BRITISH STANDARD BS EN

15484:2007
BS
2000-552:2007

Ethanol as a blending
component for petrol —
Determination of
inorganic chloride —
Potentiometric method

The European Standard EN 15484:2007 has the status of a

British Standard

ICS 71.080.60

12&23<,1*:,7+287%6,3(50,66,21(;&(37$63(50,77('%<&23<5,*+7/$:
BS EN 15484:2007

National foreword

This British Standard is the UK implementation of EN 15484:2007.

The UK participation in its preparation was entrusted to Technical Committee
PTI/13, Petroleum testing and terminology.
A list of organizations represented on this committee can be obtained on
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Energy Institute, under the brand of IP, publishes and sells all Parts of
BS 2000, and all BS EN petroleum test methods that would be Part of BS 2000,
both in its annual publication “Standard methods for analysis and testing of
petroleum and related products and British Standard 2000 Parts” and
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Further information is available from:
Energy Institute, 61 New Cavendish Street, London W1G 7AR.
Tel: 020 7467 7100. Fax: 020 7255 1472.
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 cannot confer immunity from
legal obligations.

This British Standard was Amendments issued since publication

published under the authority
of the Standards Policy and
Strategy Committee Amd. No. Date Comments
on 31 October 2007

© BSI and Energy Institute 2007

ISBN 978 0 580 56672 1

EUROPEAN STANDARD EN 15484
NORME EUROPÉENNE
EUROPÄISCHE NORM August 2007

ICS 71.080.60

English Version

Ethanol as a blending component for petrol - Determination of

inorganic chloride - Potentiometric method

Ethanol comme base de mélange à l'essence - Dosage du Ethanol zur Verwendung als Blendkomponente in
chlorure minéral - Méthode potentiométrique Ottokraftstoff - Bestimmung des Gehalts an anorganischen
Chloriden aus dem Eindampfrückstand -
Potentiometrisches Verfahren

This European Standard was approved by CEN on 30 June 2007.

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 CEN Management Centre 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 CEN Management Centre has the same status as the
official versions.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,
France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,
Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.

EUROPEAN COMMITTEE FOR STANDARDIZATION

COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG

Management Centre: rue de Stassart, 36 B-1050 Brussels

© 2007 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 15484:2007: E
worldwide for CEN national Members.
EN 15484:2007 (E)

Contents Page

Foreword..............................................................................................................................................................3
1 Scope ......................................................................................................................................................4
2 Normative references ............................................................................................................................4
3 Principle..................................................................................................................................................4
4 Reagents and materials ........................................................................................................................4
5 Apparatus ...............................................................................................................................................5
6 Samples and sampling ..........................................................................................................................5
7 Calibration ..............................................................................................................................................6
7.1 Preparation of the blank test solution .................................................................................................6
7.2 Preparation of a 5,00 ml standard solution .........................................................................................6
7.3 Titration...................................................................................................................................................6
7.4 Standardisation of 10,00 ml potassium chloride solution.................................................................7
7.5 Calculation of concentration of silver nitrate solution ......................................................................7
7.6 Calculation of value of blank test.........................................................................................................7
8 Sample analysis .....................................................................................................................................7
8.1 Preparation of the dry residue..............................................................................................................7
8.2 Preparation of the sample solution......................................................................................................7
8.3 Titration...................................................................................................................................................8
9 Calculation..............................................................................................................................................8
10 Expression of results ............................................................................................................................8
11 Precision.................................................................................................................................................8
11.1 Repeatability, r .......................................................................................................................................8
11.2 Reproducibility, R ..................................................................................................................................8
12 Test report ..............................................................................................................................................9
Annex A (informative) Measurement example ...............................................................................................10
Annex B (informative) Interferences................................................................................................................11
B.1 Introduction ..........................................................................................................................................11
B.2 Other halogens.....................................................................................................................................11
B.3 Oxidizing agents ..................................................................................................................................11
B.4 Ammonium and iron (III) salts ............................................................................................................11
B.5 Cyanides, thiocyanates and sulphides .............................................................................................11
Bibliography ......................................................................................................................................................12

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 EN 15484:2007 (E)

Foreword
This document (EN 15484:2007) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid
fuels, lubricants and related produts of petroleum, synthetic and biological origin”, the secretariat of which is
held by NEN.

This European Standard shall be given the status of a national standard, either by publication of an identical
text or by endorsement, at the latest by February 2008, and conflicting national standards shall be withdrawn
at the latest by February 2008.

The method described in this document is based on ISO 6227 [1] and a method from a European Regulation
on wine [2].

According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech
Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia,
Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain,
Sweden, Switzerland and United Kingdom.

