BRITISH STANDARD BS EN

451-1:1995
Incorporating
Corrigendum No. 1

Method of testing fly

ash —
Part 1: Determination of free calcium
oxide content

The European Standard EN 451-1:1994 has the status of a

British Standard

ICS 91.100.30
BS EN 451-1:1995

Committees responsible for this

British Standard

The preparation of this British Standard was entrusted by Technical

Committee B/516, Cement and lime, to Subcommittee B/516/101, Pozzolanas,
upon which the following bodies were represented:

British Aggregate Construction Materials Industries

British Cement Association
British Precast Concrete Federation
British Ready Mixed Concrete Association
Cementitious Slag Makers’ Association
Department of the Environment (Building Research Establishment)
Department of Transport
Electricity Association
Federation of Civil Engineering Contractors
Quality Ash Association

This British Standard, having

been prepared under the
direction of the Sector Board
for Building and Civil
Engineering, was published
under the authority of the
Standards Board and comes Amendments issued since publication
into effect on
15 September 1995 Amd. No. Date Comments
© BSI 04-1999
10174 September Indicated by a sideline in the margin
1998
The following BSI references
relate to the work on this
standard:
Committee reference B/516/101
Draft for comment 91/11363 DC

ISBN 0 580 24526 8

 BS EN 451-1:1995

Contents

Page
Committees responsible Inside front cover
National foreword ii
Foreword 2
Text of EN 451-1 3
List of references Inside back cover

© BSI 04-1999 i
BS EN 451-1:1995

National foreword

This Part of BS EN 451 has been prepared by Subcommittee B/516/101 and is

the English language version of EN 451-1:1994 Method of testing fly ash —
Part 1: Determination of free calcium oxide content published by the European
Committee for Standardization (CEN). This standard has been prepared as part
of a package of standards harmonized within the member countries of CEN to
support the essential requirements of the Construction Products Directive.
BS EN 451-1 describes a method for the determination of free calcium oxide in fly
ash by extraction with a mixture of ethyl acetoacetate and butan-2-ol followed by
titration with hydrochloric acid using bromophenol blue as indicator. The method
has been used successfully for the determination of free calcium oxide in Portland
cements but there is limited experience in the UK of applying the method to fly
ashes.
There is a technical distinction between the various states in which calcium oxide
may be present in ash, only that present as free calcium oxide having the
potential to cause long-term unsoundness in concrete. Calcium oxide present as
part of the glassy phase in ash, or otherwise bound in chemical compounds, does
not lead to unsoundness.
BS EN 451-1 supports BS EN 450 Fly ash for concrete — Definitions,
requirements and quality control. The national foreword to BS EN 450 explains
the relationship between BS EN 450 and BS 3892-1. In particular, it is noted that
whilst both standards specify ashes arising from pulverized bituminous or other
hard coals, BS EN 450 also permits ashes from sub-bituminous coals on a
national basis. Ashes from such sub-bituminous coals, which do not occur in the
UK, may contain free calcium oxide. However, the likelihood of free calcium oxide
being present in ashes from bituminous or other hard coals such as are specified
in BS 3892-1 are remote.
Hence whilst both BS EN 450 and BS 3892-1 include a requirement for the
content of total calcium oxide, only the former includes a requirement for free
calcium oxide. An autocontrol maximum of 1.0 % is specified, although a value of
up to 2.5 % is permitted provided that the ash complies with the requirement for
soundness specified in BS EN 450.

Cross-references

Publication referred to Corresponding British Standard

EN 196-7:1989 BS EN 196-7:1992 Methods of testing cement

Part 7: Methods of taking and preparing samples of
cement
ISO 3534-1:1993 BS ISO 3534 Statistics. Vocabulary and symbols
BS ISO 3534-1:1993 Probability and general statistical
terms

A British Standard does not purport to include all the necessary provisions of a
contract. Users of British Standards are responsible for their 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 4, an inside back cover and a back cover.
This standard has been updated (see copyright date) and may have had
amendments incorporated. This will be indicated in the amendment table on the
inside front cover.

ii © BSI 04-1999
EUROPEAN STANDARD EN 451-1
NORME EUROPÉENNE
September 1994
EUROPÄISCHE NORM

UDC 666.952.2:620.1:661.842.22

Descriptors: Fly ash, chemical analysis, determination of content, calcium oxides

English version

Method of testing fly ash — Part 1: Determination of free

calcium oxide content

Méthode d’essai des cendres volantes — Prüfverfahren für Flugasche —

Partie 1: Détermination de la teneur en oxyde Teil 1: Bestimmung des freien
de calcium libre Calciumoxidgehalts

This European Standard was approved by CEN on 1994-09-09. 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 version (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,
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

© 1996 Copyright reserved to CEN members

Ref. No. EN 451-1:1994 E
EN 451-1:1994

Foreword Contents
This European Standard was drawn up by the Page
Technical Committee CEN/TC 104, Concrete, the Foreword 2
Secretariat of which is held by DIN.
1 Scope 3
The preparatory work was carried out by WG 4 of
2 Normative references 3
CEN/TC 104 since June 1988 in which the following
countries participated: Austria, Belgium, Denmark, 3 General 3
France, Germany, Ireland, Italy, Netherlands, 3.1 Number of determinations 3
Norway, Portugal, Sweden and United Kingdom. 3.2 Repeatability and reproducibility 3
This European Standard has been prepared under a 3.3 Expression of masses and volumes 3
mandate given to CEN by the European
Commission and the European Free Trade 4 Reagents 3
Association, and supports essential requirements of 5 Apparatus 3
EC Directive(s). 6 Procedure 3
This European Standard shall be given the status of 6.1 Preparation of sample 3
a national standard, either by publication of an 6.2 Determination 3
identical text or by endorsement, at the latest by
March 1995, and conflicting national standards 6.3 Calculations 4
shall be withdrawn at the latest by March 1995. 7 Results 4
No existing European Standard is superseded. 8 Repeatability and reproducibility 4
According to the CEN/CENELEC Internal
Regulations, the following countries are bound to
implement this European Standard: Austria,
Belgium, Denmark, Finland, France, Germany,
Greece, Iceland, Ireland, Italy, Luxembourg,
Netherlands, Norway, Portugal, Spain, Sweden,
Switzerland, United Kingdom.

