BRITISH STANDARD BS EN ISO

3681:1998
BS 6782-2:
1996
Incorporating
Amendment No. 1 to
BS 6782-2:1996

Binders for paints and (renumbers the BS as

BS EN ISO
3681:1998)

varnishes —
Determination of
saponification value —
Titrimetric method

The European Standard EN ISO 3681:1998 has the status of a

British Standard

ICS 87.060.20
BS EN ISO 3681:1998

Committees responsible for this

British Standard

The preparation of this British Standard was entrusted to Technical

Committee STI/3, Paints, media and related products, upon which the
following bodies were represented:

British Coatings Federation Ltd.

European Resin Manufacturers’ Association
FOSFA International
Ministry of Defence
Oil and Colour Chemists’ Association
Seed Crushers’ and Oil Processors’ Association

This British Standard, having

been prepared under the
direction of the Sector Board for Amendments issued since publication
Materials and Chemicals, was
published under the authority
of the Standards Board and Amd. No. Date Comments
comes into effect on
15 November 1996 10151 November Renumbers BS 6782-2:1996 as
1998 BS EN ISO 3681:1998 with addition of EN ISO title
© BSI 06-1999
page and foreword, and changes to national
foreword
The following BSI references
relate to the work on this
standard:
Committee reference STI/3
Draft for comment 92/50270 DC

ISBN 0 580 26476 9

 BS EN ISO 3681:1998

Contents

Page
Committees responsible Inside front cover
National foreword ii
Foreword 2
1 Scope 3
2 Normative references 3
3 Definitions 3
4 Principle 3
5 Reagents 3
6 Apparatus 3
7 Sampling 3
8 Preliminary test 4
9 Procedure 4
10 Expression of results 4
11 Test report 5
Annex A (normative) Binders which are saponifiable
with difficulty — Determination of saponification value 6
Annex ZA (normative) Normative references to
international publications with their relevant
European publications Inside back cover
Table 1 — Mass of test portion 4

© BSI 06-1999 i
BS EN ISO 3681:1998

National foreword

This Part of BS 6782 has been prepared by Technical Committee STI/3 and is the
English language version of EN ISO 3681:1998 Binders for paints and
varnishes — Determination of saponification value — Titrimetric method,
published by the European Committee for Standardization (CEN). It is identical
with ISO 3681:1996, published by the International Organization for
Standardization (ISO).
This British Standard supersedes BS 6782-2:1987, which is withdrawn.
The difference between this British Standard and BS 6782-2:1987 is that the
saponification value is no longer related to 1 g of non-volatile matter of the
product but to 1 g of the product itself.
Cross-references
The British Standards which implement international or European publications
referred to in this document may be found in the BSI Standards Catalogue under
the section entitled “International Standards Correspondence Index”, or by using
the “Find” facility of the BSI Standards Electronic Catalogue. Attention is drawn
to Annex ZA, which gives the European Standards that correspond to the
international standards referred to.
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 ISO title page, pages 2 to 6, 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 06-1999
EUROPEAN STANDARD EN ISO 3681
NORME EUROPÉENNE
April 1998
EUROPÄISCHE NORM

ICS 87.060.20

Descriptors: Paints, varnishes, binders (materials), tests, chemical tests, determination, saponification number, volumetric analysis

English version

Binders for paints and varnishes — Determination of

saponification value — Titrimetric method
(ISO 3681:1996)

Liants pour peintures et vernis — Bindemittel für Beschichtungsstoffe —

Détermination de l’indice de saponification — Bestimmung der Verseifungszahl —
Méthode titrimétrique Titrimetrisches Verfahren
(ISO 3681:1996) (ISO 3681:1996)

This European Standard was approved by CEN on 9 March 1998.