3
EN 15484:2007 (E)

1 Scope
This standard specifies a potentiometric method for the determination of inorganic chloride content in ethanol
from 4 mg/l to 30 mg/l. The chloride content is determined in aqueous solution after dissolution of the
evaporation residue of the ethanol sample.

WARNING — Use of this standard may involve hazardous materials, operations and equipment. This
standard does not purport to address all of the safety problems associated with its use. It is the
responsibility of the user of this standard to establish appropriate safety and health practices and to
determine the applicability of regulatory limitations prior to use.

NOTE For the purposes of this document, the terms “% (m/m)” and “% (V/V)” are used to represent respectively the
mass fraction and the volume fraction.

2 Normative references
The following referenced documents are indispensable for the application of this document. For dated
references, only the edition cited applies. For undated references, the latest edition of the referenced
document (including any amendments) applies.

EN ISO 3170, Petroleum liquids — Manual sampling (ISO 3170:2004)

EN ISO 3696, Water for analytical laboratory use – Specification and test methods (ISO 3696:1987)

3 Principle
A weighed test portion of ethanol sample is evaporated on a water bath. The dry residue is dissolved in
deionised water. Inorganic chloride content is determined by potentiometric titration either manually or using
automated equipment.

4 Reagents and materials

All reagents shall be of analytical reagent grade or of higher purity.

4.1 Acetone.

4.2 Nitric acid, ρ approximately 1,40 g/ml, about 68 % (m/m) solution.

4.3 Potassium nitrate, solution saturated at room temperature.

4.4 Silver nitrate solution 1, c (AgNO3) = 0,1 mol/l approximately. Dissolve 8,5 g of silver nitrate in a
500 ml one-mark volumetric flask, dilute to the mark and mix. Store in a dark glass bottle.

4.5 Silver nitrate solution 2, c (AgNO3) = 0,004 mol/l approximately. Prepare the solution at the time of
use from silver nitrate solution 1 (4.4), diluting when required in a one-mark volumetric flask.

4.6 Potassium chloride standard reference solution 1, c (KCl) = 0,100 mol/l. Weigh 3,727 6 g of
potassium chloride to the nearest 0,000 1 g. Potassium chloride was previously dried for 1 h at about 130 °C
and cooled in a dessicator. Dissolve in a little water and transfer the solution quantitatively into a 500 ml one-
mark volumetric flask. Dilute to the mark and mix. This solution shall not be kept for more than one month.

4
 EN 15484:2007 (E)

4.7 Potassium chloride standard reference solution 2, c (KCl) = 0,004 mol/l. Prepare the solution at the
time of use from the standard reference potassium chloride solution 1 (4.6), diluting when required in a one-
mark volumetric flask.

4.8 Water, for analytical laboratory use, conforming to grade 3 of EN ISO 3696.

5 Apparatus
5.1 Evaporating dish, capacity 100 ml to 250 ml.

5.2 Water bath

5.3 Drying oven, thermostatically controlled at (105 ± 2) °C.

5.4 Dessicator, containing freshly activated silica gel (or equivalent desiccant) with moisture a content
indicator.

5.5 Analytical balance, capable of weighing to the nearest 0,1 mg.

5.6 Pipette, volumetric, class A, capable of delivering 25 ml.

5.7 Potentiometric titration apparatus, comprising:

5.7.1 Potentiometer, sensitivity at least 2 mV, covering the range –500 mV to +500 mV.

5.7.2 Reference electrodes.

5.7.2.1 Calomel electrode, fitted with a reservoir filled with saturated potassium chloride solution, or

5.7.2.2 Double junction silver/silver chloride electrode. The outer electrolyte must be saturated potassium
nitrate solution (4.3), the inner electrolyte may be potassium chloride 3 mol/l or saturated potassium nitrate
(4.3).

5.7.3 Bridge, containing saturated potassium nitrate solution (4.3), to be connected to the calomel
electrode (5.7.2.1) and fitted with porous diaphragms at the ends.

5.7.4 Measuring electrodes, being either

5.7.4.1 Silver electrode, or

5.7.4.2 Chloride or silver ion-selective electrode.

5.8 One-mark flasks, 25 ml volume.

5.9 Magnetic stirrer, with a polytetrafluorethylene (PFTE)-coated rod.

5.10 Burettes, with fine point tip, graduated in 0,02 ml or 0,01 ml divisions.

6 Samples and sampling

Unless otherwise specified, laboratory samples shall be obtained by the procedures described in
EN ISO 3170. High density polyethylene containers shall be used. The containers should be carefully cleaned
and rinsed with pure water before use to avoid contamination.

Samples should be analysed as soon as possible after removal from bulk supplies, to prevent loss of chloride.