2 © BSI 04-1999
 EN 451-1:1994

1 Scope 4.3 Propan-2-ol.

This European Standard describes the procedure for 4.4 Indicator (0,1 g of bromophenol blue in 100 ml of
the determination of free calcium oxide content in ethanol).
fly ash. 4.5 Hydrochloric acid (0,100 M).
The standard describes the reference procedure. If
other methods are used it shall be shown that they 5 Apparatus
give results equivalent to those obtained by the 5.1 Balance, capable of weighing to an accuracy
reference method. of 0,0001 g or better.
5.2 Test sieve, with 0,063 mm sieve cloth conforming
2 Normative references to ISO 565.
This European Standard incorporates by dated or 5.3 Mortar and pestle, or similar equipment for
undated reference, provisions from other grinding.
publications. These normative references are cited
5.4 Desiccator, containing a drying agent, e.g. silica
at the appropriate places in the text and the
gel.
publications are listed hereafter. For dated
references, subsequent amendments to or revisions 5.5 Flask, 250 ml.
of any of these publications apply to this European 5.6 Spiral reflux condenser.
Standard only when incorporated in it by 5.7 Absorption tube, filled with sodium hydroxide on
amendment or revision. For undated references the an inorganic carrier (to protect the contents of the
latest edition of the publication referred to applies. flask and the condenser from reacting with
EN 196-7:1989, Methods of testing cement — atmospheric carbon dioxide).
Methods of taking and preparing samples of cement. 5.8 Filter crucible, with pore sizes of 0,004 mm
ISO 565:1990, Test sieves — Woven metal wire cloth, to 0,010 mm.
perforated plate and electroformed sheet — Nominal NOTE Alternatively also a filter funnel, in which a filter paper
sizes of openings. with fine pores of a diameter of approximately 0,002 mm and a
filter paper with medium pores of a diameter of
ISO 3534-1:1993, Statistics — Vocabulary and approximately 0,007 mm can be placed, may be used.
symbols — Part 1: Probability and general
statistical terms. 6 Procedure
3 General 6.1 Preparation of sample
Subdivide the laboratory sample, prepared in
3.1 Number of determinations
accordance with 6.2.2 of EN 450 by a suitable
Carry out twice the procedure for determining the method to obtain a subsample of about 100 g. Pass
free calcium oxide content. this subsample through the test sieve (5.2). Grind
If the difference between two determinations is any residue in the mortar (5.3) until all the
more than twice the repeatability standard subsample passes through the sieve completely.
deviation, repeat the test and take the mean of the Homogenize the total subsample and place it in the
closest values. desiccator (5.4) until tested.
3.2 Repeatability and reproducibility 6.2 Determination
The standard deviations of repeatability and Place a weighed portion of 1,0 g to 1,5 g of the
reproducibility, as defined in ISO 3534, are subsample prepared in accordance with 6.1 into
expressed in absolute percentages by mass. the 250 ml flask (5.5) and add a mixture of 12 ml
butanoic acid, 3-oxo-ethyl ester (4.1) and 80 ml
3.3 Expression of masses and volumes
butan-2-ol (4.2). Fit the flask with the spiral reflux
Express masses in grams to the nearest 0,0001 g condenser (5.6) and the absorption tube (5.7) and
and volumes from the burette in millilitres to the boil for 1 h. Filter the warm mixture through the
nearest 0,05 ml. filter crucible (5.8). Wash the residue with
propan-2-ol (4.3) until the filtrate reaches a volume
4 Reagents of 50 ml. If the filtrate is cloudy, reject it and repeat
Use only reagents of analytical grade and distilled the extraction with a new weighed portion of the
water, or water of equal purity. subsample.
4.1 Butanoic acid, 3-oxo-ethyl ester (= ethyl Add a few drops of bromophenol blue indicator (4.4)
acetoacetate). to the flitrate and titrate with hydrochloric
acid (4.5) until the colour changes to yellow. Record
4.2 Butan-2-ol.
the volume V of hydrochloric acid used.

© BSI 04-1999 3
EN 451-1:1994

6.3 Calculations 7 Results

The free calcium oxide content (WCaO), expressed as The mean value of two determinations, calculated to
a percentage by mass of the dry fly ash, shall be two decimal places and expressed to one decimal
calculated from the following equation: place, shall be taken as the free calcium oxide
28,04 × C × V × 100 content of the sample.
W CaO = ----------------------------------------
m × 1 000
8 Repeatability and reproducibility
where
The standard deviation for repeatability is 0,02 %
C is the concentration (in mol/l) of the
by mass (provisional value).
hydrochloric acid solution;
The standard deviation for reproducibility is 0,04 %
V is the volume (in ml) of hydrochloric acid by mass (provisional value).
solution used for titration;
m is the weighed proportion (in g) of the dried
fly ash.

4 © BSI 04-1999
 BS EN 451-1:1995

List of references

See national foreword.

© BSI 04-1999
BS EN
451-1:1995
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