Effect of Alkyl Groups in Anionic Surfactants on Solution
Properties of Anionic-Nonionic Surfactant System
Eid M.S. Azzam*
Applied Surfactants Laboratory, Petrochemicals Department, Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt
ABSTRACT: The effect of different alkyl chains of anionic
surfactants on properties of binary anionic-nonionic mixed
surfactant systems was studied. These systems included octyl-,
dodecyl-, and cetylsulfoacetates mixed with isooctyl phenol
nonyl ethoxylate. The critical micelle concentration of mixed
surfactants shifted to lower values compared to those of the
single anionic surfactants. Effectiveness values increased with
decreases in the mole fraction of anionic surfactants. The neg-
ative values of interaction parameter (β) increased with in-
creases in the chain length of anionic surfactants.
Paper no. S1210 in JSD 4, 293–296 (July 2001).
KEY WORDS: Alkyl-sulfoacetates, binary mixed surfactants,
interaction parameters.
Most surfactants used in practical applications are mixtures.
Hence, understanding both the structure and properties of
mixed micelles containing anionic and nonionic surfactants
is essential for many industrial uses of surfactants. Mixed
surfactant systems are also of great theoretical interest in
their own right. In solutions containing mixtures of surfac-
tants, the tendency to form aggregates is substantially dif-
ferent from that in solutions of single surfactants. It has
been reported that the effect of a mixed surfactant system
on surface activity is superior to that of a single surfactant
system (1–3). Various investigations covering different as-
pects of solution properties relevant to monolayers formed
by mixtures of ionic and nonionic surfactants have been
published (4–8). A number of solution properties have
been measured for mixed anionic-nonionic surfactants sys-
tems (9–11).
Our approach used Rubingh’s method (12) to calculate
the mole fraction, interaction parameters, and activity coef-
ficients of binary surfactant mixtures in micelles.
EXPERIMENTAL PROCEDURES
Materials. The anionic surfactants octyl-, dodecyl-, and cetyl-
sulfoacetates (A8, A12 and A16) were prepared as reported
previously (13). The nonionic surfactant isooctyl phenol
nonyl ethoxylate [9 moles ethylene oxide (EO)] used in this
study was supplied by the Hüls Company, Germany.
*E-mail: eazzamep@yahoo.com
Copyright © 2001 by AOCS Press Journal of Surfactants and Detergents, Vol. 4, No. 3 (July 2001)
Surface tension measurements. Surface tension was measured
using a Du Nouy ring tensiometer (type 8451 Krüss; Hamburg,
Germany) with platinum ring at fixed temperature (25°C).
Preparation of mixed surfactant solutions. Doubly distilled
water from all-glass apparatus was used to prepare all solu-
tions. Surface tension of water was 72.8 dyne cm−1 at 25°C.
Into several 100-mL beakers, aliquots of a given concentra-
tion of anionic surfactants (1 × 10−2 mol/L) were placed,
followed by the addition of a given concentration of isooctyl
phenol nonyl ethoxylate (1 × 10−2 mol/L). The mixtures
were diluted stepwise with water. These mixtures were
stirred for 30 min under thermostatted conditions at 30°C
in order to establish equilibrium.
RESULTS AND DICUSSION
Change of critical micelle concentration (CMC) and effectiveness
with mole fraction under a constant total concentration. The sur-
face tension of single nonionic nonyl phenol ethoxylate,
single anionic surfactants (A8, A12, and A16), and mixed
nonionic with anionic surfactants at different mole frac-
tions (0.2–0.8) are plotted against the total concentrations
(5 × 10−6 to 1 × 10−2 mol/L) in Figures 1–3.
In the case of single anionic and single nonionic systems,
surface tension value decreased with increases in concen-
tration, but remained constant above the CMC. The surface
tension values of solutions of mixed surfactants in various
mole fractions decreased with increasing total concentra-
tion. The CMC of mixed surfactant shifted to lower values
compared to that of single anionic surfactants. The CMC
values also decreased with increases in the alkyl chain
length of anionic surfactants as shown in Tables 1–3.