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

© 1998 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national
Members
Ref. No. EN ISO 3681:1998 E
EN ISO 3681:1998

Foreword
The text of the International Standard from
Technical Committee ISO/TC 35, Paints and
varnishes, of the International Organization for
Standardization (ISO) has been taken over as an
European Standard by Technical Committee
CEN/TC 139, Paints and varnishes, the secretariat
of which is held by DIN.
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
month of October 1998, and conflicting national
standards shall be withdrawn at the latest by
October 1998.
According to CEN/CENELEC Internal Regulations,
the national standards organizations of the
following countries are bound to implement this
European Standard: Austria, Belgium,
Czech Republic, Denmark, Finland, France,
Germany, Greece, Iceland, Ireland, Italy,
Luxembourg, Netherlands, Norway, Portugal,
Spain, Sweden, Switzerland and
the United Kingdom.
NOTE Normative references to International Standards are
listed in Annex ZA (normative).

2 © BSI 06-1999
 EN ISO 3681:1998

1 Scope 4 Principle
This International Standard specifies a titrimetric After a preliminary test to determine the
method for determining the esterified-acid content saponification conditions (concentration of
in binders for paints and varnishes, free acids and potassium hydroxide solution, saponification
acid anhydrides being necessarily included in the time, etc.) for the product to be tested, a test portion
result obtained. is boiled under reflux with potassium hydroxide
Because different binders vary in their resistance to solution under these conditions. The hot solution is
saponification, this International Standard is of titrated with standard volumetric hydrochloric acid,
limited applicability. If necessary, completeness of either in the presence of a colour indicator or
saponification may be checked by repeating the test potentiometrically.
under more severe conditions achieved by the use of
longer saponification time, more concentrated 5 Reagents
potassium hydroxide solution, or a higher-boiling During the analysis, use only reagents of recognized
alcohol as solvent. analytical grade, and only water of at least grade 3
Annex A specifies a procedure suitable for binders purity as defined in ISO 3696.
that saponify with difficulty. 5.1 Toluene, or other suitable unsaponifiable
The method is not applicable to those materials that solvent.
show further reaction with alkalis beyond normal 5.2 Potassium hydroxide solution, in isopropanol,
saponification. ethanol or methanol, c(KOH) = 0,5 mol/l.
NOTE 1 If more severe conditions for saponification are
2 Normative references needed, 2 mol/l ethanolic potassium hydroxide solution may be
used, or 1,2-ethanediol (ethylene glycol) or 2,2’- oxydiethanol
The following standards contain provisions which, (diethylene glycol) may be used as the solvent
through reference in this text, constitute provisions (see clause 8 and Annex A).
of this International Standard. At the time of Where isopropanol can be used instead of ethanol or
publication, the editions indicated were valid. All methanol, it shall be used. The applicability of the
standards are subject to revision, and parties to solution in isopropanol is comparable to that of an
agreements based on this International Standard ethanolic solution and its toxicity is less than that of
are encouraged to investigate the possibility of a methanolic solution.
applying the most recent editions of the standards
5.3 Hydrochloric acid, standard volumetric
indicated below. Members of IEC and ISO maintain
solution, c(HCl) = 0,5 mol/l, in a mixture of 4 parts
registers of currently valid International Standards.
by volume of methanol and 1 part by volume of
ISO 385-1:1984, Laboratory glassware — water or in water.
Burettes — Part 1: General requirements.
5.4 Phenolphthalein or thymolphthalein, 10 g/l
ISO 648:1977, Laboratory glassware — One-mark solution in 95 % (V/V) ethanol, in methanol or in
pipettes. isopropanol (see note 1).
ISO 842:1984, Raw materials for paints and
varnishes — Sampling. 6 Apparatus
ISO 3696:1987, Water for analytical laboratory Ordinary laboratory apparatus and glassware,
use — Specification and test methods. complying with the requirements of ISO 385-1 and
ISO 648, together with the following:
3 Definitions 6.1 Conical flask, of capacity 250 ml, with a
For the purposes of this International Standard, the ground-glass joint.
following definitions apply. 6.2 Reflux condenser, with a ground-glass joint.
3.1 6.3 Burette or pipette, of capacity 25 ml or 50 ml.
saponification 6.4 Potentiometric titration apparatus, fitted with a
the formation of the alkali metal salts of derivatives glass electrode and a reference electrode. The use of
of organic acids this apparatus is an optional alternative (see 9.2).
3.2 6.5 Magnetic stirrer
saponification value 6.6 Water bath or oil bath
the number of milligrams of potassium hydroxide
(KOH) required for the saponification of 1 g of the 7 Sampling
product tested Take a representative sample of the product to be
tested, as described in ISO 842.

