16

Utration of Surfactants

The most useful methods for volumetric determination of ionic surfactants are based on
titration of an anionic surfactant with a cationic surfactant or the titration of a cationic
surfactant with an anionic surfactant. In general, equivalent results are obtained by pouring
the sample into the buret and using it to titrate a precisely known quantity of a standard
solution of opposite charge. Thus, the methods given below for determination of anionics
and determination of cationics are to a great extent interchangeable with each other; the
reader should study both sections to appreciate the choices available for the analysis.
Reiner Schulz has written a wonderfully clear book on surfactant titrations. Anyone
able to read German is urged to study that work, which contains a wealth of practical
knowledge (1).

I. ANIONIC SURFACTANTS
A. Introduction
Titrimetric methods were the first procedures to be widely applied to the analysis of an-
ionic surfactants and they remain very useful for assay purposes. Their speed and low cost
make them especially suitable for quality control. Cross has written a thorough and recent
discussion of the titration of anionic surfactants (2)

490
Titration of Surfactants 491

1. Acid-Base Titration
Most anionic surfactants are salts of moderately strong acids. As such, they can be titrated
directly with base, provided that a suitable solvent system and visual or instrumental end
point can be found. However, since anionic surfactants are generally found in the company
of other ionic materials, some of them also acidic, direct acid-base titration is not used for
most applications. For example, acid-base titration for assay of alkylarylsulfonate would
risk high results because of titration of byproduct sulfate or other ions. Acid-base titration
of LAS in a detergent formulation suffers from interference from such buffering com-
pounds as sodium silicate and sodium tripolyphosphate. Titration with alkali is therefore
limited to cases where the anionic surfactant can be isolated in pure form.
Simple acid-base titration may be used for the characterization of pure anionics (3).
This approach is most often applied to nonaqueous titration of fatty acid soap (4). Colored
indicators may be used, although potentiometric titration is generally preferred. In this ap-
proach, the free fatty acids are solubilized in acetone with excess HC1. Conventional non-
aqueous titration with tetrabutylammonium hydroxide solution neutralizes first the excess
HC1, then the total fatty acid. Care is required to characterize the sample well enough to
assure that interference from other detergent components does not occur.
Soap can be determined in mixture with oil or ester-type nonionic emulsifiers by
nonaqueous titration. The solvent system is 15:5 acetic acid/benzene, with crystal violet
indicator. The soap is titrated with HBr in glacial acetic acid. If compounds are present
which react with HBr, such as epoxides, the alkali metal cations are first extracted into
acetic acid from amyl acetate/«-butanol solution and then titrated with HBr. In either case,
the procedure is not specific for soap; any alkaline component can be expected to
interfere (5).
2. Precipitation Titration
Titration is usually performed with a cationic surfactant to form a water-insoluble ion pair.
This technique has the advantage of being selective for ionic molecules with nonpolar
"tails," i.e., those with classical surfactant structure. A few years ago, the most popular
method for determination of anionic surfactants was two-phase titration with benzetho-
nium chloride. This has very rapidly been replaced by one-phase titration with potentio-
metric end point. Several vendors provide PVC membrane electrodes suitable for
potentiometric titration of ionic surfactants.

B. Two-Phase Titration
Two-phase titration with a cationic surfactant was the most common method for determi-
nation of anionics from about 1950-1990. The technique remains in wide use and is incor-
porated into many national and international standards.
1. The Standard Method
The titration is based on the reaction of anionic surfactants with cations, normally large
cationic surfactants, to form an ion pair. With the ionic charges neutralized, the ion pair
has net nonpolar character, much more lipophilic than either free ion. In a two-phase sys-
tem the ion pair is therefore extracted continually into the organic phase as it is formed.
The reaction is monitored by addition of a water-soluble cationic dye, dimidium bromide,
and a water-soluble anionic dye, disulphine blue. The cationic dye forms an extractible ion
pair with the anionic surfactant, coloring the organic phase a pink hue. At the end point,
492 Chapter 16

