BS EN 1302 - 1999 Chemicals Used For Treatment of Water Intended For Human Consumption. Aluminium-Based Coagulants. Analytical Methods.

BRITISH STANDARD BS EN
1302:1999
Incorporating
Corrigendum No. 1
Chemicals used for

treatment of water
intended for human
consumption —
Aluminium-based
coagulants —
Analytical methods
The European Standard EN 1302:1999 has the status of a

British Standard
ICS 71.100.80
12&23<,1*:,7+287%6,3(50,66,21(;&(37$63(50,77('%<&23<5,*+7/$:
BS EN 1302:1999
National foreword
This British Standard is the English language version of EN 1302:1999,

including Corrigendum February 2002.
The UK participation in its preparation was entrusted to Technical Committee
CII/59, Chemicals for drinking water treatment, which has the responsibility to:
— aid enquirers to understand the text;
— present to the responsible European committee any enquiries on the
interpretation, or proposals for change, and keep the UK interests informed;
— monitor related international and European developments and
promulgate them in the UK.
A list of organizations represented on this committee can be obtained on request
to its secretary.
Additional information
Article 8 of the Council of the European Community Directive 80/778/EEC
relating to the quality of water intended for human consumption requires
Member States to ensure that substances used in the preparation of drinking
water do not cause any contravention of the maximum admissable concentrations
prescribed in Annex 1 to the Directive.
This requirement is given effect in England and Wales by regulation 25 of the
Water Supply (Water Quality) regulations 1989 (similar provisions apply in
Scotland and Northern Ireland). Regulation 25 makes provision for attaching
conditions of use to chemicals which are authorized for use in public water
supplies.
Details of conditions of use are contained in the Secretary of State’s List of
Approved Products published by the Drinking Water Inspectorate, Floor 2/A1,
Ashdown House, 123 Victoria Street, London SW1E 6DE.
Cross-references
The British Standards which implement international or European publications
referred to in this document may be found in the BSI Catalogue under the section
entitled “International Standards Correspondence Index”, or by using the
“Search” facility of the BSI Electronic Catalogue of or British Standards Online.
This publication does not purport to include all the necessary provisions of a
contract. Users are responsible for its correct application.
Compliance with a British Standard does not of itself confer immunity
from legal obligations.
Summary of pages
This document comprises a front cover, an inside front cover, pages i and ii,
the EN title page, pages 2 to 43 and a back cover.
This British Standard, having
been prepared under the
The BSI copyright notice displayed in this document indicates when the document
direction of the Sector was last issued.
Committee for Materials and
Chemicals, was published
under the authority of the
Standards Committee and Amendments issued since publication
comes into effect on
15 September 1999 Amd. No. Date Comments
© BSI 2 October 2002 13809 2 October 2002 Changes to Clause 4, A.4.6.1, A.4.6.2,
Corrigendum No. 1 A.11.6.1, A.11.6.2 and A.12.6.2
ISBN 0 580 32747 7

EUROPEAN STANDARD EN 1302
NORME EUROPÉENNE
EUROPÄISCHE NORM April 1999
ICS 71.100.80 Incorporating corrigendum February 2002
English version
Chemicals used for treatment of water intended for human

consumption — Aluminium-based coagulants —
Analytical methods
Produits chimiques utilisés pour le traitement de Produkte zur Aufbereitung von Wasser für den
l’eau destinée à la consommation humaine — menschilichen Gebrauch —
Coagulants à base d’aluminium — Flockungsmittel auf Aluminiumbasis —
Méthodes d’analyse Analytische Methoden
This European Standard was approved by CEN on 1 April 1999.

CEN members are bound to comply with the CEN/CENELEC Internal
Regulations which stipulate the conditions for giving this European Standard
the status of a national standard without any alteration. Up-to-date lists and
bibliographical references concerning such national standards may be obtained
on application to the Central Secretariat or to any CEN member.
This European Standard exists in three official versions (English, French,
German). A version in any other language made by translation under the
responsibility of a CEN member into its own language and notified to the
Central Secretariat has the same status as the official versions.
CEN members are the national standards bodies of Austria, Belgium,
Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland,
Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden,
Switzerland and United Kingdom.
CEN
European Committee for Standardization
Comité Européen de Normalisation
Europäisches Komitee für Normung
Central Secretariat: rue de Stassart 36, B-1050 Brussels

© 1999 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national
Members Ref. No. EN 1302:1999 E
EN 1302:1999
Foreword Contents
This European Standard has been prepared by Page
Technical Committee CEN/TC 164, Water supply, Foreword 2
the Secretariat of which is held by AFNOR.
1 Scope 3
This European Standard shall be given the status of 2 Normative references 3
a national standard, either by publication of an
identical text or by endorsement, at the latest by 3 Preparation of the test sample 4
October 1999, and conflicting national standards 4 Methods of analysis 4
shall be withdrawn at the latest by October 1999. 5 Expression of results 5
According to the CEN/CENELEC Internal Annex A (normative) Reference
Regulations, the national standards organizations methods of analysis 6
of the following countries are bound to implement Annex B (informative) Routine methods 41
this European Standard: Austria, Belgium,
Annex C (informative) Bibliography 43
Czech Republic, Denmark, Finland, France,
Germany, Greece, Iceland, Ireland, Italy, Figure A.1 — Calculation of the iron
Luxembourg, Netherlands, Norway, Portugal, concentration in the test solution 12
Spain, Sweden, Switzerland and Figure A.2 — Calculation of the iron
the United Kingdom. concentration in the blank solution 13
Figure A.3 — Calculation of the sodium
concentration in the test solution 18
Figure A.4 — Calculation of the sodium
concentration in the blank solution 18
Figure A.5 — Calculation of the calcium
Figure A.6 — Calculation of the calcium
Figure A.7 — Calculation of the metal
Figure A.8 — Calculation of the metal
Table 1 — Methods of analysis 4
Table 2 — Applicability methods of analysis 5
Table A.1 — Aliquot portion V1 for Al
determination (EDTA method) 7
Table A.2 — Aliquot portion V1 for Al
determination (CDTA method) 9
Table A.3 — Dilutions and aliquot portion V3
for Cl– determination 23
Table A.4 — Aliquot portion V1
2–
for SO 4 determination 24
Table A.5 — Dilutions and aliquot portion V5
for silicate determination 26
Table A.6 — Aliquot portion V1 for free acidity,
titrimetric method 27
Table A.7 — Aliquot portion for basicity,
titrimetric oxalate method 29
Table A.8 — Aliquot portion V1 for basicity
titrimetric KF method 32
Table B.1 41
Table B.2 42
2 © BSI 2 October 2002

EN 1302:1999
1 Scope
This European Standard is applicable to aluminium-based coagulants used for treatment of water intended
for human consumption. It specifies analytical methods to be used for products described in EN 878,
EN 881, EN 882, EN 883, prEN 885, prEN 886, prEN 887 and prEN 935.
2 Normative references
This European Standard incorporates by dated or undated reference, provisions from other publications.
These normative references are cited at the appropriate places in the text and the publications are listed
hereafter. For dated references, subsequent amendments to or revisions of any of these publications apply
to this European Standard only when incorporated in it by amendment or revision. For undated references
the latest edition of the publication referred to applies.
EN 878, Chemicals used for treatment of water intended for human consumption — Aluminium sulfate.
EN 881, Chemicals used for treatment of water intended for human consumption — Aluminium chloride,
aluminium chloride hydroxide and aluminium chloride hydroxide sulfate (monomeric).
EN 882, Chemicals used for treatment of water intended for human consumption — Sodium aluminate.
EN 883, Chemicals used for treatment of water intended for human consumption — Polyaluminium
chloride hydroxide and polyaluminium chloride hydroxide sulfate.
prEN 885, Chemicals used for treatment of water intended for human consumption — Polyaluminium
chloride hydroxide silicate.
prEN 886, Chemicals used for treatment of water intended for human consumption — Polyaluminium
hydroxide silicate sulfate.
prEN 887, Chemicals used for treatment of water intended for human consumption —
Aluminium-iron (III) sulfate.
prEN 935, Chemicals used for treatment of water intended for human consumption —
Aluminium-iron (III) chloride and aluminium-iron (III) chloride hydroxide (monomeric).
EN ISO 3696, Water for analytical use — Specification and test methods.
(ISO 3696:1987)
ISO 5666-1:1983, Water quality — Determination of total mercury by flameless atomic absorption
spectrometry — Part 1: Method after digestion with permanganate-peroxodisulfate
ISO 5725-2, Accuracy (trueness and precision) of measurement methods and results — Part 2: Basic method
for the determination of repeatability and reproducibility of a standard measurement method.
ISO 6206:1979, Chemical products for industrial use — Sampling — Vocabulary.
ISO 6227:1982, Chemical products for industrial use — General method for determination of chloride
ions — Potentiometric method.
ISO 6382:1981, General method for determination of silicon content — Reduced molybdosilicate
spectrophotometric method.
© BSI 2 October 2002 3

EN 1302:1999
3 Preparation of the test sample

3.1 Definitions
For the purposes of this European Standard, the following definitions apply.
3.1.1
laboratory sample
sample as prepared for sending to the laboratory and intended for inspection or testing
[ISO 6206:1979]
3.1.2
test sample
sample prepared from the laboratory sample and from which test portions will be taken
[ISO 6206:1979]
3.1.3
test portion
quantity of material drawn from the test sample (or from the laboratory sample if both are the same) and
on which the test or observation is actually carried out
[ISO 6206:1979]
3.2 Procedure
From the laboratory sample, prepare the test sample by grinding the solid samples until particle size is
below 2,5 mm and homogenizing, and homogenize the liquid samples.
4 Methods of analysis
The methods to be used for analysis of aluminium-based coagulants and the principles of each method are
listed in Table 1 and described in full in Annex A for reference methods and in Annex B for routine methods.
The methods which are applicable to only some of the products described in EN 878, EN 881, EN 882,
prEN 885, prEN 886, prEN 887 and prEN 935 are listed in Table 2.
Table 1 — Methods of analysis
Determination Method Principle
Aluminium A.1a EDTA complexometric titration with EDTA
Aluminium A.2 Separation of iron, CDTA complexometric titration
Iron A.3 Atomic absorption spectrometry (flame)
Iron A.4 Potentiometric titration
Sodium A.5 Atomic absorption spectrometry (flame)
Calcium A.6 Atomic absorption spectrometry (flame)
Chloride A.7 Potentiometric titration
Sulfate A.8 Barium sulfate gravimetry
Silicate A.9 Reduced molybdosilicate spectrophotometry
Free acidity A.10 Acidimetric titration
Basicity A.11 Acidimetric titration, oxalate method
Basicity A.12 Acidimetric titration, KF method
Insoluble matter A.13 Gravimetry
Arsenic A.15 Inductively coupled plasma optical emission spectrometry (ICP/OES)
(hydride)
Cadmium A.14 Inductively coupled plasma optical emission spectrometry (ICP/OES)
Chromium A.14 Inductively coupled plasma optical emission spectrometry (ICP/OES)
Mercury A.16 Atomic absorption spectrometry (flameless)
Nickel A.14 Inductively coupled plasma optical emission spectrometry (ICP/OES)
Lead A.14 Inductively coupled plasma optical emission spectrometry (ICP/OES)
Antimony A.15 Inductively coupled plasma optical emission spectrometry (ICP/OES)
(hydride)
Selenium A.15 Inductively coupled plasma optical emission spectrometry (ICP/OES)
(hydride)
a Only applicable for determination of aluminium in EN 881 for low iron grades or other grades.