5
EN 15484:2007 (E)

Thoroughly mix samples in their containers immediately prior to drawing test portions.

7 Calibration

7.1 Preparation of the blank test solution

At the same time as the determination, carry out a blank test, using 25 ml of water (4.8).

7.2 Preparation of a 5,00 ml standard solution

7.2.1 Place the blank test solution in a beaker of suitable capacity. Add, using one of the burettes (5.10),
5,00 ml of the potassium chloride solution (4.7).

7.2.2 Add a quantity of the acetone (4.1) to obtain a ratio of acetone to aqueous solution preferably equal to
80/10 (V/V) but, in any case, not lower than 50/50 (V/V).

7.3 Titration

Introduce into the beaker a magnetic stirrer rod (5.9), place the beaker on the stirrer and set it in motion.
Introduce in the solution the measuring electrode (5.7.4) and the reference electrode (5.7.2). If, however, a
calomel electrode (5.7.2.1) is used, introduce one end of the bridge (5.7.3) instead of the reference electrode
and immerse the other end in a beaker of water containing the calomel electrode. Connect the electrodes to
the potentiometer (5.7.1) and record the initial value of the potential, after having checked the zero setting of
the instruments.

Execute the titration by adding silver nitrate solution (4.5) in successive increments of 0,1 ml each. After each
addition, wait for the potential to reach the steady value.

In the first two columns of a table, note the successive volumes added and the corresponding potentials.

In a third column, note the successive increments (∆1E) of the potential E.

In a fourth column, note the differences (∆2E), positive or negative, between the successive increments (∆1E)
of the potential E.

The end of the titration corresponds to the addition of the 0,1 ml (V1) of the silver nitrate solution, which gives
the maximum value of ∆1E.

The exact volume (Veq), in ml, of silver nitrate solution (4.5) corresponding to the end of the reaction is given
by the equation (for better comprehension see the example in Annex A):

 b
Veq = V0 + V1 ⋅  (1)
 B

where

V0 is the volume, in ml, of the silver nitrate solution (4.5) which gives the maximum increment of ∆1E;

V1 is the volume, in millilitres, of the silver nitrate solution (4.5);

b is the first negative increment of ∆2E;

B is the sum of the absolute values of the last positive increment of ∆2E and the first negative increment
of ∆2E.

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 EN 15484:2007 (E)

7.4 Standardisation of 10,00 ml potassium chloride solution.

Repeat the operations specified in Error! Reference source not found. and 7.3, this time using 10,00 ml
instead of 5,00 ml, of potassium chloride solution (4.7).

7.5 Calculation of concentration of silver nitrate solution

The concentration of the silver nitrate solution, c(AgNO3), expressed as moles of AgNO3 per litre, is given by
the equation:

5
c(AgNO3 ) = c (KCl ) ⋅ (2)
(V2 − V3 )
where

c(KCl) is the concentration, in mol/l, of potassium chloride solution (4.7);

V2 is the value, in ml, of Veq corresponding to the titration of 10 ml of potassium chloride solution (4.7), in
the presence of blank test solution;

V3 is the value, in ml, of Veq corresponding to the titration of 5 ml of potassium chloride solution (4.7), in
the presence of blank test solution;

5 being the difference, in ml, between the two volumes of potassium chloride solution (4.7).

7.6 Calculation of value of blank test

The value of the reagent blank test, V4, is given, in ml, by the equation:

V4 = 2V3 − V2 (3)

where V2 and V3 are as defined in 7.5.

8 Sample analysis
IMPORTANT — One should always be aware of interferences originating from specific elements in the
sample. Some known interferences are indicated in Annex B.

8.1 Preparation of the dry residue

Add 25 ml (VE) of test portion to the evaporating dish (5.1). Place the dish with sample on the boiling water
bath (5.2) and allow to dry. Place the dish in the oven (5.3) at 105 °C for 30 min and then transfer the dish to a
desiccator (5.4). Allow the dish to cool for 30 min.

Add 10 ml of water (4.8), to the evaporating dish and heat gently until complete dissolution of the dry residue.
Transfer the solution to a 25 ml one-mark flask. Repeat the treatment with 10 ml water. Add water to the mark.

8.2 Preparation of the sample solution

Transfer the sample solution (8.1) in to a suitable beaker. Further proceed as specified in Error! Reference
source not found..2.

If the chloride ion content is very low, proceed from 8.1 using a larger volume of test portion (VE).

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EN 15484:2007 (E)

8.3 Titration

Titrate the sample solution obtained in 8.2 with silver nitrate solution (4.5), following the procedure specified in
7.3.

The volume of silver nitrate solution Veq, obtained from the equation (1), is designated V5.