the cationic titrant displaces the dye and the pink color leaves the organic phase. Further
addition of titrant carries the blue anionic dye into the organic phase. Thus, the end point is
indicated by a color change from pink to blue in the organic phase. This version of the
two-phase titration has become the standard method, a thorough study of which has been
written by Reid, Longman, and Heinerth (6-9).
The procedure is suitable for determination of anionic surfactants in concentrates
and in detergent formulations and is used for assay of alkyl aryl sulfonates, alkyl sulfates,
sulfated APE and AE, and sulfosuccinates. As described in Chapter 1, alkane monosul-
fonates require special precautions. Phosphate surfactants will generally not be deter-
mined. Since the analysis is conducted at pH 2, soap is not determined. Hydrotropes in
low concentrations do not interfere, nor do most other detergent constituents.
Procedure: Assay of an Anionic Surfactant by Two-Phase Titration (6)
Reagents:
Benzethonium chloride (Hyamine 1622) is available from chemical supply houses.
A 0.004 M solution is prepared in water and standardized against sodium lauryl
sulfate.
Mixed indicator solution is prepared by dissolving separately 0.5 g dimidium bro-
mide and 0.25 g disulphine blue in warm 10:90 ethanol/water. Mix and make up
to 250 mL with 10:90 ethanol/water. Transfer 20 mL of this solution to a 500-mL
volumetric flask, add 50 mL 1 N H2SO4, and dilute to volume with water.
Weigh a sample sufficient to give about 1 meq of anionic surfactant. For an un-
known, an equivalent weight of 360 may be assumed. Dissolve in about 100 mL water and
neutralize to phenolphthalein with 1 N NaOH or H2SO4, as required. Transfer to a 250-mL
volumetric flask, dilute to volume, and mix well. Transfer a 20-mL aliquot to the titration
vessel, which is a 100-mL graduated cylinder fitted with a ground glass stopper. Add 10 mL
water, 15 mL methylene chloride, and 10 mL indicator solution. Titrate with the benzetho-
nium chloride solution, shaking well after each addition of titrant. The end point occurs
when the pink color is completely discharged from the methylene chloride layer, which is
then a faint blue.
Notes: (a) In letters to several journals during 1995-1996, Professor Norbert Busch-
mann suggested that dimidium bromide may have mutagenic properties and that its solu-
tions should therefore be handled with all appropriate precautions, (b) Mettler has developed
titration accessories which allow this analysis to be performed automatically (10).
2. Modifications to the Standard Procedure
The precipitation titration has been studied extensively, particularly by Buschmann (11).
Sources of error include solubility of the ions at the equivalence point, which is influenced
by formation of micelles. Micelle formation is influenced by the presence of solvents and
salts in the system. A vast number of modifications have been suggested by various au-
thors, based on greater or lesser understanding of the principles at work.
(a) Indicator. Many ionic dyes have been proposed as indicators for the titration. The
first widely-used version of the two-phase titration method, sometimes called the "Epton
method," employed as indicator a single water-soluble cationic dye, methylene blue. At
the start of the titration, the methylene blue salt of the anionic surfactant is extracted into
the organic phase, where it remains until the methylene blue ion is gradually displaced
from the complex by the cationic titrant. The end point has been demonstrated to be at the
Titration of Surfactants 493