EN 1302:1999
Table 2 — Applicability methods of analysis

EN/prEN 878 881 882 883 885 886 887 935
Aluminium A.1/A.2 A.2 A.1 A.2 A.2 A.2 A.2 A.2
Aluminium A.1 A.1 A.1 A.1 A.1
Fe/Al < 0,01 % (m/m)
Iron A.3/A.4 A.3 A.3 A.3 A.3 A.3 A.4 A.4
Sodium A.5 A.5
Calcium A.6 A.6 A.6
Chloride A.7 A.7 A.7 A.7
Sulfate A.8 A.8 A.8 A.8 A.8
Silicate A.9 A.9
Free acidity A.10 A.10 A.10 A.10
Basicity Oxalate A.11 A.11 A.11 A.11 A.11 A.11
method
Basicity KF method A.12 A.12
NOTE The method given in B.2 should only be used for determination of basicity by calculation method in EN 883, prEN 885 and
prEN 886.
5 Expression of results
5.1 Aluminium content
The aluminium content shall be expressed as Al. The following equation gives the aluminium content
expressed as alumina (Al2O3):
5.2 Repeatability
Each laboratory shall calculate the repeatability of the method under their laboratory conditions according
to the procedure defined in ISO 5725-2.

EN 1302:1999
Annex A (normative)
Reference methods of analysis
A.1 Determination of aluminium (EDTA complexometric method)
A.1.1 General
This method is applicable for the determination of aluminium in aluminium-based coagulants used for
treatment of water intended for human consumption:
— as the reference method for products described in EN 878 (iron free grade) and EN 882;
— as a routine method for products described in EN 878 (low iron grade), EN 881, EN 883, prEN 885,
prEN 886 and prEN 935 containing no more than 10 g of Fe per kilogram of aluminium.
A.1.2 Principle
Dissolution in water, in the case of solid products, or dilution with water in the case of products in solution,
of a test sample.
Complexation of aluminium, in a hot acidic medium with an excess of ethylenediaminetetraacetic acid
(EDTA) solution. Titration of the excess EDTA with a standard volumetric solution of zinc in the presence
of xylenol orange as indicator.
Al3+ + EDTA4– × AlEDTA–
Zn2+ + EDTA4– × ZnEDTA2–
A.1.3 Reagents
All reagents shall be of a recognized analytical grade and the water used shall conform to grade 3 in
accordance with EN ISO 3696.
A.1.3.1 Sodium acetate solution, 80 g/l.
A.1.3.2 Sodium hydroxide solution, 100 g/l.
A.1.3.3 Hydrochloric acid
Dilute one volume of hydrochloric acid (Ô = 1,19 g/ml) with one volume of water.
A.1.3.4 Hydrochloric acid, 36,5 g/l, c(HCl) = 1 mol/l.
A.1.3.5 Disodium ethylenediaminetetraacetate dihydrate (NaEDTA), standard volumetric solution,
c(C10H14N2O8Na2.2H2O) = 0,05 mol/l. Weigh 18,625 g of NaEDTA, to the nearest 0,000 1 g. Dissolve in
water, transfer the solution quantitatively to a 1 000 ml volumetric flask. Dilute to volume with water and
homogenize.
NOTE Commercial standard volumetric solution could be used.
A.1.3.6 Zinc, standard volumetric solution, c(Zn) = 0,05 mol/l. Weigh to the nearest 0,000 1 g, 6,537 0 g(m)
of pure zinc [minimum content 99,9 % (m/m)].
Dissolve in 60 ml of hydrochloric acid solution (A.1.3.3). During the reaction, cover the beaker with a
watch-glass. At the end of the reaction, boil the solution for 10 min, then cool to room temperature. Dilute
to about 500 ml with water and add sodium acetate solution (A.1.3.1) until a pH of 5,5 ± 0,1 is obtained.
Transfer the solution quantitatively to a 2 000 ml volumetric flask. Dilute to volume with water and
homogenize.
NOTE 1 If the mass of zinc is not exactly that stated above, the zinc concentration is given by the equation:
m
c ( Zn ) = ------------------------
2 ´ 65,37
where
m is the mass in grams of zinc weighed;
65,37 is the relative molecular mass of zinc;
c(Zn) is the concentration of zinc solution, in moles per litre, calculated to the fourth significant figure.
NOTE 2 Commercial standard solution could be used.

EN 1302:1999
A.1.3.7 Buffer solution, pH 5,5.

Weigh 50 g of sodium acetate trihydrate (CH3COONa.3H2O). Dissolve in 500 ml of water and add glacial
acetic acid (CH3COOH) until a pH of 5,5 ± 0,1 is obtained.
A.1.3.8 Xylenol orange
Grind 1,0 g of xylenol orange with 99 g of potassium nitrate in a mortar until an homogeneous mass is
obtained.
A.1.4 Apparatus
Ordinary laboratory apparatus and glassware, and optionally:
A.1.4.1 Automatic titrator and photometer, with fibre optic probe.
A.1.4.2 Microwave equipment.
A.1.5 Procedure
A.1.5.1 Preparation of the test solution
Weigh, to the nearest 0,001 g, about 25 g of the test sample (m0) into a 400 ml beaker.
Add approximately 150 ml of water at 80 °C to 90 °C. Stir until dissolved, using a glass stirrer.
Transfer quantitatively to a 500 ml volumetric flask. Dilute to volume with water and homogenize. Filter
if necessary through a filter paper (particle retention size 2,5 4m) (test solution V0).
Place V1 ml of this solution (see Table A.1) into a 200 ml volumetric flask. Dilute to volume with water and
homogenize (diluted test solution V2).
Table A.1 — Aliquot portion V1 for Al determination (EDTA method)
Expected content Volume V1
Al g/kg ml
<27 100
27 to 66 50
66 to 133 20
133 to 265 10
A.1.5.2 Blank test
Perform a blank test following the same procedure and using the same quantities of all the reagents as
indicated in A.1.5.3. Record the volume used for the titration (V5).
A.1.5.3 Determination
Transfer 100,0 ml of solution (A.1.5.1) (V3) to a 250 ml beaker and adjust to pH 5 to 6 with hydrochloric
acid solution (A.1.3.3) or sodium hydroxide solution (A.1.3.2). Add 5 ml of hydrochloric acid
solution (A.1.3.4) and 50,0 ml of the standard volumetric solution of EDTA (A.1.3.5). Cover with a watch
glass. Heat the solution at 80 °C to 90 °C for at least 20 min. Cool to room temperature. Rinse the watch
glass with water into the beaker. Neutralize with sodium acetate solution (A.1.3.1). The pH value shall be
between 7 to 7,5 and add 10 ml of the buffer solution (A.1.3.7).
Add 30 mg to 50 mg of xylenol orange mixture (A.1.3.8). Titrate with the standard volumetric zinc
solution (A.1.3.6) until the indicator changes from yellow to definite red or determine the equivalence point
using an automatic titrator. Record the volume (V4) used.
If microwave equipment (A.1.4.2) is used, the volume V1 and the volume of the aliquot portion (A.1.5.1) can
be different from those indicated above. Transfer the test portion to a 250 ml conical flask and adjust to
pH 5 to 6 with hydrochloric acid (A.1.3.3) or sodium hydroxide solution (A.1.3.2). Add 5 ml of hydrochloric
acid solution (A.1.3.4) and the suitable volume of the standard volumetric solution of EDTA (A.1.3.5).
Transfer to the microwave equipment. Operate the microwave equipment at a power setting to achieve a
temperature at 80 °C to 90 °C for 15 min. Then cool to room temperature. Transfer quantitatively to
a 250 ml beaker or to the automatic titration cell.
NOTE If an automatic titrator (A.1.4.1) is used, the volume of the aliquot portion (A.1.5.1) and the volumes of the reagents can be
different from those indicated above. They should be such that the required precision is achieved.

EN 1302:1999
A.1.6 Expression of results

The aluminium content, X1 expressed in grams of aluminium per kilogram of product (Al g/kg) is given by
the equation:
where
m0 is the mass, in grams, of the test sample;
V0 is the volume, in millilitres, of the test solution;
V1 is the volume, in millilitres, of test solution diluted to V2;
V2 is the volume, in millilitres, of the diluted test solution;
V3 is the volume, in millilitres, of the aliquot for the determination;
V4 is the volume, in millilitres, of the standard volumetric solution of zinc used for the titration of
the sample test;
V5 is the volume, in millilitres, of the standard volumetric solution of zinc used for the titration of
the blank test;
c is the actual concentration, in moles per litre, of the standard volumetric solution of zinc.
0,026 98 is the mass of Al, in grams, corresponding to 1 ml of standard volumetric solution of zinc,
c(Zn) = 1 mol/l.
With V0 = 500 ml, V2 = 200 ml, V3 = 100 ml:
A.2 Determination of aluminium (CDTA complexometric method after separation of iron)

A.2.1 General
This method is applicable for the determination of aluminium in aluminium-based coagulants used for
treatment of water intended for human consumption, as the reference method for products described in
EN 878 (low iron grade or other grades), EN 881, EN 883, prEN 885, prEN 886, prEN 887 and prEN 935.
A.2.2 Principle
Dissolution in water, in the case of solid products, or dilution with water, in the case of products in solution,
of a test sample.
Separation of iron by precipitation with a solution of sodium hydroxide and filtration of the precipitate.
Complexation of aluminium, in a hot acidic medium with an excess of 1,2-cyclohexylenedinitrilo tetraacetic
acid monohydrate (CDTA) solution. Titration of the excess CDTA with a standard volumetric solution of
zinc in the presence of xylenol orange as indicator.
Al3+ + CDTA4– × AlCDTA–
Zn2+ + CDTA4– × ZnCDTA2–
A.2.3 Reagents
A.2.3.1 Sodium acetate solution, 80 g/l.
A.2.3.2 Sodium hydroxide solution, 100 g/l.
A.2.3.3 Hydrochloric acid
Dilute one volume of hydrochloric acid (Ô = 1,19 g/ml) with one volume of water.
A.2.3.4 Hydrochloric acid, 36,5 g/l, c(HCl) = 1 mol/l.