© BSI 06-1999 3
EN ISO 3681:1998

8 Preliminary test 9.2 Determination

If no special saponification conditions are specified Dissolve the test portion, if necessary, in a
or agreed, carry out the procedure specified in measured volume of toluene or other suitable,
clause 9 using 25 ml of potassium hydroxide unsaponifiable solvent (5.1), warming, if necessary,
solution (5.2) and a boiling time of 1 h. To test under the reflux condenser (6.2). Add, from the
whether the saponification value can be determined burette or pipette (6.3), one of the following:
under these conditions, intensify the conditions by a) 25 ml of 0,5 mol/l potassium hydroxide
increasing the saponification time to at least 2 h solution (5.2);
and/or by using a 2 mol/l potassium hydroxide b) 25 ml of a different potassium hydroxide
solution or a solution of potassium hydroxide in an solution (see clause 8 and note 1 to 5.2);
alcohol that has a boiling point distinctly higher
c) the specified or agreed volume of a potassium
than that of ethanol, for example 1,2-ethanediol
(ethylene glycol) or 2,2’-oxydiethanol hydroxide solution.
(diethylene glycol). Heat, while stirring, the contents of the flask to
boiling in a water bath or oil bath (6.6) and reflux
If no increase in the final (i.e. mean) result
for 1 h or the specified or agreed time, or the time
(see 10.1) is obtained using the more intense
found necessary in the preliminary test
conditions, the test may be carried out using this
(see clause 8).
International Standard. If a higher value is
obtained which is not further increased by again Titrate the hot solution with hydrochloric acid (5.3)
intensifying the test conditions, this International after addition of 3 drops of phenolphthalein or
Standard may be followed but using and noting the thymolphthalein solution (5.4).
intensified conditions applied. If a constant result is If the potentiometric titration is used, the glass
not obtained even under the most severe conditions electrode shall have a suitable response time.
of saponification, the method to be used shall be If precipitation occurs, bring the precipitate back
agreed between the interested parties. into solution by the addition of water, which acts as
a solvent.
9 Procedure
9.3 Blank test
Carry out the determination in duplicate.
Carry out a blank test, following the same procedure
9.1 Test portion but omitting the test portion.
By reference to Table 1, select the appropriate mass
of test portion to be taken. This mass shall be chosen 10 Expression of results
so that less than half of the volume of potassium 10.1 Calculation
hydroxide solution added is sufficient to saponify
the test portion. Calculate the saponification value SV, in milligrams
of KOH per gram of product, using the equation
Table 1 — Mass of test portion
( V 0 – V 1 ) × c × 56,1
Expected saponification Approximate mass SV = --------------------------------------------------
-
value of test portion m
mg KOH/g g where
up to 10 20 V0 is the volume, in millilitres, of hydrochloric
acid (5.3) required for the blank test (9.3);
above 10 to 20 10
V1 is the volume, in millilitres, of hydrochloric
above 20 to 50 5
acid (5.3) required for the
above 50 to 100 2,5 determination (9.2);
above 100 to 200 1,5 c is the actual concentration, in moles per
above 200 to 300 1 litre, of the hydrochloric acid (5.3);
above 300 to 500 0,5 56,1 is the factor for the conversion of millilitres
above 500 0,2 of hydrochloric acid, c(HCl)= 1 mol/l, to
milligrams of potassium hydroxide;
Weigh, to the nearest 1 mg, the test portion into the
m is the mass, in grams, of the test
conical flask (6.1).
portion (9.1).