point where the blue color of the aqueous and organic phases is of equal intensity. (12,13)
This end point is somewhat indistinct and the methylene blue method is sensitive to inter-
ference from chloride and other anions. The cationic dye dimethyl yellow is said to give a
sharper end point than the standard mixed indicator. Since the dye has low water solubil-
ity, the aqueous phase remains nearly colorless, and the organic phase changes sharply
from red to yellow at the end point, as the dye responds to the change in its environment
(14,15). The cationic dye safranine T is used for assay of alkylethercarboxylates at pH 8.6,
taking as the end point the titrant volume when the color intensity of each phase is the
same (16).
Replacement of the acidic titration medium with a basic medium has been suggested
as a way to minimize the interference of weakly cationic surfactants, such as amine ox-
ides, which are not ionized at higher pH (17). Titration under these conditions allows de-
termination of soap (18,19). Since cationic dyes do not generally retain their ionic
character at high pH, an anionic dye, such as bromcresol green or bromophenol blue, is
used as indicator. With such a system, the color remains in the aqueous phase until the end
point, when it is extracted into the organic layer. (The dimidium bromide/disulfine blue
mixed indicator may also be used in alkaline conditions, but the color change is different
and less sharp than when used in acid solution.)
If interference from soap is not a problem, anionic dyes have certain advantages
over the cationic dyes as indicators. With tetrabromophenolphthalein, ethyl ester, the need
for color-matching of the phases is avoided. During the titration, the aqueous phase re-
mains colorless, while the organic phase changes sharply from yellow to blue at the end
point (20). Similarly, thymolphthalein is recommended for the titration of acylsarcosines
at high pH (21). Phenol red gives quantitative results for titration of tetrahydronaphthalene
sulfonate as well as surfactants, while with bromcresol green, only the surfactants are ti-
trated (22). Use of phenol red in conjuction with titration at pH 9-10 permits determina-
tion of both carboxylate and sulfonate groups in an unesterified oc-sulfo fatty acid, while
use of methylene blue at lower pH allows titration of the sulfonate group alone (23); with
bromcresol green only the a-sulfo fatty acid ester is measured (24).
(b) Other end points. Instead of shaking the mixture after each addition of titrant, a
special stirred glass vessel resembling a Soxhlet extractor may be used for the titration.
Values obtained are comparable to the shaking method, with much less operator fatigue (25).
A turbidimetric end point has been found to make the two-phase titration easily au-
tomated (26). The indicator is omitted, and the titration is followed by monitoring the tur-
bidity of the aqueous phase, which suddenly increases at the end point. The titration is, in
other respects, similar to the standard method, although methanol is added to the system to
optimize end point detection. Hendry and Hockings found that the organic phase could be
omitted altogether, as described below under one-phase titration (27). Pinazo and Dom-
ingo performed a similar titration with only a small amount of chloroform finely dispersed
by stirring. In this case, the end point corresponds to an inflection point on the turbidity
curve (28).
An automated two-phase titration may be conducted to a spectrophotometric end
point. Various researchers have demonstrated this technique with specially made glass
vessels or by using membranes to separate the aqueous and organic phases. Nowadays, the
manufacturers of automatic titrators supply equipment and optimized conditions to permit
this type of titration (1,29). Usually, the vessel is stirred after each increment of titrant,
then the phases are allowed to separate and the transmittance of the organic phase is deter-
494 Chapter 16

mined. Spectrophotometric methods are not used for most surfactant titrations, since the
single-phase potentiometric titration works quite well. They are used for special cases,
such as determination of polyelectrolytes.
As described below, the two-phase titration has been largely supplanted by aqueous
titration with a potentiometric end point. The aqueous titration fails for certain samples,
such as those containing oily material which fouls the electrode or those containing sur-
factants which do not form an insoluble ion pair with the titrant. Such problems can be
solved by going to a two-phase system but keeping the potentiometric end point detection
in the aqueous phase. Oil is extracted into the organic layer, as well as the ion pair formed
during the titration. At the end point, the electrode responds to the increase in concentra-
tion of the titrant in the organic phase. It is essential that the electrode used be resistant to
organic solvents, a property not enjoyed by most commercial PVC-membrane surfactant-
selective electrodes. The best design is a coated-wire electrode made with plasticized PVC
containing a polymeric ionophore based on silicone (1).
(c) Titrant. Although most cationic surfactants will function as titrants, a compound is
usually chosen which consists of a single pure compound, rather than containing a range
of alkyl chain lengths like typical surfactant quaternary amines. The most frequently used
material is the disinfectant benzethonium chloride (often referred to by the Rohm & Haas
brand name, Hyamine® 1622). TEGO®trant A100 (l,3,-didecyl-2-methylimidazolium
chloride, available from Metrohm) is a commercially available alternative titrant which is
more hydrophobic than benzethonium chloride. This allows the formation of hydrophobic
ion pairs with anionics of shorter alkyl chain length than can be titrated with benzetho-
nium chloride. It also leads to sharper end points when using an electrode for end point
detection as discussed below.
In eastern Europe, a well-characterized disinfectant, Septonex (carbethoxypentade-
cyltrimethylammonium bromide), is sometimes used as titrant (14,15). Results are compa-
rable with benzethonium chloride. Benzyldimethyldodecylammonium bromide is also
suitable (30).
(d) Sample pretreatment by hydrolysis. Some classes of anionic surfactants are readily
hydrolyzed under acidic or basic conditions, while others are not. Procedures have there-
fore been developed to analyze surfactant mixtures by titration before and after hydrolysis.
Acid hydrolysis for 3 hours with 1 M sulfuric acid will decompose alkyl sulfates, alkyl
hydroxysulfates, alcohol ether sulfates, and alkylphenolether sulfates so that they no
longer respond to titration, while sulfonates are not affected (7,31-33). Alkaline
hydrolysis for 30 minutes with 2 M sodium hydroxide will saponify dialkylsulfosuccinates
and fatty acid glyceride sulfates so that they are no longer surface active and are not
titrated (34).
Saponification for four hours will decompose a-sulfo fatty acid methyl esters so that
they can no longer be titrated by the standard two-phase procedure, either in acidic or ba-
sic media. A one-hour saponification will cleave the ester, but will remove only about 20%
of the sulfonate group, so that these compounds are still titrated. Reflux with HC1 has no
effect. On the other hand, reflux with either acid or base will decompose fatty alcohol sul-
foacetates so that they are no longer titratible (35).
3. Extending the Application of Two-Phase Titration
The standard method is effective for determination of most detergent sulfonates and sul-
fates, as well as dialkylsulfosuccinates. Interference is not usually encountered from inor-
Titration of Surfactants 495