9 Calculation
The content C, in mg/l, of inorganic chloride in the test ethanol sample, is given by the equation

C=
(V5 − V4 )⋅ a ⋅ 35,45 ⋅1 000 (4)
VE

where

V5 is the volume, in ml, of silver nitrate solution (8.3);

V4 is the value, in ml, of the blank test on the reagents (7.6);

a is the actual concentration, in mol/l, of the silver nitrate solution used for standardisation (7.5);

VE is the volume in ml, of the test portion;

35,45 is the atomic mass of chlorine in g/mol.

10 Expression of results
The content of inorganic chlorides is rounded to the nearest 0,1 mg/l.

11 Precision
NOTE The precision given was determined by statistical examination of interlaboratory test results using
EN ISO 4259 [3].

11.1 Repeatability, r

The difference between two test results, obtained by the same operator with the same apparatus under
constant operating conditions on identical test material, would in the long run, in the normal and correct
operation of the test method, exceeds the value calculated from the following equation only in one case in
twenty:

r = 0,9 mg/l

11.2 Reproducibility, R

The difference between two single and independent test results, obtained by different operators working in
different laboratories on identical test material, would in the long run, in the normal and correct operation of
the test method, exceeds the value calculated from the following equation only in one case in twenty:

R = 1,6 mg/l

8
 EN 15484:2007 (E)

12 Test report
The test report shall contain at least the following information:

a) type and identification of the product under test;

b) reference to this European standard, i.e. EN 15484;

c) result of the test (see Clause 10);

d) any deviation from the procedure described;

e) date of the test.

9
EN 15484:2007 (E)

Annex A
(informative)

Measurement example

Table A.1 gives an example of a measurement with an electrode pair of silver-calomel.

Table A.1

Volume of silver nitrate Potential ∆ 1E ∆ 2E

solution E
C(AgNO3) = 0,004 mol/l
V
ml mV mV mV
4,8 140
4,9 161 21
5,0 239 78 +57
5,1 293 66 -12
5,2 315 22 -44

This then results in:

 12 
V eq = 5,0 −  0,1 ⋅  = 4,983
 57 + 12 

10
 EN 15484:2007 (E)

Annex B
(informative)

Interferences

B.1 Introduction
This Annex is not complete. A check for possible interferences should always be carried out. Furthermore, the
treatments given in this Annex may not cover all possible cases

B.2 Other halogens

All halogens (except for fluorine) may be determined at the same time. If their contents are all of the same
order, iodide, bromide and chloride can be determined simultaneously, taking advantage of the different
potential end points. The order of titration is: iodide, bromide, and finally chloride.

NOTE Because of the possible formation of mixed crystals the separation chloride/bromide is not an exact
stoichiometric one.

If only the chloride has to be titrated, the bromides and iodides may be eliminated beforehand by oxidation (for
example with hydrogen peroxide) in a dilute nitric acid medium, followed by extraction with a suitable solvent.

B.3 Oxidizing agents

Oxidizing agents may oxidize the silver electrode. They can be destroyed by treatment with sodium sulphite,
with ascorbic acid solution or with other reducing agents that do not affect the determination.

B.4 Ammonium and iron (III) salts

If present in large quantities, these salts can reduce the difference in potential ∆1E approaching the
equivalence point.

The influence of these salts may be eliminated by boiling in sodium hydroxide medium in presence of
hydrogen peroxide, filtration of the precipitated iron (III) hydroxide, re-dissolution of the precipitate in a small
quantity of nitric acid and second precipitation of iron (III) under the same conditions. After filtration, the
precipitate is discarded and the combined filtrate acidified with nitric acid solution.

Interference by iron (III), if present in small quantities, can also be eliminated by complexing, for example, with
ethylene diamine tetraacetic acid (EDTA).

B.5 Cyanides, thiocyanates and sulphides

These ions interfere by competing for silver in titration. They can be eliminated by oxidation in sodium
hydroxide medium with hydrogen peroxide and prolonged boiling.

11
EN 15484:2007 (E)

Bibliography

[1] ISO 6227, Chemical Products for industrial use – General method for determination of chloride ions –
Potentiometric method.

[2] Method 10, Determination of dry residue of alcohol, Annex I of Commission Regulation (EC) No.
625/2003, of 2 April 2003, amending Regulation (EC) No 1623/2000 laying down detailed rules for
implementing Council Regulation (EC) No 1493/1999 on the common organization of the market in
wine with regards to market mechanism.

[3] EN ISO 4259:2006, Petroleum products — Determination and application of precision data in relation to
methods of test (ISO 4259: 2006).

[4] EN ISO 1042, Laboratory glassware – One-mark volumetric flasks (ISO 1042:1998).

12
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