International Standard

INTERNATIONAL ORGANIZATION FOR STANDARDIZATION*MEIKKG[YHAPO,4HAR OPTAHI43AUIR I-IO CTAH~APTl43A~l4M.ORGANISATION INTERNATIONALE DE NORMALISATION

Non-ionic surface active agents - Polyalkoxylated

derivatives - Determination of hydroxyl value - Phthalic
anhydride method
Agents de surface non ioniques - D&iv& polyoxyalkyl&Gs - Determination de l’indice d’hydroxyle - Methode 6 l’anhydride
ph talique
iTeh STANDARD PREVIEW
First edition - 1979-12-15 (standards.iteh.ai)
ISO 4327:1979
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35804d9b04fc/iso-4327-1979

UDC 661.185.4 : 543.854 Ref. No. ISO 4327-1979 (E)

Descriptors : surfactants, non-ionic surfactants, polyalkoxylated derivatives, Chemical analysis, determination, hydroxyl value.

Price based on 8 pages

FOREWORD

ISO (the International Organization for Standardization) is a wortdwide federation

of national Standards institutes (ISO member bodies). The work of developing
lnternational Standards is carried out through ISO technical committees. Every
member body interested in a subject for which a technical committee has been set
up has the right to be represented on that committee. International organizations,
governmental and non-governmental, in liaison with ISO, also take part in the work.

Draft International Standards adopted by the technical committees are circulated

to the member bodies for approval before their acceptance as International
Standards by the ISO Council.

International
ISO/TC 91, Surface
Standard ISO 4327
iTeh STANDARD PREVIEW
was developed
active agents, and was circulated
by Technical Committee
to the memher bodies in
June 1976.
(standards.iteh.ai)
It has been approved by the member bodies of the following countries :
ISO 4327:1979
Austral ia
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I reland Romania
Austria Japan 35804d9b04fc/iso-4327-1979
South Africa, Rep* of
Belgium Korea, Rep. of Seitzerland
Brazil Mexico Turkey
France Netherlands United Kingdom
Germany, FR. New Zealand
lndia Poland

The member bodies of the following countries expressed disapproval of the

document on technical grounds :

Chile
Spain

EI International Organkation for Standardization, 1979 e

Printed in Switzerland
INTERNATIONAL STANDARD ISO 43274979 (E)

Non-ionic surface active agents - Polyalkoxylated

derivatives - Determination of hydroxyl value - Phthalic
anhydride method

0 INTRODUCTION - Other free acids interfere by reacting with the

Standard volumetric sodium hydroxide solution; bases,
The classical method for the determination of the hydroxyl including some tertiary amines, interfere by reacting
value described in this International Standard requires, with the phthalic acid produced. In these cases a
because of the toxic effects of pyridine and phthalic anhy- correction may be made for the acidity or alkalinity (see
dride, that all handling and the titration be conducted ISO 4314).
under a well ventilated fume hood. However, annex C
provides a procedure using a special apparatus which Although epoxides interfere, the method may still be used
reduces the danger due to pyridine and phthalic anhydride. if the epoxides tan be eliminated, without altering the
hydroxyl value, by cold vacuum distillation.

1 SCOPE
iTeh STANDARD PREVIEW The presence of water in the Sample is revealed by reaction
with the phthalic anhydride, but the method may never-
This International Standard (standards.iteh.ai)
specifies a method for the theless be used without
the procedure are followed.
risk if the precautions described in
determination of the hydroxyl value of polyalkoxylated
condensates by esterification of the hydroxyl groups
ISOwith
4327:1979
phthalic anhydride.
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3 REFERENCES
35804d9b04fc/iso-4327-1979
ISO 607, Surface active agen ts and de tergen ts - Me thods o f
2 FIELD OF APPLICATION Sample division. 1)

This method is applicable to the determination of the ISO 1392, Determination of crystallizing Point - General
hydroxy groups of polyalkoxylated condensates of me thod.
aliphatic and alicyclic compounds (in particular, of
ethylene Oxide, propylene Oxide or mixed adducts of ISO 2211, Liquid Chemical products - Measurement of
primary and secondary fatty alcohols, alkylphenols and colour in Hazen units (pla tinum-Cobalt scale).
fatty aci ds, and tan be used for the determination of ISO 4314, Surface active agents - Determination of free
hydroxyl values from 10 to 1 000. alkalinity or free acidity - Jitrimetric me thod.