4 © BSI 06-1999
 EN ISO 3681:1998

If the two results (duplicates) differ by more 11 Test report

than 3 % (relative to the mean), repeat the
The test report shall contain at least the following
procedure described in clause 9.
information:
Report as the final result the mean, rounded to the
a) all details necessary to identify the product
nearest 0,1 mg KOH/g, of two valid results
(replicates). tested;
b) a reference to this International Standard
10.2 Precision
(ISO 3681);
No precision data are currently available. c) the result of the test as indicated in 10.1;
d) the solvent and the concentration and volume
of the potassium hydroxide solution used;
e) the period of boiling;
f) the type of titration: in the presence of a colour
indicator (phenolphthalein or thymolphthalein)
or potentiometric;
g) any deviation from the test method specified;
h) the date of the test.

© BSI 06-1999 5
EN ISO 3681:1998

Annex A (normative) A.3 Preliminary test

Binders which are saponifiable with See clause 8.
difficulty — Determination of A.4 Procedure
saponification value Carry out the determination in duplicate.
A.1 Reagents A.4.1 Test portion
During the analysis, use only reagents of recognized Weigh, to the nearest 0,1 mg, about 0,5 g of the
analytical grade, and only water of at least grade 3 sample into a 100 ml conical flask (see A.2.1).
purity as defined in ISO 3696. A.4.2 Determination
A.1.1 Hydrochloric acid, aqueous standard By means of the pipette (A.2.2), add 10 ml of
volumetric solution, c(HCl) = 0,25 mol/l. potassium hydroxide solution (A.1.2) to the flask
A.1.2 Potassium hydroxide, solution containing the test portion (A.4.1).
in 1,2-ethanediol. Stopper the flask and mix the contents by swirling.
Weigh about 6 g of potassium hydroxide into Secure the stopper and heat the contents in the oil
a 100 ml conical flask (see A.2.1) and add 25 ml bath (A.2.3) to 70 °C to 80 °C. Maintain this
of 1,2-ethanediol. Warm until the potassium temperature for 2 min to 3 min.
hydroxide is dissolved. It is advisable to insert a Swirl the contents of the flask, as before, during
thermometer in the solution whilst carrying out the heating.
dissolving procedure in order to avoid exceeding a Remove the flask from the oil bath. Shake the
temperature of 130 °C. If this occurs, a deep yellow contents vigorously and allow the flask to stand.
colour develops in the solution.
Remove the stopper carefully so as to permit air to
When the potassium hydroxide is completely escape.
dissolved, transfer the solution to a 150 ml conical
Again secure the stopper in the flask and return the
flask (see A.2.1) containing 75 ml of 1,2-ethanediol.
flask to the oil bath heated to 120 °C to 130 °C.
Shake the resultant solution carefully and allow it
NOTE 2 If necessary, a temperature higher than 130 °C may be
to cool. used. Saponification under pressure is also possible.
A.1.3 Phenolphthalein, 10 g/l solution in 95 % (V/V) Heat for 3 min at this temperature, cool the flask
ethanol. to 80 °C to 90 °C, remove the stopper and rinse it
A.2 Apparatus with water, collecting the washings in the flask.
A.2.1 Conical flasks, of capacity 100 ml and 150 ml, Add a further 15 ml of water to the flask and a few
with ground-glass stoppers. drops of phenolphthalein solution (A.1.3). Titrate
A.2.2 Pipette, capacity 10 ml, the delivery end of the mixture, whilst stirring, with hydrochloric
which has been modified so that its internal acid (A.1.1).
diameter is between 2 mm and 3 mm in order to A.4.3 Blank test
facilitate the delivery of the potassium hydroxide Carry out a blank test, using the same procedure
solution. but omitting the test portion.
The modified pipette shall be recalibrated A.5 Expression of results
before use.
See clause 10.
A.2.3 Oil bath, capable of being maintained at
A.6 Test report
temperatures to 150 °C to within 1 °C.
See clause 11.
A.2.4 Magnetic stirrer

6 © BSI 06-1999
 EN ISO 3681:1998

Annex ZA (normative)
Normative references to international publications with their
relevant European publications
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.
Publication Year Title EN Year

ISO 3696 1987 Water for analytical laboratory use — Specification and EN ISO 3696 1995
test methods

© BSI 06-1999 7
BS EN ISO
3681:1998
BS 6782-2: BSI — British Standards Institution
1996
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