EN 1302:1999
A.2.3.5 Trans-1,2-diaminocyclohexane-N,N,N½,N½-tetraacetic acid monohydrate (CDTA), standard

volumetric solution c(C14H22N2O8.H2O) = 0,05 mol/l.
Weigh, to the nearest 0,000 1 g, 18,255 g of this product. Dissolve in 80 ml of the sodium hydroxide
solution (A.2.3.2), transfer the solution quantitatively to a 1 000 ml volumetric flask. Dilute to volume with
water and homogenize.
A.2.3.6 Zinc, standard volumetric solution, c(Zn) = 0,05 mol/l.
Weigh to the nearest 0,000 1 g, 6,537 0 g (m) of pure zinc (minimum content 99,9 % [m/m]). Dissolve
in 60 ml of hydrochloric acid solution (A.2.3.3). During the reaction, cover the beaker with a watch-glass.
At the end of the reaction, boil the solution for 10 min, then cool to room temperature. Dilute to
about 500 ml with water and add sodium acetate solution (A.2.3.1) until a pH of 5,5 ± 0,1 is obtained.
Transfer the solution quantitatively to a 2 000 ml volumetric flask. Dilute to volume with water and
homogenize.
NOTE 1 If the mass of zinc is not exactly that stated above, the zinc concentration is given by the equation:
m
c ( Zn ) = ------------------------
2 ´ 65,37
where
m is the mass in grams of zinc weighed;
65,37 is the relative molecular mass of zinc;
c(Zn) is the concentration of zinc solution, in moles per litre, calculated to the fourth significant figure.
NOTE 2 Commercial standard solution could be used.
A.2.3.7 Buffer solution, pH 5,5

Weigh 50 g of sodium acetate trihydrate (CH3COONa.3H2O). Dissolve in 500 ml of water and add glacial
acetic acid (CH3COOH) until a pH of 5,5 ± 0,1 is obtained.
A.2.3.8 Xylenol orange
Grind 1,0 g of xylenol orange with 99 g of potassium nitrate in a mortar until an homogeneous mass is
obtained.
A.2.4 Apparatus
A.2.4.1 Automatic titrator and photometer, with fibre optic probe.
A.2.4.2 Microwave equipment.
A.2.5 Procedure
Place V1 ml of this solution (see Table A.2) into a beaker.
Table A.2 — Aliquot portion V1 for Al determination (CDTA method)
Expected content Volume V1
Al g/kg ml
<27 100
27 to 66 50
66 to 133 20
133 to 265 10

EN 1302:1999
Add while stirring 40 ml of sodium hydroxide solution (A.2.3.2). Boil for 10 min. Cool to room temperature
and transfer the solution quantitatively to a 200 ml volumetric flask. Dilute to volume with water and
homogenize. Filter the solution on a dry filter paper for rapid filtration. Wash the filter with three 5 ml
portions of water. Collect the wash waters together with filtrate in a clean and dry 200 ml volumetric flask.
Dilute to volume with water and homogenize (diluted test solution V2).
A.2.5.2 Blank test
indicated in A.2.5.3. Record the volume (V5) used for the titration.
Transfer 100,0 ml of solution (A.2.5.1) (V3) to a 250 ml beaker and add hydrochloric acid solution (A.2.3.3)
so that the pH reaches about 1. Then add a suitable volume of the standard volumetric solution of
CDTA (A.2.3.5). Cover with a watch glass. Heat the solution at 80 °C to 90 °C for 1 h. Cool to room
temperature. Rinse the watch glass with water into the beaker. Neutralize with sodium acetate
solution (A.2.3.1), the pH value shall be between 7, 0 and 7,5. Add 10 ml of the buffer solution (A.2.3.7).
Add 30 mg to 50 mg of xylenol orange mixture (A.2.3.8). Titrate with the standard volumetric zinc
solution (A.2.3.6) until the indicator changes from yellow to definite red or determine the equivalence point
using an automatic titrator. Record the volume (V4) used.
If microwave equipment (A.2.4.2) is used, the volume V1 and the volume of the aliquot portion (A.2.5.1) can
be different from those indicated above. Transfer the aliquot portion into a 250 ml conical flask and add
hydrochloric acid solution (A.2.3.3) so that the pH reaches about 1. Then add a suitable volume of the
standard volumetric solution of CDTA (A.2.3.5). Transfer to the microwave equipment. Operate the
microwave equipment at a power setting to achieve a temperature at 80 °C to 90 °C for 15 min. Then cool
to room temperature. Transfer quantitatively to a 250 ml beaker or to the automatic titration cell.
NOTE If an automatic titrator (A.2.4.1) is used, the volume of the aliquot portion (A.2.5.1) and the volumes of the reagents can be
different from those indicated above. They should be such that the required precision is achieved.

The aluminium content, X2, expressed in grams of aluminium per kilogram of product (Al g/kg) is given by
the equation:
where
V4 is the volume, in millilitres, of the standard volumetric solution of zinc used for the titration of the
sample test;
V5 is the volume, in millilitres, of the standard volumetric solution of zinc used for the titration of the
blank test;
c is the actual concentration, in moles per litre of the standard volumetric solution of zinc.
0,026 98 is the mass of Al, in grams, corresponding to 1 ml of standard volumetric solution of zinc,
c(Zn) = 1 mol/l.
With V0 = 500 ml, V2 = 200 ml, V3 = 100 ml:

EN 1302:1999
A.3 Determination of iron (atomic absorption spectrometry)

A.3.1 General
This method is applicable for the determination of iron in aluminium based coagulants used for treatment
of water intended for human consumption, as the reference method for products described in EN 878
(iron free grade), EN 881, EN 882, EN 883, prEN 885 and prEN 886.
A.3.2 Principle
Dissolution of a test sample in nitric acid. Determination of the iron content by atomic absorption
spectrometry in an acetylene-air flame at a wavelength of 248,3 nm, using the method of standard
additions.
A.3.3 Reagents
A.3.3.1 Nitric acid, Ô = 1,42 g/ml (approximately 14 mol/l).
A.3.3.2 Hydrochloric acid, Ô = 1,19 g/ml (approximately 12,5 mol/l).
A.3.3.3 Iron, standard solution containing 1,000 g of iron (as Fe) per litre.
Dissolve 1 000 g of iron wire in 20 ml of hydrochloric acid (A.3.3.2) and 5 ml of nitric acid (A.3.3.1). Dilute
to volume with water in a 1 000 ml volumetric flask and homogenize.
NOTE Commercial standard titrated solution could be used.
A.3.3.4 Iron, standard solution containing 100,0 mg of iron (as Fe) per litre, prepared by dilution of
solution A.3.3.3.
A.3.4 Apparatus
Ordinary laboratory apparatus and glassware, and:
A.3.4.1 Atomic absorption spectrometer, fitted with an acetylene-air burner and a non-specific absorbance
correction system.
A.3.4.2 Iron hollow cathode lamp
The spectrometer shall be capable of detection of 0,1 mg/l of iron in solution.
A.3.5 Procedure
A.3.5.1 Preparation of the test solution.
A.3.5.1.1 Solid products
Weigh, to the nearest 0,000 1 g, about 10 g of the test sample (m0) into a 250 ml beaker.
Add 100 ml of water and 40 ml of nitric acid solution (A.3.3.1) and dissolve the test sample by heating
at 80 °C to 90 °C. After complete dissolution and cooling, transfer the contents of the beaker to a 200 ml
volumetric flask. Rinse the beaker with water, adding the rinsings to the solution. Dilute to volume with
water and homogenize (test solution V0).
A.3.5.1.2 Products in solution
Weigh, to the nearest 0,000 1 g, about 10 g of the test sample (m0) into a 200 ml volumetric flask.
Add 40 ml of nitric acid solution (A.3.3.1). Dilute to volume with water and homogenize (test solution V0).
A.3.5.2 Blank test
indicated in A.3.5.3.

EN 1302:1999
To each of five 50 ml volumetric flasks add 5,0 ml of the test solution (A.3.5.1) V1. Add to the series of
volumetric flasks, 0 ml, 0,5 ml, 1,0 ml, 1,5 ml and 2,5 ml of the standard iron solution (A.3.3.4). This
corresponds to added concentrations of 0 mg/l, 1,0 mg/l, 2,0 mg/l, 3,0 mg/l and 5,0 mg/l of iron.
Dilute to volume with water and homogenize (measurement solution V2).
Determine the iron concentration using the iron hollow cathode lamp (A.3.4.2) at 248,3 nm after
optimization of the instrument (A.3.4.1) as recommended by the manufacturer, by using the standard
addition method.
A.3.5.4 Calculation of results
Determine the correlation line by plotting the measured absorbances of the spiked measurement solutions
in relation to the iron content. The spiked measurement solutions are produced by adding defined
quantities of iron to the measurement solution V2. They contain stepwise increasing contents of iron to be
determined.
The concentration of iron in the test solution is to be read by extrapolation of the correlation line to
absorbance A = 0 (Figure A.1). Similarly determine the iron concentration of the blank solution
(Figure A.2) and subtract from the result obtained for the test solution. Alternatively the evaluation can be
carried out by linear regression.
Figure A.1 — Calculation of the iron concentration in the test solution

EN 1302:1999
Figure A.2 — Calculation of the iron concentration in the blank solution

The iron content, X3, expressed in grams of iron per kilogram of product (Fe g/kg) is given by the equation:
where
V1 is the volume, in millilitres, of the aliquot for analysis;
V2 is the volume, in millilitres, of the measurement solution;
c1 is the concentration, in milligrams per litre of Fe in the blank solution;
c2 is the concentration, in milligrams per litre of Fe in the test solution.
With V0 = 200 ml, V1 = 5 ml, V2 = 50 ml:
The iron content X½3 expressed in grams per kilogram of aluminium is given by the equation:
where A is the concentration, in grams per kilogram, of aluminium in the product.

