BRITISH STANDARD BS EN

15490:2007
BS
2000-557:2007

Ethanol as a blending
component for petrol —
Determination of pHe

The European Standard EN 15490:2007 has the status of a

British Standard

ICS 71.080.60

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BS EN 15490:2007

National foreword

This British Standard is the UK implementation of EN 15490:2007.

The UK participation in its preparation was entrusted to Technical Committee
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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 56678 3

EUROPEAN STANDARD EN 15490
NORME EUROPÉENNE
EUROPÄISCHE NORM August 2007

ICS 71.080.60

English Version

Ethanol as a blending component for petrol - Determination of

pHe

Ethanol comme base de mélange à l'essence - Ethanol zur Verwendung als Blendkomponente in
Détermination du pHe Ottokraftstoff - Bestimmung des pHe-Wertes

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 15490:2007: E
worldwide for CEN national Members.
EN 15490:2007 (E)

Contents Page

Foreword ............................................................................................................................................................. 3
1 Scope...................................................................................................................................................... 4
2 Normative references ........................................................................................................................... 4
3 Terms and definitions........................................................................................................................... 4
4 Principle ................................................................................................................................................. 4
5 Reagents and materials........................................................................................................................ 4
6 Apparatus .............................................................................................................................................. 5
7 Sampling and sample handling ........................................................................................................... 5
8 Apparatus preparation.......................................................................................................................... 5
9 pH meter and electrode system calibration ....................................................................................... 5
10 Apparatus verification .......................................................................................................................... 6
11 Procedure .............................................................................................................................................. 6
12 Expression of results............................................................................................................................ 7
13 Precision ................................................................................................................................................ 7
13.1 General ................................................................................................................................................... 7
13.2 Repeatability, r ...................................................................................................................................... 7
13.3 Reproducibility, R ................................................................................................................................. 7
14 Test report ............................................................................................................................................. 8
Annex A (informative) Background to actual fuel specification needs ........................................................ 9
Bibliography ..................................................................................................................................................... 10

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 EN 15490:2007 (E)

Foreword
This document (EN 15490:2007) has been prepared by Technical Committee CEN/TC 19 “Gaseous
and liquid fuels, lubricants and related products 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.

This document was prepared by CEN/TC 19’s Ethanol Task Force and is based on an extract and
translation from a French Wine Regulation [1]. This method has been developed for European fuel
ethanol specifications. Interlaboratory studies found that the method is not robust enough. Therefore it
is better not to use it to determine the presence of any strong acids or alkalis that may be present in
fuel ethanol. This Standard has insufficient precision to fulfill actual fuel specification needs (see
Annex A). A test for strong acid and for the presence of alkaline substance will be developed by
CEN/TC 19 to replace the pHe test method.

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 15490:2007 (E)

1 Scope
This European Standard describes a procedure for the determination of acid strength, as a pHe value,
of ethanol to be used as a blend component for gasoline.

For further background on the applicability of this document, the user is referred to the information in
Annex A.

NOTE For the purposes of this European Standard, the term “% (V/V)” is used to represent 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 Terms and definitions

For the purposes of this European Standard, the following terms and definitions apply.

3.1
pHe
measure of the acid strength

4 Principle

The pHe of a test portion of ethanol held at 22 °C ± 2 °C is measured using an electrode containing
lithium chloride (LiCl) in an ethanol medium connected to a pH meter system.

NOTE In non-aqueous media, it is not possible to carry out absolute pH measurements and a pHe
value is not directly comparable to pH values of water solutions.

5 Reagents and materials

Use only reagents of recognized analytical grade.

5.1 Buffer solutions, of pH (4,00 ± 0,02), pH (7,00 ± 0,02) and pH (10,00 ± 0,02), within their valid
period for use.

CAUTION — Buffer solutions can deteriorate with time and it is important that they are used
within their valid period of use.

NOTE Buffer solutions may be prepared from either commercially available tablets dissolved in
water or commercially available aqueous solutions.