Effectiveness of surface tension reduction has been de-
fined as the solution phase concentration required to pro-
duce the maximal surface tension reduction. Tables 1–3
show the effectiveness values of anionic surfactants mixed
with nonionic surfactants. Mixing 0.2 mole fraction of octyl-
sulfoacetate A8 with nonionic surfactant resulted in the best
effectiveness (42.1 dyne cm−1) with minimum total concen-
tration. The effectiveness values in Tables 1–3 increased
with decreases in the mole fraction of anionic surfactants in
the mixed systems.
Micellar mole fraction of surfactant mixtures. The micellar
mole fraction of anionic surfactants in a mixed surfactant
293
294
FIG. 1. Variation of surface tension vs. concentration of single anionic
surfactant A8 (a), single nonionic surfactant (b), and the mixed anionic
with nonionic at 0.8 (c), 0.6 (d), 0.4 (e), and 0.2 (f) mole fractions at
25°C.
solution can be expressed by the following equation, sug-
gested by Rubingh (12):
−(C − ∆ ) + [(C − ∆ ) 2 + 4YC∆ ]1 / 2
Xm =
2∆
where Xm = micellar mole fraction of anionic surfactants, C
= total concentration (1 × 10−2 mol/L), Y = mole fraction of
FIG. 2. Variation of surface tension vs. concentration of single anionic
surfactant A12 (a), single nonionic surfactant (b), and the mixed anionic
with nonionic at 0.8 (c), 0.6 (d), 0.4 (e) and 0.2 (f ) mole fractions at 25°C.
Journal of Surfactants and Detergents, Vol. 4, No. 3 (July 2001)
E.M.S. AZZAM
[1]
FIG. 3. Variation of surface tension vs. concentration of single anionic
surfactant A16 (a), single nonionic surfactant (b), and the mixed anionic
with nonionic at 0.8 (c), 0.6 (d), 0.4 (e) and 0.2 (f) mole fractions at 25°C.
anionic surfactants in mixed solution, and ∆ = the differ-
ence between the two CMC of single anionic and single
nonionic surfactants. Tables 4–6 show that the micellar
mole fraction of anionic surfactants in the mixed system in-
creases with increases in the initial mole fraction (Y) when
the total surfactant concentration is held constant at 1 × 10−2
mol/L.
The interaction parameter (β). The surface parameter equa-
tion of the regular solution approximation for nonideal
mixing surfactants in micelles utilized by Rubingh is applied
by calculating the interaction parameter between two or
more surfactant components using the following equation
(6):
ln(CM Y / CM1 X m )
β= [2]
(1 − X m ) 2
where CM = CMC of mixed surfactants and CM1 = CMC of
single anionic surfactant. From Equation 2, β is a measure
of the deviation of the mixture from ideality and is related
to molecular interaction between anionic and nonionic sur-
factants.
As shown in Tables 4–6, all β values were negative, rang-
ing from −0.6 to −20.6, and the negativity increased with in-
creases in alkyl chain length of the anionic surfactants. This
indicated that the synergism between anionic and nonionic
systems increased with increase in hydrophobic moiety of
the anionic surfactants. The greater synergism was observed
 EFFECT OF ALKYL GROUPS IN ANIONIC SURFACTANTS 295

TABLE 1 TABLE 4
CMC and Maximum Effectiveness of Single A8, Single Nonionic, Mole Fractions, Interaction Parameters, and Activity Coefficients
and Mixed A8 with Nonionic at 25°C in Micelles of Mixed A8 with Nonionic Surfactant
Maximum Mole
effectiveness fraction Y Mole
Solutions CMCa (mol/L) (dyne cm−1) of A8 in fraction in Interaction
Single A8 3.5 x 10−3 26.6 mixed micelles parameters Activity coefficients
Single nonionic 1.5 × 10−3 31.6 surfactants (Xm ) β f1 f2
Mixtures (mol fraction Y of A8 surfactant solution)
0.2 0.24 −0.62 0.699 0.964
0.8 2.5 × 10−3 34.6
0.4 0.45 −1.39 0.657 0.755
0.6 5 × 10−3 37.6
0.6 0.65 −2.26 0.758 0.385
0.4 6 × 10−3 40.6
0.8 0.83 −12.92 0.688 0.0001
0.2 6 × 10−3 42.1
a
CMC, critical micelle concentration.