EN 1302:1999
A.4 Determination of iron (total and Fe2+) (volumetric method)

A.4.1 General
This method is applicable for the determination of total iron and iron (II) in aluminium-based coagulants
used for treatment of water intended for human consumption, as the reference method for products
described in EN 878 (low iron grade or other grades), prEN 887 and prEN 935.
A.4.2 Principle
Dissolution in water in the case of solid products, or dilution with water, in the case of products in solution,
of a test sample.
Reduction of iron (III) with tin (II) chloride solution and addition of mercury (II) chloride solution.
Determination of iron (II) by titration with potassium dichromate solution, in the presence of phosphoric
acid (to complex iron (III) produced). Detection of the equivalence point with a volumetric method using
barium diphenylamine sulfonate or a potential method titration with redox platinum and reference
electrodes.
Cr2O72– + 6Fe2+ + 14H+ × 6Fe3+ + 2Cr3+ + 7H2O
If necessary, titration of iron (II) without any previous reduction, with potassium dichromate solution.
A.4.3 Reagents
A.4.3.1 Hydrochloric acid, Ô = 1,19 g/ml (approximately 12,5 mol/l).
A.4.3.2 Phosphoric acid, Ô = 1,70 g/ml (approximately 15 mol/l).
A.4.3.3 Mercury (II) chloride solution
Place about 100 g of mercury (II) chloride in a 1 l bottle. Add sufficient water to almost fill the bottle and
shake until no more of the salt dissolves. Decant and retain the solution.
A.4.3.4 Tin (II) chloride solution
Dissolve about 5 g of tin (II) chloride in 60 ml of hydrochloric acid (A.4.3.1). Dilute to 100 ml with water.
A.4.3.5 Potassium dichromate, standard volumetric solution, c(K2Cr2O7) = 0,0167 mol/l.
Dry about 5 g of potassium dichromate in an oven at 105 °C to 110 °C for 4 h. Cool in a desiccator. Weigh
to the nearest 0,001 g about 4,903 g of the dry salt and dissolve it in water. Transfer quantitatively to
a 1 000 ml volumetric flask. Dilute to volume with water and homogenize.
NOTE Commercial standard volumetric solution could be used.
A.4.3.6 Barium diphenylamine sulfonate solution

Dissolve about 1 g of barium diphenylamine sulfonate in 100 ml of water.
A.4.4 Apparatus
Ordinary laboratory apparatus and glassware, and optionally automatic titrator with redox platinum and
reference electrodes.

EN 1302:1999
A.4.5 Procedure
SAFETY PRECAUTIONS Mercury (II) chloride and potassium dichromate solutions are
harmful to the environment. Refer to local regulations for disposal.
A.4.5.1 Determination of total iron
Weigh to the nearest 0,001 g, about 6 g of the test sample of solid product or 12 g of the test sample of
product in solution (m1).
Transfer to a 400 ml beaker. Add 200 ml of water and stir until dissolved. Add 10 ml of hydrochloric
acid (A.4.3.1). Heat to boiling and add tin (II) chloride solution (A.4.3.4) dropwise until a single drop
discharges the yellow colour completely (ignore any slight background colour). Add two drops only of tin (II)
chloride solution (A.4.3.4) in excess. Cool to room temperature and dilute to 200 ml with water. Add 20 ml
of mercury (II) chloride solution (A.4.3.3) as rapidly as possible. Mix and allow to stand for 1 min to 2 min.
Add 5 ml of phosphoric acid (A.4.3.2) and 3 or 4 drops of barium diphenylamine sulfonate
solution (A.4.3.6). Titrate with potassium dichromate solution (A.4.3.5) with a volumetric burette to the
appearance of a purple colour, or determine the equivalence point of the titration curve using an automatic
titrator. Record the volume V1 of potassium dichromate required for the complete titration.
A.4.5.2 Determination of iron (II)
Weigh, to the nearest 0,001 g, about 6 g of the test sample of solid product or 12 g of the test sample of
product in solution (m2).
Transfer to a 400 ml beaker. Add 200 ml of water and stir until dissolved. Add 10 ml of hydrochloric
acid (A.4.3.1), 5 ml of phosphoric acid (A.4.3.2) and 3 or 4 drops of barium diphenylamine sulfonate
solution (A.4.3.6). Titrate with potassium dichromate solution (A.4.3.5) with a volumetric burette to the
appearance of a purple colour, or determine the equivalence point of the titration curve using an automatic
titrator. Record the volume V2 of potassium dichromate required for the complete titration.
RECOMMENDATION FOR SAFETY PRECAUTIONS The residual solutions obtained from
titrations should be collected and then treated in accordance with Annex B of ISO 5790:1979, in
order to prevent pollution of waste water.
A.4.6.1 Total iron
The total iron content, X4.1, expressed in grams of iron per kilogram of product (Fe g/kg) is given by the
equation:
V1
X4.1 = 55,85 × 6 × c × --------
m1
where
m1 is the mass, in grams, of the test sample used in A.4.5.1;
V1 is the volume, in millilitres, of the standard volumetric solution of potassium dichromate used
in A.4.5.1;
55,85 is the mass, in grams, of one mole of iron corresponding to 1 ml of the potassium dichromate
solution c(K2Cr2O7) = 0,016 7 mol/l;
c is the actual concentration, in moles per litre of the potassium dichromate solution.
The total iron content X½4.1 expressed in grams per kilogram of aluminium is given by the equation:

EN 1302:1999
A.4.6.2 Iron (II)

The iron (II) content, X4.2, expressed in grams of iron per kilogram of product (Fe g/kg) is given by the
equation:
V2
X4.2 = 55,85 × 6 × c × --------
m2
where
m2 is the mass, in grams, of the test sample used in A.4.5.2;
V2 is the volume, in millilitres, of the standard volumetric solution of potassium dichromate used
in A.4.5.2;
55,85 is the mass, in grams, of one mole of iron corresponding to 1 ml of the potassium dichromate
solution c(K2Cr2O7) = 0,016 7 mol/l;
c is the actual concentration, in moles per litre of the potassium dichromate solution.
The iron (II) content X½4.2 expressed in grams per kilogram of aluminium is given by the equation:

A.5 Determination of sodium (atomic absorption spectrometry)
A.5.1 General
This method is applicable for the determination of sodium in aluminium-based coagulants used for
prEN 885 and prEN 886.
A.5.2 Principle
Dissolution of the test sample in nitric acid.
Determination of the sodium content by atomic absorption spectrometry in an acetylene-air flame at a
wavelength of 589,0 nm, using the method of standard additions.
A.5.3 Reagents
A.5.3.2 Sodium, standard solution containing 1,000 g of sodium (Na) per litre prepared from sodium
chloride (NaCl).
NOTE Commercial standard solution could be used.
A.5.3.3 Sodium, standard solution containing 100,0 mg of sodium (Na) per litre prepared by dilution of
solution A.5.3.2.
A.5.4 Apparatus
A.5.4.1 Atomic absorption spectrometer, fitted with an acetylene-air burner.
A.5.4.2 Sodium hollow cathode lamp, capable of detection of 0,01 mg/l of sodium in solution.

EN 1302:1999
A.5.5 Procedure
Transfer 5 ml (V1) of this solution to a 1 000 ml volumetric flask. Dilute to volume with water and
A.5.5.2 Blank test
To each of five 100 ml volumetric flasks add 10,0 ml of the diluted test solution (A.5.5.1)
(aliquot solution V3).
Add to the series of volumetric flasks, 0 ml, 0,1 ml, 0,2 ml, 0,3 ml and 0,5 ml of the standard sodium
solution (A.5.3.3). This corresponds to added concentrations of 0 mg/l, 0,1 mg/l, 0,2 mg/l, 0,3 mg/l
and 0,5 mg/l of sodium.
Determine the sodium concentration using the hollow cathode lamp (A.5.4.2) at 589,0 nm after
optimization of the instrument (A.5.4.1) as recommended by the manufacturer, using the standard
addition method.
in relation to the sodium content. The spiked measurement solutions are produced by adding defined
quantities of sodium to the measurement solution V4. They contain stepwise increasing contents of sodium
to be determined.
The concentration of sodium in the test solution is to be read by extrapolation of the correlation line to
absorbance A = 0 (Figure A.3). Similary determine the iron concentration of the blank solution (Figure A.4)
and subtract from the result obtained for the test solution. Alternatively the evaluation can be carried out
by linear regression.

EN 1302:1999
Figure A.3 — Calculation of the sodium concentration in the test solution
Figure A.4 — Calculation of the sodium concentration in the blank solution

EN 1302:1999

The sodium content, X5, expressed in grams of sodium per kilogram of product (Na g/kg) is given by the
equation:
where
c1 is the concentration, in milligrams per litre, of sodium in the blank solution;
c2 is the concentration, in milligrams per litre, of sodium in the test solution.
With V0 = 200 ml, V1 = 5 ml, V2 = 1 000 ml, V3 = 10 ml, V4 = 100 ml:
A.6 Determination of calcium (atomic absorption spectrometry)

A.6.1 General
This method is applicable for the determination of calcium in aluminium-based coagulants used for
EN 883, prEN 885 and prEN 886.
A.6.2 Principle
Dissolution of a test sample in nitric acid.
Determination of the calcium content by atomic absorption spectrometry in an acetylene-nitrous oxide
flame at a wavelength of 422,7 nm, using the method of standard additions.
A.6.3 Reagents
A.6.3.2 Calcium, standard solution containing 1 000 g of calcium (Ca) per litre, prepared from calcium
chloride (CaCl2).
NOTE Commercial standard solution could be used.
A.6.3.3 Calcium, standard solution containing 100,0 mg of calcium (Ca) per litre, prepared by dilution of
solution A.6.3.2.
A.6.4 Apparatus
A.6.4.1 Atomic absorption spectrometer, fitted with an acetylene-nitrous oxide burner and a non-specific
absorbance correction system.
A.6.4.2 Calcium hollow cathode lamp, capable of detection of 0,01 mg/l of calcium in solution.

EN 1302:1999
A.6.5 Procedure
Transfer 5 ml (V1) of this solution to a 500 ml volumetric flask. Dilute to volume with water and
A.6.5.2 Blank test
To each of five 100 ml volumetric flasks add 10,0 ml of the diluted test solution (A.6.5.1) (aliquot
solution V3)
Add to the series of volumetric flasks, 0 ml, 0,1 ml, 0,2 ml, 0,4 ml and 0,6 ml of the standard calcium
solution (A.6.3.3). This corresponds to added concentrations of 0 mg/l, 0,1 mg/l, 0,2 mg/l, 0,4 mg/l
and 0,6 mg/l of calcium.
Determine the calcium concentration using the calcium hollow cathode lamp (A.6.4.2) at 422,7 nm after
optimization of the instrument (A.6.4.1) as recommended by the manufacturer, using the standard
addition method.
in relation to the calcium content. The spiked measurement solutions are produced by adding defined
quantities of calcium to the measurement solution V4. They contain stepwise increasing contents of calcium
to be determined.
The concentration of calcium in the test solution is to be read by extrapolation of the correlation line to
absorbance A = 0 (Figure A.5). Similarly determine the calcium concentration of the blank solution

EN 1302:1999
Figure A.5 — Calculation of the calcium concentration in the test solution
Figure A.6 — Calculation of the calcium concentration in the blank solution

EN 1302:1999

The calcium content, X6, expressed in grams of calcium per kilogram of product (Ca g/kg) is given by the
equation:
where
c1 is the concentration, in milligrams per litre, of calcium in the blank solution;
c2 is the concentration, in milligrams per litre, of calcium in the test solution.
With V0 = 200 ml, V1 = 5 ml, V2 = 500 ml, V3 = 10 ml, V4 = 100 ml:
A.7 Determination of chloride (potentiometric method)