However, certain substances present in these materials may ISO 43 17, Surface active agen ts - Determination of water
react with the phthalic anhydride or with the Standard content - Karl Fischer method.
volumetric sodium hydroxide Solution used and
consequently falsify the results.
4 DEFINITION

The possible interferences are detailed below : hydroxyl value I(OH) : The number of milligrams of
potassium hydroxide needed to neutralize the acidity
- Primary and secondary amines and amides, tertiary which appears during the esterification, by phthalic anhy-
alcohols, thiols and epoxides undergo side reactions dride, of the hydroxyl groups in 1 g of the material, or the
which affect the accuracy of the method. number of milligrams of potassium hydroxide correspond-
- Long-chain fatty acids and esters may interfere by ing to the hydroxyl groups in 1 g of the material.
forming anhydrides which are more stable than phthalic NOTE - The number of moles of potassium hydroxide correspond-
anhydride and are not completely decomposed at the ing to the hydroxyl value is equal to the number of hydroxyl groups
end of the method. present in 1 kg of the material.

1) In preparation. (Revision of ISO/R 607.)

1
ISO 4327-1979 (E)

5 PRINCIPLE 9.2.1 Prepara tion

Es terif ication of the hydroxyl groups by phthalic anhydride Place 140 + 1 g of phthalic anhydride (melting Point
pyridine solut ion. 131 + 1 ‘C, determined by ISO 1392; and minimum
purity 99,5 %, determined by the method specified in
Hydrolysis of the excess of phthalic anhydride with water annex A) in a brown glass bottle of capacity 2 litres.
contained in the sodium hydroxide Solution used for the
neutralization. Add 1 litre of the pyridine (7.1) and Shake vigorously
until completely* dissolved. DO not use this solution id its
Neutralization of the acidity which appears during the colour exceeds 200 Hazen units on the platinum-cobalt
esterification, and of the phthalic acid formed during the scale (determined by ISO 2211).
hydrolysis, by sodium hydroxide Solution in the presence
of phenolphthalein as indicator. 9.2.2 Verifica tion of reagen t concen tra tion
Calculation of the hydroxyl value from the differente Using a pipette (8.4), transfer exactly 25,0 ml sf the
between the volumes of sodium hydroxide Solution used Solution (7.2) to a 250 ml conical flask.
for the titration of the blank and of the test solution.
Titrate with the Standard volumetric sodium hydroxide
Solution (7.3) in the presence of the phenolphthalein
6 REACTIONS Solution (7.4).

A volume of 83 to 87 ml of the Standard volumetric sodium

The reactions occurring are as follows :
hydroxide Solution (7.3) should be required.
Esterif ication
9.3 Sodium hydroxide, 0,5 N Standard volumetric solution.

co\ 0+ ROH -
COOR
9.4 Phenolphthalein [3,3-bis (4-hydroxyphenyl) phthalide],
CO’ iTeh STANDARD PREVIEW
COOH IO g/l Solution in pyridine.

b) Hydrolysis of the excess phthalic (standards.iteh.ai)

anhydride
Dissolve
pyridine
1g
(7.1).
of phenolphthalein in 100 ml of the

co\ O+H,O -
COOH ISO 4327:1979
8 APPARATUS
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CO’ COOH
35804d9b04fc/iso-4327-1979
Ordinary laboratory apparatus and :

Cl Neutralization of acid the 8.1 Burette, capacity 50 ml, complying with the require-
esterification ments of class A of ISO/R 385.

