Escolar Documentos
Profissional Documentos
Cultura Documentos
ABSTRACT: The effect of different alkyl chains of anionic Surface tension measurements. Surface tension was measured
surfactants on properties of binary anionic-nonionic mixed using a Du Nouy ring tensiometer (type 8451 Krüss; Hamburg,
surfactant systems was studied. These systems included octyl-, Germany) with platinum ring at fixed temperature (25°C).
dodecyl-, and cetylsulfoacetates mixed with isooctyl phenol Preparation of mixed surfactant solutions. Doubly distilled
nonyl ethoxylate. The critical micelle concentration of mixed water from all-glass apparatus was used to prepare all solu-
surfactants shifted to lower values compared to those of the
tions. Surface tension of water was 72.8 dyne cm−1 at 25°C.
single anionic surfactants. Effectiveness values increased with
Into several 100-mL beakers, aliquots of a given concentra-
decreases in the mole fraction of anionic surfactants. The neg-
ative values of interaction parameter (β) increased with in- tion of anionic surfactants (1 × 10−2 mol/L) were placed,
creases in the chain length of anionic surfactants. followed by the addition of a given concentration of isooctyl
Paper no. S1210 in JSD 4, 293–296 (July 2001). phenol nonyl ethoxylate (1 × 10−2 mol/L). The mixtures
were diluted stepwise with water. These mixtures were
KEY WORDS: Alkyl-sulfoacetates, binary mixed surfactants, stirred for 30 min under thermostatted conditions at 30°C
interaction parameters. in order to establish equilibrium.
Copyright © 2001 by AOCS Press Journal of Surfactants and Detergents, Vol. 4, No. 3 (July 2001) 293
294 E.M.S. AZZAM
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