A.7.1 General
This method is applicable for the determination of chloride in aluminium-based coagulants used for
EN 881, EN 883, prEN 885 and prEN 935.
A.7.2 Principle
Dissolution in water, in the case of solid products, or dilution with water, in the case of products in solution
of a test sample.
Potentiometric titration with silver nitrate, in an acetone and water medium to reduce the solubility of
silver chloride:
Cl– + Ag+ × AgCl
A.7.3 Reagents
Use the reagents described in ISO 6227:1982, Clause 4.
A.7.4 Apparatus
Use the apparatus described in ISO 6227:1982, Clause 5.
A.7.5 Procedure
A.7.5.2 Blank test

EN 1302:1999
If necessary, dilute the test solution as indicated in Table A.3.
Pipette the volume (V3) of solution or of diluted solution indicated in Table A.3.
Proceed as described in ISO 6227:1982, Clause 6.
Table A.3 — Dilutions and aliquot portion V3 for Cl– determination
Expected Cl– content Dilution V1/V2 Expected Cl– in test Volume V3 Corresponding mass
solution of Cl–
g/kg ml/ml mg/l ml mg

5 to 25 250 to 1 250 50 12,5 to 62,5
25 to 50 1 250 to 2 500 25 31,25 to 62,5
50 to 125 2 500 to 6 250 10 25 to 62,5
125 to 250 20/100 1 250 to 2 500 25 31,25 to 62,5
250 to 625 20/100 2 500 to 6 250 10 25 to 62,5
The chloride content, X7, expressed in grams of chloride per kilogram of product (Cl– g/kg) is given by the
equation:
where
c is the actual concentration, in moles per litre, of the silver nitrate solution used for the
determination (ISO 6227:1982, 6.2.4);
V3 is the volume, in millilitres, of the diluted test solution used for the determination;
V4 is the volume, in millilitres, of silver nitrate solution used for the determination;
V5 is the volume, in millilitres, of silver nitrate solution used for the blank test;
0,035 45 is the mass of chloride, in grams, corresponding to 1 ml of a standard volumetric solution of
silver nitrate, c(Ag+) = 1 mol/l.
A.8 Determination of sulfate (gravimetric method)
A.8.1 General
This method is applicable for the determination of sulfate in aluminium-based coagulants used for
EN 878, EN 881, EN 883, prEN 886 and prEN 887.
A.8.2 Principle
of a test sample.
Gravimetric determination of sulfate as barium sulfate.

EN 1302:1999
A.8.3 Reagents
A.8.3.1 Hydrochloric acid, Ô = 1,19 g/ml, (approximately 12,5 mol/l).
A.8.3.2 Barium chloride, 100 g/l.
A.8.3.3 Silver nitrate, 20 g/l.
A.8.4 Apparatus
A.8.4.1 Ash-free filter paper, with slow filtration speed.
A.8.4.2 Electric furnace, capable of being controlled at (800 ± 20) °C.
A.8.4.3 Platinum crucible
A.8.5 Procedure
Place V1 ml of this solution (see Table A.4) into a 250 ml beaker.
Table A.4 — Aliquot portion V1 for SO 2–
4 determination
2– Volume V1
Expected SO4 content
ml
g/kg
< 50 100
50 to 300 50
> 300 20
If necessary, dilute to about 100 ml with water. Adjust the pH to 2,0 to 2,5 by dropwise addition of
hydrochloric acid solution (A.8.3.1). Heat the solution to boiling and add slowly 5 ml barium chloride
solution (A.8.3.2).
Allow the solution to stand for 2 h to 3 h at 70 °C to 80 °C to allow the precipitate to coagulate.
Transfer quantitatively the precipitate of barium sulfate to the filter (A.8.4.1). Filter the solution. Wash
the filter and the precipitate repeatedly, with hot water (60 °C to 70 °C) until the filtrate is chloride free on
testing with silver nitrate solution (A.8.3.3). Place the filter in a weighed (to the nearest 0,000 1 g)
platinum crucible (A.8.4.3) (m1). After drying for combustion place the crucible in the furnace (A.8.4.2)
at 800 °C for 30 min. After cooling in a desiccator, weigh the crucible (m2) to the nearest 0,000 1 g.

EN 1302:1999

2–
The sulfate content, X8, expressed in grams of sulfate per kilogram of product ( SO 4 g/kg) is given by the
equation:
where
m0 is the mass, in grams, of the test sample (A.8.5.1);
m1 is the mass in grams of the crucible used (dry);
m2 is the mass in grams of the crucible containing the precipitate;
2–
0,411 568 is the ratio of relative molecular masses ( SO 4 /BaSO4).
With V0 = 500 ml:
A.9 Determination of silicate (reduced molybdosilicate spectrometric method)

A.9.1 General
This method is applicable for the determination of silicate in aluminium-based coagulants used for
A.9.2 Principle
of a test sample.
Depolymerization of polymerized silica by treatment with sodium fluoride in the presence of hydrochloric
acid. Formation of yellow molybdosilicate in the presence of boric acid. Reduction of this complex in the
presence of oxalic acid. Spectrometric determination of the blue reduced molybdosilicate at a wavelength
of about 800 nm.
A.9.3 Reagents
Use the reagents described in ISO 6382:1981, Clause 4.
A.9.4 Apparatus
Use the apparatus described in ISO 6382:1981, Clause 5.
A.9.5 Procedure
Transfer quantitatively into a 500 ml volumetric flask. Dilute to volume with water and homogenize. Filter
A.9.5.2 Blank test

EN 1302:1999
Dilute the test solution as indicated in Table A.5. Pipette the volume (V5) of diluted solution indicated in
Table A.5. Proceed as described in ISO 6382:1981, Clause 6.
Table A.5 — Dilutions and aliquot portion V5 for silicate determination
Expected SiO32– Dilution Expected SiO32– in Aliquot portion Corresponding mass of
content diluted test solution V5 SiO32–
V1/V2 V3/V4
g/kg ml/ml ml/ml 4g/ml ml 4g

6 to 25 10/500 5 to 20 10 50 to 200
25 to 50 10/500 20 to 40 5 100 to 200
30 to 125 10/500 10/500 2,5 to 10 20 50 to 200
60 to 250 10/500 10/100 5 to 20 10 50 to 200
125 to 500 10/500 10/100 10 to 40 5 50 to 200
The silicate content, X9, expressed in grams of silicate per kilogram of product (SiO32– g/kg) is given by the
equation:
where
m1 is the mass, in micrograms, of silica in the aliquot portion of the test solution;
m2 is the mass, in micrograms, of silica in the aliquot portion of the blank test;
V1 is the volume, in millilitres, of the test solution diluted to V2;
V3 is the volume, in millilitres, of the aliquot portion of V2 diluted to V4;
V4 is the volume, in millilitres, of the diluted test solution analysed;
V5 is the volume, in millilitres, of the diluted test solution used for the determination;
1,266 4 is the ratio of relative molecular masses SiO32–/SiO2.
A.10 Determination of free acidity (titrimetric method)

A.10.1 General
This method is applicable for the determination of free acidity in aluminium-based coagulants used for
EN 878, and prEN 887:free acidity expressed as sulfuric acid, and in EN 881 and prEN 935:free acidity
expressed as hydrochloric acid.
A.10.2 Principle
of a test sample.
Addition of an excess of sulfuric acid. Addition of potassium fluoride to complex aluminium. Titration of the
excess sulfuric acid with a titrated solution of sodium hydroxide in the presence of phenolphthalein or using
an automated titrimetric procedure with a pH electrode.

EN 1302:1999
A.10.3 Reagents
A.10.3.1 Potassium fluoride solution, 200 g/l.
Dissolve 200 g of potassium fluoride in 1 l of water in a 2 l beaker. Add 1 ml of phenolphthalein
solution (A.10.3.4) and potassium hydroxide solution (5 g/l) dropwise until the appearance of a permanent
faint pink colour. Transfer into a flask.
A.10.3.2 Sodium hydroxide, standard volumetric solution, c(NaOH) = 0,1 mol/l.
A.10.3.3 Sulfuric acid, standard volumetric solution, c(H2SO4) = 0,05 mol/l.
A.10.3.4 Phenolphthalein
Dissolve 1,0 g of phenolphthalein in 100 g of ethanol.
A.10.4 Apparatus
Ordinary laboratory apparatus and glassware and optionally automatic titrator with glass and reference
electrodes.
A.10.5 Procedure
Weigh to the nearest 0,001 g, about 25 g of the test sample (m0) into a 400 ml beaker.
A.10.5.2 Blank test
indicated in A.10.5.3. Record the volume (V3) used for the titration.
Transfer an appropriate volume V1 of the test solution (A.10.5.1) (see Table A.6) depending on the expected
free acidity content, to a 250 ml beaker.
Table A.6 — Aliquot portion V1 for free acidity, titrimetric method
Expected free acidity Volume of solution V1
g/kg ml
as H2SO4 as HCl
<50 <35 100
>50 >35 25
Add 25,0 ml of sulfuric acid (A.10.3.3), 20 ml of potassium fluoride solution (A.10.3.1) and 3 or 4 drops of
phenolphthalein solution (A.10.3.4). Titrate the solution with sodium hydroxide solution (A.10.3.2) to the
appearance of a faint permanent pink colour, or to the equivalence point using an automatic titrator.
Record the volume (V2) used for the titration.