ganic anions, chelates, soap, or common hydrotropes (8). Other anionics, such as
phosphate esters, must be tested individually for applicability. Li and Rosen reported that
the standard method gives low recoveries (as low as 89%) for anionic surfactants with an
alkyl chain length less than C\2 (36). Complete recovery can be obtained by changing the
extraction solvent from chloroform to 40:60 chloroform/1-nitropropane, and by drawing
off the organic layer after the end point is reached, replacing it with fresh solvent, and
titrating to a second end point.
While the two-phase titration will not determine alkanedisulfonates if monosul-
fonates are absent, the presence of disulfonate impurities in commercial alkanesulfonate
products will cause a variable interference (37). The response of the two-phase titration to
molecules containing more than one sulfate or sulfonate group must be determined for
each individual case. Lew reports stoichiometric reaction with each functional group for a
€22 surfactant with two anionic sulfate groups separated by four carbon atoms (38). Wick-
bold suggests addition of 10 mL 20% sodium sulfate solution to eliminate interference
from disulfonates, and this was adopted in the ISO procedure (39). Alternatively, modifi-
cation of the organic solvent to a 93:7 chloroform/1-hexanol mixture will allow complete
recovery of disulfonates, regardless of pH (40).
Two-phase titration is effective in determination of diesters of sulfosuccinic acid,
whether the titration is conducted in acidic or basic medium. Results with monoesters are
variable due to their hydrophilic nature. Each product must be tested individually. Gener-
ally, half esters cannot be titrated in basic media and can be titrated in acid medium only if
they have good solubility in organic solvents (41).
By performing the titration twice, once at acidic and once at basic pH, soap can be
differentiated from synthetic anionic surfactants (18,40). Under acid conditions, only the
sulfate and sulfonate type surfactants are determined, while under basic conditions both
soap and synthetic surfactants are measured.
Most cationic surfactants interfere quantitatively with the titration of the anionics
because of their similarity in properties to the titrant. Their presence leads, therefore, to
low values. This is not generally a serious problem, because the antagonism of anionic and
cationic surfactants insures that they are rarely formulated together. If the level of anionic
surfactant is lower than that of the cationic, both components may be determined by titra-
tion of the cationic with tetraphenylborate (42). In this procedure, the total cationic is
titrated at pH 12.5, using 1,2-dichloroethane as the second phase and potassium tetra-
bromophenolphthalein, ethyl ester, as indicator. A similar titration is performed at pH 6.0,
giving a value for that amount of cationic which is not neutralized by the anionic surfac-
tant (which quantitatively interferes at the lower pH value). This procedure was developed
specifically for analysis of a hospital wastewater stream which contained anionic surfac-
tant as well as cationic biocides. A similar approach is used if the level of the cationic is
lower than that of the anionic (43). The sample is first titrated at pH 9.0 with cationic sur-
factant mixture, using ethylene dichloride as second phase and Victoria Blue B as indica-
tor. This value corresponds to the anionic surfactant not neutralized with cationic
surfactant. Another sample aliquot is then titrated at high pH with tetraphenylborate solu-
tion to give the total cationic concentration. The anionic concentration is calculated from
the sum of the two titrations.
Alkylbetaine amphoteric surfactants behave as cationics at pH 1, at which the stan-
dard two-phase titration of anionics is performed. Their presence thus leads to low results
for anionics (1).