5.2 Ethanol, 99 % (V/V) containing 1 % (V/V) water.

5.3 Water, conforming to Grade 3 of EN ISO 3696.

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 EN 15490:2007 (E)

5.4 Lithium chloride solution, 1mol/l in 99 % (V/V) ethanol (5.2).

5.5 Sodium hydroxide aqueous solution, approximately 1 mol/l

5.6 Hydrochloric acid aqueous solution, approximately 1 mol/l

6 Apparatus
6.1 pH Meter, capable of reading to 0,01 pH with an accuracy of ± 0,01 pH (or ± 1 mV), preferably
fitted with a temperature compensator.

6.2 Combined pH electrode, filled with a 1 mol/l solution of lithium chloride (LiCl) in 99 % (V/V)
ethanol.

6.3 Magnetic stirrer

6.4 PTFE covered magnetic follower.

6.5 Glass beakers, approximately 100 ml capacity fitted with a cover to minimise the ingress of
carbon dioxide from the air.

NOTE The cover should either be a rigid plastic cover with a hole to allow the electrode to pass through or a
film of disposable plastic placed over the top of the beaker after the electrode has been inserted.

6.6 Timer, capable of measuring seconds.

7 Sampling and sample handling

7.1 Samples shall be taken as described in EN ISO 3170.

7.2 Take care to minimise the uptake of atmospheric water during sampling and sample handling.

NOTE The use of a glass bottle that can be sealed with a septum has been found suitable for sampling and
sample handling. A test portion of the sample can be taken through the septum with a syringe fitted with a needle.

8 Apparatus preparation
8.1 Clean/rehydrate new electrodes before use in alcoholic solutions and after measuring the pHe
of 10 ethanol samples by alternatively soaking them in 1 mol/l sodium hydroxide solution (5.5) for
approximately 30 s then 1 mol/l hydrochloric acid solution (5.6) for approximately 30 s. Repeat this
procedure 3 times.

8.2 Wash the electrode free of acid and alkali with water (5.3) and allow draining. If the electrode is
not to be used immediately, place in and store in a solution of lithium chloride in ethanol (5.4).

9 pH meter and electrode system calibration

9.1 Set up the pH meter in accordance with the manufacture's instructions and, if fitted, adjust the
temperature compensator to 22 °C ± 2°C.

9.2 Remove the combined electrode from the lithium chloride solution (5.4), wash with water (5.3)
and allow draining.

9.3 Rinse the combined electrode (6.2) with pH 4,00 buffer solution (5.1).

5
EN 15490:2007 (E)

9.4 In a 100 ml beaker (6.5), place sufficient volume of pH 4,00 buffer solution (5.1) at 22 °C ± 2°C
to cover the electrode. Insert the magnetic follower (6.6).

9.5 Place the beaker and its contents on the magnetic stirrer (6.3).

NOTE Automatic pH meters may require the user to input the pH value of the buffer solution.

9.6 Place the combined electrode (6.2) into the pH 4,00 buffer solution (5.1). Cover the beaker (see
NOTE under 6.5).

9.7 Switch on the magnetic stirrer (6.3) and allow the pH meter reading to stabilize.

9.8 If necessary adjust the reading to 4,00.

9.9 Remove the combined electrode and rinse it with water (5.3).

9.10 Repeat 9.3 to 9.9 using the pH 10 buffer solution (5.1) (see NOTE under 9.5). If necessary,
adjust the pH meter reading to 10,00 using the slope adjustment.

10 Apparatus verification
10.1 Before testing each day and after cleaning/rehydrating the electrode, see clause 8, verify the
correct functioning of the electrode/pH meter system using a pH 7,00 buffer solution (5.1) in
accordance with 10.2 to 10.7.

10.2 Rinse the combined electrode with water (5.3) then with pH 7,00 buffer solution (5.1).

10.3 In a 100 ml beaker (6.5), place sufficient volume of pH 7,00 buffer solution (5.1) at 22 °C ± 2°C
to cover the electrode. Insert the magnetic follower (6.4).

10.4 Place the beaker and its contents on the magnetic stirrer (6.3).

10.5 Place the combined electrode (6.2) into the pH 7,00 buffer solution (5.1), cover the beaker (see
NOTE under 6.5).

10.6 Switch on the magnetic stirrer (6.3) and allow the pH meter reading to stabilize (see NOTE
under 9.5).

10.7 The pH meter shall read pH 7,00 ± 0,04.

10.8 If the reading is not within the tolerance in 10.7, remove the combined electrode, clean in
accordance with 8.1 and repeat 10.1 to 10.6.