EN 1302:1999

A.10.6.1 Expression as sulfuric acid
The free acidity, X10, expressed in grams of sulfuric acid per kilogram of product (H2SO4 g/kg) is given by
the equation:
where
V2 is the volume, in millilitres, of the standard volumetric solution of sodium hydroxide used
for the titration of the aliquot;
for the titration of the blank test;
c is the actual concentration, in moles per litre, of the standard volumetric solution of sodium
hydroxide;
0,049 is the mass of sulfuric acid, in grams, corresponding to 1 ml of standard volumetric solution
of sodium hydroxide, c(NaOH) = 1,000 mol/l.
With V0 = 500 ml, c = 0,100 0 mol/l:
A.10.6.2 Expression as hydrochloric acid

The free acidity, X½10, expressed in grams of hydrochloric acid per kilogram of product (HCl g/kg) is given
by the equation:
where
for the titration of the aliquot;
for the titration of the blank test;
hydroxide;
0,036 5 is the mass of hydrochloric acid, in grams, corresponding to 1 ml of standard volumetric
solution of sodium hydroxide, c(NaOH) = 1,000 mol/l.
With V0 = 500 ml, c = 0,100 0 mol/l:

EN 1302:1999
A.11 Determination of basicity (titrimetric oxalate method)

A.11.1 General
This method is applicable for the determination of basicity in aluminium-based coagulants used for
EN 878, EN 881, EN 882, EN 883, prEN 887, and prEN 935.
This method is applicable only to aluminium-based coagulants that do not contain silicates. For product
which contains silicates the basicity shall be estimated using the titrimetric potassium fluoride method
with silicate coefficient correction (see A.12).
A.11.2 Principle
of a test sample.
Addition of an excess of hydrochloric acid in the presence of an excess of potassium oxalate solution
(complexing agent).
Depolymerization by heating.
Determination of the basicity of aluminium salts solutions using an NaOH potentiometric back titration
method.
A.11.3 Reagents
A.11.3.1 Hydrochloric acid, standard volumetric solution, c(HCl) = 0,1 mol/l
A.11.3.2 Sodium hydroxide, standard volumetric solution, c(NaOH) = 0,1 mol/l
A.11.3.3 Potassium oxalate (K2C2O4.H2O) solution, 200 g/1.
A.11.4 Apparatus
A.11.4.1 Potentiometric titrator, with a pH glass electrode and a reference electrode.
A.11.4.2 Hotplate (optionally a microwave oven).
A.11.5 Procedure
Select the required aliquot portion (in grams for solid products or millilitres for liquids) for the expected
basicity according to Table A.7. Weigh the aliquot portion (m) to the nearest 0,001 g. Dissolve in water
at 80 °C to 90 °C, transfer to a 50 ml volumetric flask, dilute to volume with water and homogenize.
Table A.7 — Aliquot portion for basicity, titrimetric oxalate method
Expected basicity Aliquot portion
(OH– g/kg of product) ml or g
from 25 to 70 2
> 70 to 120 1
> 120 0,5
A.11.5.2 Blank test
In the titration vessel, add 20 ml of hydrochloric acid (A.11.3.1) and 5 ml of the potassium oxalate
solution (A.11.3.3).
Titrate the solution with the sodium hydroxide solution (A.11.3.2). Record the volume V1 delivered at the
equivalent point.

EN 1302:1999
In a 100 ml beaker, add:
— 5 ml of the potassium oxalate solution (A.11.3.3);
— 20 ml of hydrochloric acid (V) (A.11.3.1);
— 2 ml to 5 ml of the diluted aluminium salt solution (V0).
Cover with a watch glass, place on the hotplate (A.11.4.2) and bring to boiling point, continue to boil
for 15 min. Cool the solution. If necessary, transfer to a titration vessel of potentiometric
titrator (A.11.4.1).
Rinse the watch glass with water. Add sufficient water to enable the titration.
Titrate with the sodium hydroxide solution (A.11.3.2). Record the volume V2 delivered at the equivalent
point.
NOTE 1 If microwave equipment is used, the volumes and masses given in this procedure should be adapted to the requirements of
the equipment.
NOTE 2 When using an open microwave oven, precautions should be taken to avoid exposure to hydrochloric acid fumes which can
be formed.

A.11.6.1 Basicity
The basicity, X11, expressed in grams of hydroxide per kilogram of product (OH– g/kg) is given by the
equation:
50 1
X 11 = 17 ´ c ( V 1 – V 2 ) ´ ------ ´ -----
Vo m
where
m is the mass, in grams, of the test sample (A.11.5.1);
V0 is the volume, in millilitres, of the aliquot of diluted sample (A.11.5.3);
V1 is the volume, in millilitres, of the sodium hydroxide solution used for the blank
determination (A.11.5.2);
V2 is the volume, in millilitres, of the sodium hydroxide used for the determination (A.11.5.3);
hydroxide (A.11.3.2);
0,017 is the mass of hydroxide OH–, in grams, corresponding to 1 ml of standard volumetric
solution of sodium hydroxide c(NaOH) = 1,000 mol/l.
A.11.6.2 Relative basicity
The relative basicity, X½11, expressed in moles of OH– per third of a mole of aluminium (i.e. as the mole ratio
OH13 Al) is given by the equation:
where
X11 is the basicity expressed in grams of hydroxide per kilogram of product (A.11.6.1);
Al is the content of aluminium (X1 or X2) expressed in grams of aluminium per kilogram of
product.

EN 1302:1999
A.12 Determination of basicity (titrimetric potassium fluoride method)

A.12.1 General
This method is applicable for the determination of basicity in aluminium-based coagulants used for
A.12.2 Principle
of a test sample.
Addition of an excess of sulfuric acid.
Depolymerization by heating in acidic medium. Addition of potassium fluoride to complex aluminium.
Titration of the excess sulfuric acid with a standard volumetric solution of sodium hydroxide in the
presence of phenolphthalein or using an automated titrimetric procedure with a pH electrode.
SiO32– correction taking into account OH– release when complexing depolymerized Al by KF.
SiO32– + 6 KF + 3 H2O × 6OH– + SiF62– + 6 K+
A.12.3 Reagents
A.12.3.1 Potassium fluoride solution, 200 g/l.
Dissolve 200 g of potassium fluoride in 1 l of water in a 2 l beaker. Add 1 ml of phenolphthalein
solution (A.12.3.4) and potassium hydroxide solution (5 g/l) dropwise until the appearance of a permanent
faint pink colour. Transfer to a conical flask.
A.12.3.2 Sodium hydroxide, standard volumetric solution, c(NaOH) = 0,2 mol/l.
A.12.3.3 Sulfuric acid, standard volumetric solution, c(H2SO4) = 0,2 mol/l.
A.12.3.4 Phenolphthalein
Dissolve 1,0 g of phenolphthalein in 100 g of ethanol.
A.12.4 Apparatus
A.12.4.1 Automatic titrator, with glass and reference electrodes.
A.12.4.2 Microwave oven.
A.12.5 Procedure
A.12.5.2 Blank test
indicated in A.12.5.3. Record the volume V3 used for the titration.
Transfer an appropriate volume (V1) of solution (A.12.5.1) (see Table A.8) depending on the expected
aluminium (Al) and relative basicity contents, to a 250 ml beaker.

EN 1302:1999
Table A.8 — Aliquot portion V1 for basicity titrimetric KF method

Aliquot portion, V1 (ml)
OH/3Al Al g/kg
mol/mol < 27 27 to 53 54 to 106 107 to 212 > 212
<0,05 100 100 50 20 20
0,05 to 0,10 100 50 20 20 10
0,11 to 0,20 50 20 10 5 5
0,21 to 0,40 20 10 5 5 2a
>0,40 10 5 2a 2a 2a
a Dilution: 10 ml to 100 ml, then 20 ml of diluted solution.
Add 50 ml of sulfuric acid (A.12.3.3). Cover with a watch glass, heat for 1 h at 80 °C to 90 °C avoiding any
loss of solution. After cooling, rinse the watch glass with water into the beaker. Add 20 ml of potassium
fluoride solution (A.12.3.1) and 3 or 4 drops of phenolphthalein solution (A.12.3.4). Titrate the solution
with sodium hydroxide solution (A.12.3.2) to the appearance of a faint permanent pink colour, or to the
equivalence point using an automatic titrator. Record the volume (V2) used.
If microwave equipment (A.12.4.2) is used, the volume of the solution (A.12.5.1) and the volume V1 of the
aliquot portion (A.12.5.3) can be different from those indicated above and in Table A.8. Transfer the aliquot
portion to a 250 ml conical flask and adjust to pH 5 to 6 with sulfuric acid (A.12.3.3) or sodium hydroxide
solution (A.12.3.2). Add 10 ml of sulfuric acid solution (A.12.3.3). Transfer to the microwave equipment.
Operate the microwave equipment at a power setting to achieve a temperature at 80 °C to 90 °C for 15 min.
Then cool to room temperature. Transfer quantitatively to a 250 ml beaker or into the automatic titration
cell.
NOTE If an automatic titrator (A.12.4.1) is used, the volume V1 of the aliquot portion (A.12.5.3) and the volume of potassium
fluoride solution (A.12.3.1) can be different from those indicated in Table A.8 and above. They should be such that the required
precision is achieved.

A.12.6.1 Basicity
The basicity, X12, expressed in grams of hydroxide per kilogram of product (OH– g/kg) is given by the
equation:
where
V2 is the volume, in millilitres, of the standard volumetric solution of sodium hydroxide used for
the titration of the aliquot;
V3 is the volume, in millilitres, of the standard volumetric solution of sodium hydroxide used for
the titration of the blank test;
hydroxide;
0,017 is the mass of hydroxide, OH–, in grams corresponding to 1 ml of standard volumetric solution,
c(NaOH) = 1,000 mol/l;
X9 is the content of silicates in grams of silicate per kilogram of product (SiO32– g/kg) (see A.9).
With V0 = 500 ml, c = 0,200 0 mol/l:

EN 1302:1999
A.12.6.2 Relative basicity

The relative basicity, X½12, expressed in moles of OH– per third of a mole of aluminium (i.e. as the mole
ratio OH13 Al) is given by the equation:
where
X12 is the basicity expressed in grams of hydroxide per kilogram of product (A.12.6.1);
Al is the content of aluminium (X1 or X2) expressed in grams of aluminium per kilogram of
product.
A.13 Determination of insoluble matter (gravimetric method)
A.13.1 General
This method is applicable for the determination of insoluble matter in aluminium-based coagulants used
for treatment of water intended for human consumption.
A.13.2 Principle
Dissolution of a test sample in water, in the case of solid products.
In the case of products in solution, the product is tested “as is”.
Vacuum filtration, drying and weighing.
A.13.3 Reagents
A.13.3.1 Hydrochloric acid (HCl), c(HCl) = 0,01 mol/l.
A.13.4 Apparatus
A.13.4.1 Vacuum filtration device, arranged on a filtration flask connected to a water-jet pump or a vacuum
pump via a safety bottle.
A.13.4.2 Glass microfibre filters, 40 4m to 100 4m porosity.
A.13.4.3 Electric oven, capable of being controlled at 105 °C ± 3 °C.
A.13.5 Procedure
A.13.5.1 Preparation of the test solutions
Solids: weigh, to the nearest 0,001 g, about 25 g of the test sample (m0) into a 400 ml beaker. Add
approximately 150 ml of water at 80 °C to 90 °C. Stir until dissolved, using a glass stirrer.
Liquids: homogenize liquid test sample. Weigh, to the nearest 0,001 g, approximately 50 g of test
sample (m0).
Dry the filter (A.13.4.2) in the oven (A.13.4.3) adjusted to 105 °C for 30 min. Cool the filter in a desiccator
then weigh to the nearest 0,000 1 g (m1).
Place the filter (A.13.4.2) in the filtration device (A.13.4.1) and attach to the vacuum line.
Quantitatively transfer the test solution to the filter and filter under vacuum. Wash the beaker, filter and
insoluble matter repeatedly with hydrochloric acid solution (A.13.3.1) using a total volume of 100 ml.
Remove the filter from the filtration device, transfer it to the oven (A.13.4.3) adjusted to 105 °C and leave
it to dry for 1 h.
Cool the filter in a desiccator, then weigh to the nearest 0,000 1 g (m2).