COOR COOR 8.2 Four flat-bottomed flasks, capacity 250 ml, with
+ NaOH - + H,O conical ground glass joint.
COOH COONa

8.3 Four condensers, of effective length 400 mm, with

d) Neutralization of the phthalic acid formed during conical ground glass joints fitting the flasks (8.2), and
hydrolysis complying with the requirements of ISO 4799.

COOH COONa 8.4 One-mark pipettes, capacity 25 ml, complying with

+- 2 NaOH e + 2 H,O the requirements of ISO 648.
COOH COONa

9 SAMPLING
9 REAGENTS
Laboratory samples of polyal koxylated surface active
During the analysis, use only reagents of recognized agents shall be prepared and stored according to the
analytical grade, and only distilled water or water of instructions given in ISO 607.
equivalent purity.

9.1 Pyridine, if necessary distilled in the presence of 5 %

10 PROCEDURE
of phthalic anhydride. The boiling temperature shall be
between 114,5 and 115,5 “C. All the necessary apparatus shall be absolutely clean and
dry. Consequently, prepare all apparatus necessary for
9.2 Phthalic anhydride Solution in pyridine (phthalation carrying out two simultaneous determinations on two
reagent). different test portions, and two blank tests.

2
 ISO 4327-1979 (E)

10.1 Test Portion lntroduce exactly 50,O ml of the Standard volumetric

sodium hydroxide Solution (7.3) into the flask, from the
lt is essential that the approximate water content of the burette (8.1).
test Portion be known; if necessary, determine the water
content of the sample by the method specified in ISO 4317. Add, by means of a 1 ml pipette, 4 or 5 drops of the
phenolphthalein Solution (9.4). Continue the titration with
Weigh, to the nearest 0,001 g, into a dry and previously
the Standard volumetric sodium hydroxide Solution (7.3)
tared flask (8.2), a mass of the laboratory Sample calculated
until the Solution remains pink for 15 s.
as follows :

- For a water content Iower than % (m/m) , the mass,

10.3 Blank tests
in grams, of the test Portion shall b e such that
Carry out two blank tests at the same time as the
365
determination, using the same reagents, but without the
m”=I(OH) test Portion.
where I(OH) is the est imated hydroxy I value, in milli-
NOTE - For the results to be valid, the differente between the
grams of potassium hYd roxide per gram. volume Vo for the blank test and the volume VI used for each
test Portion should lie between 10 and 15 ml.
The maximum mass of the test Portion will therefore
If this differente is greater than 15 ml, the test Portion is too large,
be 36,5 g as the method is restricted to a minimum and it is necessary to recommence the test with smaller test portions
hydroxyl value of 10. [the hydroxyl value, I(OH), will have been greater than the value
estimated initially].
- For a water content greater than 1 % (m/m) and
If the differente is less than IO ml, the test Portion is too small, and
up to 40 % (m/m), the mass, in grams, of the test
it is necessary to recommence the test with larger test portions [the
Portion shall be such that : hydroxyl value, I(OH), will have been lower than estimated
initially].
31 000
1770 % ,100 - [H,Oj/ iTeh STANDARD
I(OH) [H,O]
+ 740 PREVIEW
(standards.iteh.ai)
11 EXPRESSION OF RESULTS
42 000
m. < ISO 4327:1979
‘100 - [H,O] ’ i(OH) + 1 040 [H,O]
‘1 I 11.1 Method of calculation
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35804d9b04fc/iso-4327-1979
The hydroxyl value, IO-U corresponding to the test
[H2 0] is the percentage, by mass, of water in the Portion, is given by the formu ia
test sampl e;
w o-V,) xTx56,lO
-C
I(OH) is the estimated hydroxyl value, in milligrams
m0
of potassium hydroxide per gram.

