopted different definitions of the concept.
Some definitions are given in clause A.1 as examples.

A.1 Definitions

A.l.l total hardness: The total concentration of calcium and magnesium.

A.1.2 carbonate hardness: Part of the total hardness, equivalent to the carbonate and hydrogen carbonate contents of the
water.

A.2 Scales of hardness

A.2.1 German hardness degrees

1 German hardness degree (I ODH) is the hardness caused by a calcium oxide content of 10 mg/l, or as an amount of substance con-
centration, 0,178 mmol/l.
NOTE - German hardness degrees are no longer in use.

A.2.2 UK hardness degrees

1 UK hardness degree (1 ‘Xlark) is the hardness caused by a calcium carbonate content of 1 grain per imperial gallon, i.e. 14,3 mg/l or
as an amount of substance concentration, 0,143 mmol/l.

A.2.3 French hardness degrees

1 French hardness degree is the hardness caused by a calcium carbonate content of 10 mg/l, or as an amount of substance concen-
tration, 0,l mmol/l.

A.2.4 US hardness degrees

In the USA the hardness is reported in parts per million (ppm) of calcium carbonate, or milligrams of calcium carbonate per litre.
1 mg/l of calcium carbonate corresponds to an amount of substance concentration of 0,Ol mmol/l.

A.3 Conversion table

For conversion of hardness values the following table may be useful.