EN 1302:1999

The content of insoluble matter in water, X13, expressed in grams per kilogram of product, is given by the
equation:
where
m0 is the mass in grams, of the test sample (A.13.5.1);
m1 is the mass in grams of the filter used (dry);
m2 is the mass in grams of the filter plus the insoluble matter.
The content of insoluble matter X½13 expressed in grams per kilogram of aluminium is given by the
equation:

A.14 Determination of cadmium (Cd), chromium (Cr), nickel (Ni) and lead (Pb) [inductively
coupled plasma optical emission spectrometry (ICP-OES)]
A.14.1 General
This method is applicable for the determination of Cd, Cr, Ni and Pb in aluminium based coagulants used
for treatment of water intended for human consumption, as specified in EN 878, EN 881, EN 882, EN 883,
prEN 885, prEN 886, prEN 887 and prEN 935.
A.14.2 Principle
Dissolution of the test sample in diluted acid and determination of the metal content by ICP-OES. Possible
interferences due to the matrix of the test solution are compensated by using the method of standard
addition.
A.14.3 Reagents
A.14.3.1 Hydrochloric acid, 30 % (m/m) (Ô = 1,15 g/ml).
A.14.3.2 Element stock solutions of Cd, Cr, Ni and Pb
Commercial standard solutions of each element at 1 g/l.
A.14.3.3 Standard element solutions (Cd, Cr, Ni, Pb), at 100 mg/l
Prepare by making up 1 ml of element (Cr, Cd, Ni and Pb) stock solution at 1 g/l (A.14.3.2) with 1 ml of
hydrochloric acid (A.14.3.1) and diluting to 10 ml with water in a 10 ml volumetric flask.
A.14.4 Apparatus
A.14.4.1 Atomic emission spectrometer, equipped with:
— ICP;
— suitable pneumatic nebulizer system for high salt concentration;
— computer system for instrument control and data processing.

EN 1302:1999
A.14.4.2 Argon gas supply.

A.14.5 Procedure
A.14.5.1 Preparation of test solution
Weigh, to the nearest 0,000 1 g, about 10 g of the test sample (m0) into a 250 ml beaker. Add 100 ml of
water and 4 ml of hydrochloric acid (A.14.3.1) and dissolve the test sample by heating at 80 °C to 90 °C.
After complete dissolution and cooling, transfer the content of the beaker to a 200 ml volumetric flask.
Rinse the beaker with water, adding the rinsings to the solution. Dilute to volume with water and
homogenize.
Weigh, to the nearest 0,000 1 g, about 20 ml of the test sample (m0) and transfer to a 200 ml volumetric
flask. Add 4 ml of hydrochloric acid (A.14.3.1). Dilute to volume with water and homogenize (the sample
mass needs to be determined in order to calculate result as mg/kg Al).
A.14.5.2 Blank test
Perform a blank test following the same procedure and using the same quantities of the reagents.
A.14.5.3 Preparation of the calibration solutions for the standard addition method.
A.14.5.3.1 Principle
Equal volumes of test solution are taken; to all of them except one are added known and increasing
amounts of the component to be analysed. All solutions are diluted to the same volume and measured. It is
necessary to verify that the test solutions with the standard solutions are analysed in the linear working
range.
A.14.5.3.2 Calibration solutions
To each of five 20 ml volumetric flasks, add the standard solution (A.14.3.3) in order to give the following
added concentrations:
Cr, Cd, Ni: 0 4g/l, 30 4g/l, 60 4g/l, 90 4g/l, 120 4g/l;
Pb: 0 4g/l, 100 4g/l, 200 4g/l, 300 4g/l, 400 4g/l.
Dilute to volume with the test solution (A.14.5.1.1 or A.14.5.1.2).
Proceed in the same way for the blank test solution.
A.14.5.4 Spectrometer settings
Before starting the determinations, set the operating parameters of the spectrometer as stated in the
operating manual. Check the stability of the spectrometer with the solution used for quality control.
Optimize the nebulization and the plasma conditions to obtain the maximum signal for the wavelength
used.
Examples of wavelengths which can be used are:
Element Wavelength Background
Cd 228,802 nm +0,020 nm
Cr 267,716 nm +0,020 nm
Ni 232,003 nm +0,020 nm
Pb 261,418 nm +0,020 nm
A.14.5.5 Spectrometric measurements
Rinse the nebulizer system with the blank test solution and nebulize the calibration solutions (A.14.5.3)
successively into the plasma and measure the emission of each of them.

EN 1302:1999

in relation to the metal content. The spiked measurement solutions are produced by adding defined
quantities of metal to the measurement solution. They contain stepwise increasing contents of the metals
to be determined.
The concentration of each metal in the test solution is to be read by extrapolation of the correlation line to
absorbance A = 0 (Figure A.7). Similary determine the metal concentration of the blank solution
Figure A.7 — Calculation of the metal concentration in the test solution
Figure A.8 — Calculation of the metal concentration in the blank solution

EN 1302:1999
A.14.5.7 Expression of results

The element content (Cd, Cr, Ni, Pb), X14, expressed in milligrams per kilogram of product, is given by the
following equation:
where
c0 is the concentration of the element, in micrograms per litre, in the blank test solution;
c1 is the concentration of the element, in micrograms per litre, in the test solution without
addition of element.
The element content X½14 expressed in milligrams per kilogram of aluminium is given by the equation:

A.15 Determination of arsenic (As), selenium (Se) and antimony (Sb) by ICP-OES
(hydride technique)
A.15.1 General
This method is applicable for the determination of As, Se and Sb in aluminium based coagulants used for
treatment of water intended for human consumption, as specified in EN 878, EN 881, EN 882, EN 883,
prEN 885, prEN 886, prEN 887 and prEN 935.
A.15.2 Principle
Dissolution of the test sample in diluted acid and determination of the metal content by ICP-OES hydride
technique test. This technique is used because with hydride generation, detection limits for As, Se and Sb
can be decreased to micrograms per litre level. With this technique, the element (As, Se, Sb) is present as
a gaseous hydride, there is no matrix and so an external calibration can be used.
A.15.3 Reagents
A.15.3.1 Hydrochloric acid, 30 % (m/m) (Ô = 1,15 g/ml).
A.15.3.2 Hydrochloric acid, diluted 15 ml HCl + 85 ml water.
A.15.3.3 Sodium hydroxide solution, prepared by dissolving 1,5 g of NaOH in 100 ml of water.
A.15.3.4 Sodium tetrahydroborate solution, prepared by dissolving 2 g of NaHB4 in 100 ml of sodium
hydroxide solution (A.15.3.3).
A.15.3.5 Element stock solutions of As, Se and Sb
Commercial standard solutions of each element at 1 g/l.
A.15.3.6 Standard element solution (As, Se, Sb), at 10 mg/l.
Prepare by making up 1 ml of element (As, Se, Sb) stock solution at 1 g/l (A.15.3.5) with 1 ml of
hydrochloric acid (A.15.3.1) to 10 ml with water in a 10 ml volumetric flask.

EN 1302:1999
A.15.4 Apparatus
A.15.4.1 Atomic emission spectrometer, equipped with:
— ICP;
— suitable pneumatic nebulizer system for high salt concentration;
— an appropriate hydride attachment;
— computer system for instrument control and data processing.
A.15.4.2 Argon gas supply
A.15.5 Procedure
A.15.5.1 Preparation of test solution
Add 100 ml of water and 30 ml of hydrochloric acid (A.15.3.1) and dissolve the test sample by heating
at 80 °C to 90 °C. After complete dissolution and cooling, transfer the content of the beaker to a 200 ml
water and homogenize.
Weigh, to the nearest 0,000 1 g, about 20 ml of the test sample (m0) and transfer to a 200 ml volumetric
flask. Add 30 ml of hydrochloric acid (A.15.3.1). Make up to volume with water and homogenize.
A.15.5.2 Blank test
Perform a blank test following the same procedure and using the same quantities of the reagents.
A.15.5.3 Calibration solutions for external calibration
Pipette the corresponding volumes of standard element solution (A.15.3.6) into a series of 20 ml volumetric
flasks and make up with diluted hydrochloric acid (A.15.3.2).
For instance:
As, Se, Sb: 0 4g/l (blank), 20 4g/l, 40 4g/l, 60 4g/l, 80 4g/l and 100 4g/l.
A.15.5.4 Spectrometer settings
Before starting the determinations, set the operating parameters of the spectrometer as stated in the
operating manual. Optimize the nebulization, the plasma conditions with the hydride configuration, to
obtain the maximum signal for the wavelength used.
Examples of the wavelengths which can be used are:
Element Wavelength Background
As 234,984 nm +0,020 nm
Se 196,026 nm +0,020 nm
Sb 231,147 nm +0,020 nm
A.15.5.5 Spectrometric measurements
Rinse the nebulizer system with the blank solution and nebulize the blank test solution and the calibration
solutions (A.15.5.3) successively into the plasma and measure the emission of each of them.
A.15.5.6 Calibration curve
Draw a curve by plotting the concentrations (in micrograms per litre) of the calibration solutions along the
x-axis and the corresponding emission along the y-axis. The curve obtained is rectilinear.

EN 1302:1999
Before nebulizing the test solution (A.15.5.1.1 and A.15.5.1.2), rinse the system with the blank test
solution to eliminate any memory effect.
Calculate the element concentration (c) in the test solution with the calibration curve.
A.15.5.8 Expression of results
The element content (As, Se, Sb), X15, expressed in milligrams per kilogram of product, is given by the
following equation:
where
c is the concentration of the element, in micrograms per litre, in the test solution;
c0 is the concentration of the element, in micrograms per litre, in the blank test solution;
m0 is the mass, in grams, of the test sample.
The element content X½15 expressed in milligrams per kilogram of aluminium is given by the equation:

A.16 Determination of mercury (cold vapour atomic absorption spectrometry)
A.16.1 General
This method is applicable for the determination of mercury in aluminium-based coagulants used for
treatment of water intended for human consumption.
The limit of detection of this method is 0,02 mg of mercury per kilogram of product.
A.16.2 Principle
Oxidation of the mercury to mercury (II) ions by a solution of nitric and hydrochloric acids. Reduction of
the mercury (II) ions to mercury by tin (II) chloride. Entrainment of the mercury by a gaseous flow and
determination as a monatomic vapour by cold flameless atomic absorption spectrometry at a wavelength
of 253,7 nm.
A.16.3 Reagents
A.16.3.1 Hydrochloric acid, HCl 37 % (m/m) density Ô = 1,19 g/ml.
A.16.3.2 Nitric acid, HNO3 65 % (m/m) density Ô = 1,4 g/ml.
A.16.3.3 Tin (II) chloride, SnCl2.2H2O, 100 g/l solution.
Dissolve 50 g SnCl2.2H2O in 167 ml HCl (A.16.3.1) and dilute to 500 ml.
A.16.3.4 Potassium dichromate, (K2Cr2O7) 4 g/l solution.
Dissolve 4 g K2Cr2O7 in 500 ml water. Add 500 ml HNO3 (A.16.3.2) and homogenize.
A.16.3.5 Mercury (II) chloride, HgCl2.
A.16.3.6 Mercury stock solution, c(Hg) = 100 mg/l.
Dissolve 0,135 4 g HgCl2 in 25 ml HCl (A.16.3.1). Add with a measuring cylinder 25 ml of potassium
dichromate solution (A.16.3.4). Dilute with water to 1 000 ml in a volumetric flask and homogenize.
A.16.3.7 Mercury standard solution, c(Hg) = 100 4g/l.