TABLE 5
Mole Fractions, Interaction Parameters, and Activity Coefficients
in Micelles of Mixed A12 with Nonionic Surfactant
TABLE 2
CMC and Maximum Effectiveness of Single A12, Single Nonionic, Mole
and Mixed A12 with Nonionic at 25°C fraction Y Mole
of A12 in fraction in Interaction
Maximum
effectiveness mixed micelles parameters Activity coefficients
Solutions CMCa (mol/L) (dyne cm−1) surfactants (Xm ) β f1 f2
Single A12 1 × 10−3 27.6 0.2 0.21 −2.5 0.21 0.896
Single nonionic 1.5 × 10−3 31.6 0.4 0.41 −3.9 0.257 0.519
Mixtures (mol fraction Y of A12 surfactant solution) 0.6 0.61 −5.9 0.407 0.111
0.8 2 × 10−3 34.6 0.8 0.81 −18.8 0.507 4 × 10−6
0.6 2.5 × 10−3 37.1
0.4 4 × 10−3 38.1
0.2 5 × 10−3 40.6 tions 3 and 4 show that the activity coefficients are directly
a
CMC, critical micelle concentration. related to both the interaction parameter of mixing (β) and
the micellar mole fraction (Xm) of anionic surfactants.
Activity coefficients are less than unity, owing to interac-
tion between anionic and nonionic surfactants as in Tables
between the nonionic and the synthesized cetylsulfoacetate 4–6. Increases in the attraction or repulsion forces between
at a 0.8 mole fraction of anionic surfactant. The β values various molecules in the mixed systems change the activity
also increased with increases of the anionic micellar mole coefficients of the components. The activity coefficient (f1)
fraction. of a component achieves unity only when the mole fraction
Activity coefficients (f1,f2). Activity coefficients were calcu- (Xm) is equal to 1. In a binary system, the main nonideal ef-
lated as defined by Rosen and Hua et al. (6) in Equations 3 fects attributable to the constituent activity coefficients are
and 4: due to the change in the electrostatic repulsion energy of
the head groups. It was observed from Tables 4–6 that the
f1 = exp β (1 − Xm)2 [3]
activity coefficient of anionic surfactants f2 decreased with
f2 = exp β (Xm)2 [4] increase in the micellar mole fraction (Xm). This is due to
the attraction forces between the hydrophilic groups of
where f1 is the activity coefficient of the nonionic surfactant mixed surfactants. The high value of f2 was obtained from
and f2 is the activity coefficient of anionic surfactant. Equa- the mole fraction (0.2) for A8 compound which also gave
the greatest effectiveness (42.1 dyne cm−1).
TABLE 3
CMC and Maximum Effectiveness of Single A16, Single Nonionic,
TABLE 6
and Mixed A16 with Nonionic at 25°C
Mole Fraction Interaction Parameters, and Activity Coefficients
Maximum in Micelles of Mixed A16 with Nonionic Surfactant
effectiveness
Mole
Solutions CMCa (mol/L) (dyne cm−1)
fraction Y Mole
Single A16 2.5 × 10−4 24.6
of A16 in fraction in Interaction
Single nonionic 1.5 × 10−3 31.6
mixed micelles parameters Activity coefficients
Mixtures (mol fraction Y of A16 surfactant solution)
0.8 5 × 10−4 33.6 surfactants (Xm) β f1 f2
0.6 1.5 × 10−3 33.6 0.2 0.22 −1.53 0.395 0.927
0.4 8 × 10−4 34.1 0.4 0.43 −3.36 0.336 0.537
0.2 6 × 10−4 34.6 0.6 0.63 −12.7 0.176 0.006
a
Critical micelle concentration 0.8 0.82 −20.6 0.531 9 × 10−7

Journal of Surfactants and Detergents, Vol. 4, No. 3 (July 2001)

296 E.M.S. AZZAM
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[Received July 26, 2000; accepted April 17, 2001]
Dr. E.M.S. Azzam, researcher of petrochemicals, is a member of the
Egyptian Petroleum Research Institute. His research interests are in
the physicochemical properties and applications of surfactants.