CHARACTERIZATION OF CATIONIC

SURFACTANTS
I. DESCRIPTION AND TYPICAL
SPECIFICATIONS
A. ALKYL QUATERNARY AMMONIUM SALTS
1. Description:
2. Typical Specifications
B. BENZYLALKYLDIMETHYLAMMONIUM SALTS
1. Description
2. Typical Specifications
C. AMIDOAMINE QUATERNARIES
1. Description
2. Typical Specifications
D. QUATERNARY IMIDAZOLIUM COMPOUNDS
1. Description
2. Typical Specifications
E. ESTER QUATS
1. Description:
2. Typical Specifications
II. GENERAL TEST METHODS
GENERAL TEST METHODS
A. Assay
 Quaternary amines may be assayed by titration with an
anionic surfactant by the potentiometric or two-phase
procedures.
 The ISO procedure specifies titration with sodium
dodecyl sulfate, which is available in high purity (7).
 Sodium tetraphenylborate may also be used if potassium
and ammonium ions are absent.
B. ACID-BASE TITRATION
1. General Considerations

 Quaternary amine salts may be titrated with acid by

conventional nonaqueous procedures.
 In the case of halides, mercuric acetate is added to
replace free halide ion with easily titratable acetate
ion.
 A more specific assay of cationic surfactants is the
two-phase titration with an anionic surfactant.
2. ACID VALUE
3. AMINE VALUE
C. IODINE VALUE
 The usual procedure for determining
unsaturation in quaternaries is the Wijs method,
described in Chapter 2.
 The ASTM test optimized for determination of
unsaturation of the alkyl group in fatty
quaternary ammonium chlorides is D2078 (12).
 The corresponding AOCS method is Tg 3a-64
(11). For other compounds, the recommended
AOCS method is Cd 1-25 (13).
D. ANIONS AND SALTS
Procedure: Determination of Halide, Sulfate, p-
Toluenesulfonate and Methyl Sulfate Ions in
Quaternary Compounds by Ion Chromatography

Procedure: Determination of Mono- and

Dichloroacetic acid in Betaines and Formulations
by Gas Chromatography
E. ALKYL CHAIN LENGTH DISTRIBUTION
The homolog distribution of the fatty alkyl portion
of surfactants such as the lkyltrimethylammonium
chlorides and the benzylalkyldimethylammonium
chlorides is determined by HPLC or, after propriate
decomposition of the sample, by GC.
F. N-NITROSAMINES
Cationic surfactants are generally free of . N-
nitrosamines, those used in cosmetics may
casionally be analyzed by the method for total
nitrosamines described under characterization of
nonionic surfactants
III. ANALYSIS OF INDIVIDUAL
SURFACTANTS
A. Fatty Quaternary Ammonium Salts
1. Average Molecular Weight
The ASTM and AOCS standards specify
determination of molecular weight by titration
after addition of mercuric acetate. Mercuric ion
complexes halides, resulting in the replacement of
halide ions in solution with acetate ion. Acetate is
titrated potentiometrically with perchloric acid in
acetic acid solvent
2. UNREACTED PRIMARY AND SECONDARY
AMINES
Amines may be reacted with carbon disulfide to
form the dithiocarbamic acids, which are titrated
potentiometrically with base
3. MONO-, DI-, AND TRIALKYLAMMONIUM
COMPOUNDS
HPLC methods are the most convenient for
determining, for example, monoalkyltrimethyl- and
trialkylmethylammonium chloride impurities in
dialkyldimethylammonium chloride
B. BENZYLALKYLDIMETHYLAMMONIUM SALTS
 The compendial method for assay of enzalkonium
chloride is based upon reversal of the quaternization
reaction
 Quats made from reaction of benzyl chloride with
tertiary amines potentially contain residual benzyl
chloride
C. QUATERNARY IMIDAZOLINIUM COMPOUNDS
 These compounds are readily titrated with nionic
surfactants, either according to the twophase
method or to the potentiometric end point, as
discussed in Chapter 16.
 Alcohol is added as necessary for solubility (19).

 Determination of the alkyl chain length

distribution may be performed directly, by HPLC,
or after liberation of the fatty acids, by GC.
D. ESTER QUATS
 Fabric softeners based on quaternized triethanolamine
esters of long-chain fatty acids can be analyzed by HPLC,
 These compounds can be titrated with anionic surfactants,
but special care is necessary to minimize hydrolysis during
the analysis
 NMR analysis can give the gross characterization of the
material, including the average composition in terms of
alkyl chain length, unsaturation, ester number, and degree
of quaternization
 Ester quats may be separated using a silica solid phase
extraction cartridge into fractions consisting of
unquaternized triesteramine, mixed triesterquat
/diesteramine/ diesterquat, diester quat, and monoester
quat