EN 1302:1999
Pipette 100 ml of mercury stock solution (A.16.3.6). Add with a measuring cylinder 25 ml
of HCl (A.16.3.1). Add with a measuring cylinder 25 ml of potassium dichromate solution (A.16.3.4). Dilute
with water to 1 000 ml in a volumetric flask and homogenize.
A.16.4 Apparatus
A.16.4.1 Atomic absorption spectrometer, with Hg lamp (253,7 nm) and equipment for mercury stripping
described in ISO 5666-1:1983, Clause 5.
A.16.4.2 Conical flasks, 100 ml, with ground joint.
A.16.4.3 Air condenser, to fit the conical flasks (A.16.4.2).
A.16.4.4 Glass beads, 3 mm to 5 mm diameter.
A.16.4.5 Reaction bottle, with 50 ml mark.
A.16.5 Procedure
A.16.5.1 Blank test
Perform a blank test following the same procedure and using the same quantities of all the reagents.
A.16.5.2 Calibration curve
Prepare a calibration curve by using the calibration solutions (A.16.3.7), using the atomic absorption
apparatus (A.16.4.1) under the conditions recommended by the instrument manufacturer. Plot the masses
of mercury (in nanograms) along the x-axis and the corresponding measured absorbances along the y-axis.
Water vapour absorbs at the same wavelength as Hg. The carrier gas is therefore dried by passing it over
concentrated sulfuric acid. The analysis shall be done with varying aliquots of solution (A.16.5.3.1) to check
that all Hg is stripped off.
A.16.5.3.1 Weigh, to the nearest 0,000 1 g, 5 g of the test sample (m0) into a 100 ml conical flask (A.16.4.2).
Add 15 ml nitric acid (A.16.3.2) and 5 ml hydrochloric acid (A.16.3.1). Add some glass beads (A.16.4.4) and
attach the air condenser (A.16.4.3). Boil carefully for 15 min then cool. Rinse the condenser into the flask
with water, dilute with water to 100 ml and homogenize. Transfer with a pipette an aliquot, V, of
approximately 1 ml to 5 ml of the solution to the reaction bottle (A.16.4.5). Dilute to the 50 ml mark with
water. Add 2 ml SnCl2 solution (A.16.3.3). Connect the reaction bottle to the instrument quickly. Measure
the mercury content using the atomic absorption apparatus (A.16.4.1) under the conditions recommended
by the instrument manufacturer, and the calibration curve (A.16.5.2).
The mercury content, X16, expressed in milligrams of mercury per kilogram of product (Hg mg/kg) is given
by the equation:
where
m2 is the mass, in nanograms of mercury found in the blank test solution;
m1 is the mass, in nanograms of mercury found in the test portion;
V is the volume, in millilitres of aliquot for determination.
The mercury content X½16 expressed in milligrams per kilogram of aluminium is given by the equation:
where A is the concentration, in grams per kilogram of product, of aluminium in the product.

EN 1302:1999
Annex B (informative)
Routine methods
B.1 General
Other methods, commonly used for quality control, are given in this informative annex.
B.2 Methods for metals other than aluminium
The principles of suitable methods are listed in Table B.1.
Table B.1
Determination Principle
Antimony Atomic absorption spectrometry methods, ICP/OESa, ICP/MSb
Arsenic Silver diethyldithiocarbamate spectrophotometry
Atomic absorption spectrometry methods, ICP/OES, ICP/MS
Cadmium Atomic absorption spectrometry, ICP/MS
Chromium Atomic absorption spectrometry, ICP/MS
Iron 1,10-phenanthroline method spectrophotometry
Atomic absorption spectrometry, ICP/OES, ICP/MS
Lead Atomic absorption spectrometry methods, ICP/OES, ICP/MS
Nickel Atomic absorption spectrometry, ICP/MS
Selenium Atomic absorption spectrometry methods, ICP/OES, ICP/MS
a ICP/OES: inductively coupled plasma optical emission spectrometric method.
b ICP/MS: inductively coupled plasma mass spectrometric method.
B.3 Evaluation of relative basicity (calculation method)

B.3.1 General
The method is applicable to the calculation of basicity in aluminium-based coagulants used for treatment
of water intended for human consumption, as a routine method for products described in EN 881, EN 883,
prEN 885, prEN 886 and prEN 935.
The calculated relative basicity is a characteristic used for classification of these products (monomeric or
polymeric).
NOTE All ions present should be taken into account in calculating basicity.
B.3.2 Principle
Determination of the contents of aluminium, iron, chloride and/or sulfate and of other ions such as sodium,
calcium, silicate which influence basicity.
Calculation of the molar concentration of hydroxide by difference between anions and cations.
If the product is free from some ions, these ions will not appear in the expression of the basicity.
B.3.3 Procedure
Determine the contents of the elements given in Table B.2 in accordance with the methods listed.

EN 1302:1999
Table B.2
Determination Method
Aluminium see A.2
Iron see A.4
Sodium (if necessary) see A.5
Calcium (if necessary) see A.6
Chloride see A.7
Sulfate see A.8
Silicate (if necessary) see A.9
B.3.4 Expression of results
The calculated basicity, XB, expressed in grams of hydroxide per kilogram of product (OH– g/kg) is given by
the equation:
where
X2 is the content of aluminium expressed in grams of aluminium per kilogram of product;
X4.1 is the content of iron (III) expressed in grams of total iron per kilogram of product;
X4.2 is the content of iron (II) expressed in grams of iron (Fe II) per kilogram of product;
X5 is the content of sodium expressed in grams of sodium per kilogram of product;
X6 is the content of calcium expressed in grams of calcium per kilogram of product;
X7 is the content of chloride expressed in grams of chloride per kilogram of product;
X8 is the content of sulfate expressed in grams of sulfate per kilogram of product;
X9 is the content of silicate expressed in grams of silicate (SiO32–) per kilogram of product;
17 is the mass, in grams, of one mole of hydroxide;
26,98 is the mass, in grams, of one mole of aluminium;
55,85 is the mass, in grams, of one mole of iron;
22,99 is the mass, in grams, of one mole of sodium;
40,08 is the mass, in grams, of one mole of calcium;
96,06 is the mass, in grams, of one mole of sulfate;
35,45 is the mass, in grams, of one mole of chloride;
76,09 is the mass, in grams, of one mole of silicate.
B.3.5 Calculated relative basicity
The calculated relative basicity, X½B, expressed in moles of hydroxide per three moles of aluminium is given
by the equation:
where
XB is the content of hydroxide expressed in grams per kilogram of product (B.3.4);
X2 is the content of aluminium expressed in grams of aluminium per kilogram of product;
17 is the mass, in grams, of one mole of hydroxide;
26,98 is the mass, in grams, of one mole of aluminium.

EN 1302:1999
Annex C (informative)
Bibliography
ISO 5790:1979, Inorganic chemical products for industrial use — General method for determination of
chloride content — Mercurimetric method.

BS EN
1302:1999
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BS EN 1302 - 1999 Chemicals Used For Treatment of Water Intended For Human Consumption. Aluminium-Based Coagulants. Analytical Methods.

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BS EN 1302 - 1999 Chemicals Used For Treatment of Water Intended For Human Consumption. Aluminium-Based Coagulants. Analytical Methods.

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BRITISH STANDARD BS EN

Chemicals used for

The European Standard EN 1302:1999 has the status of a

This British Standard is the English language version of EN 1302:1999,

ISBN 0 580 32747 7

ICS 71.100.80 Incorporating corrigendum February 2002

Chemicals used for treatment of water intended for human

This European Standard was approved by CEN on 1 April 1999.

Central Secretariat: rue de Stassart 36, B-1050 Brussels

2 © BSI 2 October 2002

© BSI 2 October 2002 3

3 Preparation of the test sample

4 © BSI 2 October 2002

Table 2 — Applicability methods of analysis

© BSI 2 October 2002 5

6 © BSI 2 October 2002

A.1.3.7 Buffer solution, pH 5,5.

© BSI 2 October 2002 7

A.1.6 Expression of results

A.2 Determination of aluminium (CDTA complexometric method after separation of iron)

8 © BSI 2 October 2002

A.2.3.5 Trans-1,2-diaminocyclohexane-N,N,N½,N½-tetraacetic acid monohydrate (CDTA), standard

A.2.3.7 Buffer solution, pH 5,5

© BSI 2 October 2002 9

A.2.6 Expression of results

10 © BSI 2 October 2002

A.3 Determination of iron (atomic absorption spectrometry)

© BSI 2 October 2002 11

Figure A.1 — Calculation of the iron concentration in the test solution

12 © BSI 2 October 2002

Figure A.2 — Calculation of the iron concentration in the blank solution

A.3.6 Expression of results

where A is the concentration, in grams per kilogram, of aluminium in the product.

© BSI 2 October 2002 13

A.4 Determination of iron (total and Fe2+) (volumetric method)

A.4.3.6 Barium diphenylamine sulfonate solution

14 © BSI 2 October 2002

where A is the concentration, in grams per kilogram, of aluminium in the product.

© BSI 2 October 2002 15

A.4.6.2 Iron (II)

where A is the concentration, in grams per kilogram, of aluminium in the product.

16 © BSI 2 October 2002

© BSI 2 October 2002 17

Figure A.3 — Calculation of the sodium concentration in the test solution

Figure A.4 — Calculation of the sodium concentration in the blank solution

18 © BSI 2 October 2002

A.5.6 Expression of results

A.6 Determination of calcium (atomic absorption spectrometry)

© BSI 2 October 2002 19

20 © BSI 2 October 2002

Figure A.5 — Calculation of the calcium concentration in the test solution

Figure A.6 — Calculation of the calcium concentration in the blank solution

© BSI 2 October 2002 21

A.6.6 Expression of results

A.7 Determination of chloride (potentiometric method)

22 © BSI 2 October 2002

g/kg ml/ml mg/l ml mg

© BSI 2 October 2002 23

24 © BSI 2 October 2002

A.8.6 Expression of results

With V0 = 500 ml:

A.9 Determination of silicate (reduced molybdosilicate spectrometric method)

© BSI 2 October 2002 25