The table in annex B gives the Iimiting values of m. for

water contents from 1 to 40 % (m/m) and estimated V. is the volume, in millilitres, of the Standard
hydroxyl values from 10 to 1 100. volumetric sodium hydroxide Solution (7.3) used for the
blank test;
WARNING - All the operations specified below shall be
conducted under a well ventilated fume hood. VI is the volume, in millilitres, of the Standard
volumetric sodium hydroxide Solution (7.3) used for the
10.2 Determination determination;

T is the exact normality of the Standard volumetric

10.2.1 Es terifica tion
sodium hydroxide Solution (7.3);
Using a pipette (8.4), add 25,0 ml of the phthalation
m0 is the mass, in grams, of the test Portion;
reagent (7.2) to the flask containing the test Portion (10.1).
Attach a condenser (8.3), previously rinsed with the C is the positive acid value, or the negative alkali
pyridine (7.1), to the flask. Swirl to mix the contents. Heat value, of the material (see ISO 4314); this value shall
the flask at gentle reflux for 1 h. Allow to cool to room be ignored if it is 0,3 or less.
temperature.
Take as the result the arithmetic mean of the duplicate
10.2.2 Hydrolysis and titration determinations.

Rinse the condenser with the pyridine (7.1). Remove the

flask from its condenser and rinse the ground glass joints 11.2 Precision
with water from a wash bottle. Place a bar magnet in the
flask, place the flask on a magnetic stirrer and switch on the The precision of the determination is 1,5 % of the result,
stirrer. which should be rounded in consequence.

3
ISO 4327-1979 (E)

11.3 Reproducibility 12 TEST REPORT

The following information is the result of analyses carried The test report shall include the following particulars :
out in 21 laboratories, in each by an analyst giving at least
a) all information necessary for the complete identi-
two resu Its.
fication of the Sample;

b) the reference of the method used (reference to this

Sample A B International Standard) ;
1 1
Mean /(OH) 51,9 172,3 c) the results and the method of expression used;

r Standard deviation of reproducibility, 0~ I 1,15 3,80 I d) the test conditions;

e) any operational details not specified in this Inter-

national Standard, or regarded as optional, as well as any
incidents likely to have affected the results.

iTeh STANDARD PREVIEW

(standards.iteh.ai)
ISO 4327:1979
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35804d9b04fc/iso-4327-1979

ANNEX A

DETERMINATION OF THE PURITY OF THE PHTHALIC ANHYDRIDE

Place 1,5 g, weighed to the nearest 0,001 g, of phthalic where

anhydride in a 250 ml conical flask. Add 100 ml of a 50 %
V2 is the volume, in millilitres, of the Standard
(WV) mixture of pyridine (7.1) and water, previously
volumetric sodium hydroxide Solution (7.3) used;
neutralized with a 0,l N sodium hydroxide or hydrochloric
acid Solution in the presence of the phenolphthalein T is the exact normality of the Standard volumetric
Solution (7.4). Titrate with the Standard volumetric sodium sodium hydroxide Solution (7.3);
hydroxide Solution (7.3) to a permanent pink colour.
1731 is the mass, in grams, of the Sample of phthalic
anhydride;
The purity, expressed as a percentage by mass, is given by
the formula 74 is a factor representing the fact that 2 moles of
sodium hydroxide are needed to neutralize the phthalic
acid formed by the hydrolysis of 1 mole of phthalic
v,xTx74x100
- anhydride (relative molecular mass = 148). (See
1 OOOm, clause 6.)