10.9 If the reading is still not within the tolerance in 10.7, recalibrate the electrode and pH meter in
accordance with clause 9.

11 Procedure
11.1 If a temperature compensator is fitted to the pH meter, check and, if necessary, adjust it to
22 °C ±2 °C.

11.2 Bring the ethanol (5.2) to be tested to 22 ºC ± 2 ºC and place sufficient volume of it to cover the
electrode in a 100 ml beaker (6.5).

11.3 Place the beaker and the test portion on a magnetic stirrer (6.3). Insert the magnetic follower
(6.4) and the electrode and cover the beaker to minimise the ingress of atmospheric carbon dioxide.

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 EN 15490:2007 (E)

11.4 Stir the test portion, allow the pHe reading to stabilize, see note. Record the pHe to the nearest
0,01.

NOTE For some samples this may be in excess of 4 min. In such circumstances extra care should be taken to
minimise the ingress of atmospheric carbon dioxide during the measurement.

12 Expression of results

Report the pHe of the sample to the nearest 0,01.

13 Precision

13.1 General

The precision given was derived from statistical analysis by EN ISO 4259 [2] of the results of
interlaboratory testing of a matrix of ethanol samples produced in Europe from bio materials such as
raw wine, molasses, pulp and corn. Typical values are given in Table 1.

NOTE The interlaboratory testing and the statistical evaluation are detailed in an UNGDA Report,
September 2006 (UNGDA, 174 blvd Camélinat, 92247 MALAKOFF Cedex, France, www.ungda.org).

13.2 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, exceed the following value in only one case in twenty.

r = 0,033 X (1)

where

X is the average of results being compared.

13.3 Reproducibility, R

The difference between two single and independent 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, exceed the following value only in one case in twenty.

R = 0,096 X (2)

where

X is the average of results being compared.

7
EN 15490:2007 (E)

Table 1 — Calculated values for repeatability and reproducibility

pHe Repeatability Reproducibility
r R

5 0,165 0,48

5,5 0,181 5 0,528

6 0,198 0,576

6,5 0,214 5 0,624

7 0,231 0,672

7,5 0,247 5 0,72

8 0,264 0,768

8,5 0,280 5 0,816

9 0,297 0,864

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

a) reference to this European Standard, i.e. EN 15490;

b) type and complete identification of the product tested;

c) result of the test (see 12);

d) any deviation, by agreement or otherwise, from the procedure specified;

e) date of the test.

8
 EN 15490:2007 (E)

Annex A
(informative)

Background to actual fuel specification needs

The test method described in this document is able to identify the presence (in fact the absence) of
strong acids and alkalis in ethanol for fuel (blending) purposes. In general, ethanol for those purposes
in Europe requires a minimum pHe of 6,5 and a maximum pHe of 9,0. This has been studied based
on the method's reproducibility and it has been found unfit for compliance testing at the boundaries of
the ethanol specification.

The reason behind this is that the result is greatly influenced by the amount of water in the test
sample. In general, the water content required in European fuels is rather low compared to similar
specifications in other regions of the world.

The pH meter readings are not very stable and there can be a lot of reading drift caused by effects of
the test sample on the glass electrode and possibly by take up of atmospheric carbon dioxide.
Although guidance can be given on the length of time the operator waits until making the readings,
laboratories reported that the time taken for their instrument varied and some laboratories reported
that up to 4 minutes were required to obtain a stable reading. Having the test sample exposed to
atmospheric carbon dioxide for this period would undoubtedly affect the test result.

The water content of the ethanol used to make up the lithium chloride electrolyte is critical and
different results can be obtained if 95% ethanol is used as opposed to 99% ethanol.

In general, more water gives more reproducibility. The user should note this when applying this
document.

9
EN 15490:2007 (E)

Bibliography

[1] Recueil des Méthodes Internationales d’Analyse des Boissons Spiritueuses, des Alcools, et de
la Fraction Aromatique des Boissons, pages 113 – 118, Office International de la Vigne et du
Vin (O.I.V.), 1994

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

10
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