4
 ISO 43274979 (E)

ANNEX B

MASS OF THE TEST PORTION, IN GRAMS, AS A FUNCTION OF I(OH) AND WATER CONTENT

Estimated
I(OH)
r 1 2 3 4 5 6
Water content,

7 8
% (m/m)

9 10 G-j-T 25

10 18
21
20 11,5
14 IO,3

30 80 7,O
IO,5 8,3 69
40 66 5,7 5,l
8,4 7,O 60 5,25

50 5,5 43 4,4 4,O

7,O 60 5,3 4,7 4,2
60 4,6 4,2 33 3,6 3,3
60 5,3 4,7 4,2 39
100 22 23 Z6 2,5 2,4
3,s 3,5 3,3 3,O 23 2,7
200 1,5
280
iTeh STANDARD
1,5
1 ,g lt6 PREVIEW
IR4
19
19
1 ,g
1,4
lt7
1,3
1 t-7
300 1,o
1,4
(standards.iteh.ai)
1 ,o
1,3
1 ,o
12 12
1,3
0,98
1,3
0,96
12
0,95
12
0,94

400 0,77 0,76 0,75 0,75 0,74 0,74 0,73 0,73

1 ,o 1 ,o 1 .o ISO0,96
0,98 4327:1979
0,94
0,97 0,93 0,92

500 https://standards.iteh.ai/catalog/standards/sist/7e03b4c9-9bd1-492e-b1b2-
0,61 0,61 0,61 0,60 0,60 0,60 0,60 0,60 0,60
0,83 0,82 0,81 35804d9b04fc/iso-4327-1979
0,80 0,80 0,79 0,78 0,77 0,76 OJ6

600 0,51 0,51 0,51 0,51 0,51 0,51 0,51 0,51 0,50 0,50
0,69 0,69 0,68 0,68 0,68 0,67 0,67 0,66 0,66 0,65 0,63

700 0,44 0,44 0,44 0,44 0,44 0,44 0,44 0,44 0,44 0,44 0,44
0,59 0,59 0,59 0,59 0,59 0,58 0,58 0,58 0,57 0,57 0,56 0,55

800 0,39 0,39 0,39 0,39 0,39 0,39 0,39 0,39 0,39 0,39 0,39 0,39
0,52 0,52 0,52 0,52 0,52 0,52 0,51 0,51 0,51 0,51 0,50 0,49 0,49

1 000 0,31 0,31 0,31 0,31 0,31 0,31 0,32 0,32 0,32 0,32 0,32 0,33 0,33
0,42 0,42 0,42 0,42 0,42 0,42 0,42 0,42 0,42 0,42 0,42 0,42 0,42 0,41 0,41 0,41

1 100 0,28 0,28 0,28 0,28 0,28 0,29 0,29 0,30 0,29 0,29 0,29 0,30 0,30 0,31 0,32 0,32
0,38 0,38 0,38 0,38 0,38 0,38 0,38 0,38 0,38 0,38 0,38 0,38 0,39 0,39 0,39 0,39

Example : For a Sample with an estimated hydroxyl value of between 100 and 200, the mass of the test Portion will depend
on the water content as follows :

a) if the water content is 1 % (m/m), take a test Portion of between 2,9 and 20 g;
b) if the water content is 4 % (m/m), take a test Portion of between 2,5 and 1,9 g;
c) if the water content is IO % (m/m), the table does not indicate a mass of test Portion; it is necessary to eliminate part
of the water, which tan be left at a maximum of 5 % (m/m), and then between 2,4 and 1,7 g of the Sample tan be taken.
ISO 4327-1979 (E)

ANNEX C

SPECIAL METHOD APPLICABLE WITHOUT FUME HOOD

C.0 INTRODUCTION C.2.3 Determination

This annex specifies a special apparatus and a special proce- C.2.3.1 Esterification
dure for the determination of hydroxyl value for the case
where the determination has to be carried out outside a Introduce exactly 25,0 ml portions of the phthalation
ventilated fume hood. reagent (7.2) from the special burette (C.1.7) into the flask
through the central hole of the stopper (C.1.5).

C.l APPARATUS (See figure 1) Fit the flask onto the Iower end sf the condenser, i.e. in the
place of the flask which was used to collect the pyridine
Ordinary laboratory apparatus and : washings. Then close this flask, using a stopper (C.1.4) at
the upper end of the condenser.
C.l.l Burette, capacity 50 ml, complying with the require-
ments of class A of ISO/R 385. Heat the flask, fitted with its condenser, at gentle reflux
for 1 h. Allow to cool to room temperature.

C.1.2 Flat-bottomed flasks, capacity 250 ml, with conical

ground glass joint. C.2.3.2 Hydrolysis and titration

Rinse the condenser with the pyridine (7.1) from the

C.l.3 Condensers, of effective length 400 mm, with rinsing test tube (C.1.8).
conical ground glass joints, fitting the flasks (C.l.2), and
with drip collectors (see figure 2). iTeh STANDARD PREVIEW Remove the flask from
glass joints with distilled
its condenser and rinse the ground
water from a wash bottle.
C.l.4 Ground glass Stoppers fitting (standards.iteh.ai)
the flasks (Cl .2). Refit the flask containing the initial rinsing pyridine to the
condenser and close the condenser using a solid stopper
C.1.5 Ground glass Stoppers fitting the flasks (C.l.2), ISO 4327:1979
(C.l.4).
with central holes [see figure 1 a)].https://standards.iteh.ai/catalog/standards/sist/7e03b4c9-9bd1-492e-b1b2-
Place a bar magnet in the flask. Fit the stopper with central
35804d9b04fc/iso-4327-1979
hole and side-arm (Cl .6) to the flask. Attach the side-arm
6.1.6 Ground glass Stoppers fitting the flasks (C.l.2),
to a vent by means of rubber tube (in Order to avoid release
with central holes and side-arms [see figure 1 b)].
of pyridine into the Iaboratory atmosphere): Place the
assembly on the magnetic stirrer and switch on the stirrer.
C.1.9 Special burette, capacity 25 ml [see figure 1 c)].
Introduce exactly 50,O ml of the Standard volumetric
C.1.8 Rinsing test tubes, capacity 200 ml [see figure 1 d)]. sodium hydroxide Solution (7.3) through the central
opening of the stopper, from the burette (C.1.1).

C.2 PROCEDURE Add, by means of a 1 ml pipette, again through the central

hole in the stopper, 4 to 5 drops of the phenolphthalein
Solution (7.4).
C.2.1 Preparation of the apparatus
Continue the titration with the Standard volumetric sodium
All the necessary apparatus shall be absolutely clean and
hydroxide Solution (7.3) until the Solution remains pink for
dry.
15 s.
Rinse the condensers (C.l.3) in succession, using the rinsing
Record the volume of the Standard volumetric sod ium
test tubes (C.1.8) with about 10 ml of the pyridine (7.1),
hydroxide solution (7.3 used for the titration of the test
collecting the washings in the flasks (C.1.2).
Solution.
After rinsing, close the tops of the condensers with one of
the Stoppers (C. 1.4).
Carry out two simul t aneous determinations on two
different test portions.
Fit a stopper (C.1.5) on the flask (C.l.2) reserved for the
test Portion and weigh to the nearest 0,001 g. C.2.4 Blank tests

See 10.3.
C.2.2 Test Portion

Remove the stopper (C.1.5). Place the test Portion (10.1) in

the flask (C.1.2) reserved for this purpose. Refit the stopper C.3 EXPRESSION OF RESULTS
(C.1.5). Reweigh the assembly to the nearest 0,001 g. Let
m. be the mass, in grams, of the test Portion. See clause 11.

6
 ISO 4327-1979 (E)

w-___.
~-
_--
--
Ia (29132)
for example

t
for exam Ne

a) Ground glass stopper (C.1.5) b) Ground glass stopper (Cl.61

Dropping funnel

Plastic tube 1
Capillary tube

iTeh STANDARD PREVIEW 7

ml
(standards.iteh.ai)
0 ml ISO 4327:1979 -.-
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35804d9b04fc/iso-4327-1979 --- -
-.-

25 ml

Capillary hole

for example-
c ! 1I
@ext. 14mmJ j_

c) Special burette (C.1.7) d) Rinsing test tube (C.1.8)

FIGURE 1 - Apparatus