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Floculantes Anionicos Cationicos
Floculantes Anionicos Cationicos
1065
Copyright @ 1992 by the American Chemical Society and reprinted by permission of the copyright owner.
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Ce~S MOLEfRACTION 3
RESIDUAL SURFACTANT CONC kmol/m
Figure 2. Measuredcmc and theoretical cmc calculatedfrom Figure (. Adsorption of C.. benzenesulfonate and C1zEOealcohol
ideal mixing and regular mixing for Ca-benzeneaulfonate
and from mixtures at initial composition of 50 mol % sulfonate-50
ClzEOealcoholand mixtures as a function of composition. mol % alcohol as a function of individual residual surfactant
concentrationa: (a) adaorption of 100% Crbenzeneaulfonate. (b)
p-octylbenzenesulfonate (CsPhS) are given in Figure 1. adsorption of 100% C'2EOs alcohol; 50 °C; 0.03 M NaCI.
Surface activity is greater for the nomonic species and
decreases as the percentage of sulfonate is increased. cohol (CI2EOs) on alumina are given in Figure 3. The
Critical micelle concentrations of the mixtures determined shape of CsPhS adsorption isotherm is typical of that
by surface tension measurements plotted in Figure 2 as obtained for long-chain alkanesulfonates on mineral
a function of surfactant composition suggests a regular oxides.I. Above a concentrationof 4.5 x lQ-4 kmol/m3,
solution behavior with an interaction parameter of -3.5. hemimicellization occurs and this region of accelerated
Literature values for the interaction parameter between adsorption extends to a concentration of 6.5 x 10-3kmol/
ethoxylated alcohols and anionic surfactants range from m3,which corresponds to the critical micelle concentration
-2 to -511-13and the interaction parameters for the present (cmc). Compared to the adsorption of sulfonate, the
system are within this range. plateau adsorption level of the nonionic Cl2EOa is more
The adsorption isotherms of sodium p-octylbenzene- than 3 orders of magnitude lower. It is apparent that
sulfonate (CsPhS) and dodecyloxyheptaethoxyethyl al- hemimicellization doesnot occur in this system, as a region
of accelerated adsorption is absent.
(11) Rosen,M.J.;Hua,X. Y.J.Am.0iIChem.Soc.198Z,59,S&.DI68. Figure 4 shows the isotherms for adsorption of sodium
(12) Oebome-Lee, I. W.; Schechter, R. S.; Wade, W. H.; Barakat, Y.
J. Colloid Interface Sci. 1985,108,60. p-octylbenzenesulfonate (CsPhS) and dodecyloxyhepta-
(13) Holland. P. M. In Structure! Performance Relotionships in Sur-
factant.; ACS Sympoeium Series 253; Rosen, M. J., Ed.; American (14)Somaaundaran,
P.; Fuerstenau,D. W. J. Plays.Chem.1*,70,
Chemical Society: Washington, DC, 1984; pp 141-151. 90.
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Coadsorption of Surfactant Mixtures Langmuir, Vol. 8, No.4, 1992 1067
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and 26 mol % alcohol are given in Figure 6. The general Ficare 7. Surface tension VB total surfactant concentration for
shape of the curves and relative surface activities are mixtures of Ca-benzenesulfonate and C12EOa alcohol before and
after contact with alumina: initial molar composition 74 mol %
similar to the results discussed above for the 1:1 system.
sulfonate-26 mol % alcohol; 50 °C; 0.03 M NaCI.
However, one striking feature of this system is the increased
curvature of the alcohol adsorption isotherm. The slope additional nonionic surfactant to reduce electrostatic
changes sign between 2 x 10-5and 3 X 10-5kmol/m3 and repulsion, such that the concentration of the nonionic C1r
residual concentrations are reduced to 1 X 10-5 kmol/m3 EOs can actually decrease.
before the onset of adsorption plateau. The surface tension Component adsorption isotherms for 24 mol % sul-
results obtained with the solutions after contact with the fonate/76 mol % alcohol compositions are given in Figure
mineral clearly support these results. The maximum in 8. It is apparent that the relative surface activities of the
surface tension asshown in Figure 7 is causedby the excess species are closer to each other and the slope of the
depletion of the alcohol from solution. A similar trend is adsorption isotherm le88 than those of the two mixtures
alsoapparent in Figure 5 for the 50 mol % sulfonate system, discussed previously. The reason for these differences
but to a much lesser extent. Such behavior indicates an becomesobvious upon examining the surface tension curve
increase in the adsorption energy of the nonionic species of this system given in Figure 9. Surface tension results
relative to that of the anionic one. As adsorption of sul- show the cmc to be below 1 x 10-' kmol/m3, which cor-
fonate increases, the surface becomes more negative and responds to a point in the initial hemimicellar region.
further adsorption of sulfonate becomesunfavorable. The Therefore, adsorption through most of the concentration
change in the curvature of Cl2EOs isotherm in Figure 6 range occurs from micellar solutions. The variation in
indicates that incremental sulfonate adsorption requires monomer concentrations for each component in this
1068 Langmuir, Vol. 8, No.4, 1992 Somasundaran et at.
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RESIDUAL SURFACTANT CONC kmol/mJ z
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Figure8. Adsorption ofCrbenzenesulfonate
andC12EOealcohol
on alumina from mixtures at initial molar composition of 24 mol
0
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10-4 10-3 10-2 10-1
% sulfonate -76 mol % alcohol: (a) adsorption of 100% Ca- 3
benzenesulfonate. (b) adsorption of 100% C12EOaalcohol; 50 °C; TOTAL SURFACTANT CONC kmol/m
0.03 M NaCl. Figure 10. Monomer concentrationscalculatedfrom regular
mixing theory for mixtures of (a) 24% Crbenzenesulfonate-
45 76% C'2EOsaicoholand(b) 50%Cs-benzenesulfonate-50% C'T
EOsalcohol: 50 .C; 0.03 M NaCI.
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TOTAL SURFACTANT CONC . kmol/m
Firure 9. Surface tension va total surfactant concentration for 10-13 10-12 10-11 10-10 10-9
mixtures of Cs-benzenesulfonate and ClzEO. alcohol before and 2
SULFONATE ADSORPTION DENSITY. mol/cm
after contact with alumina: initial composition 24 mol % sul-
fonate-76 mol % alcohol; 50 DC. 0.03 M NaCl Figure 11. Zeta potential of alumina after adsorption of Cr
benzenesulfonate and CI2EO. alcohol as a function of sulfonate
system is calculated in Figure lOa using the "best fit" adsorption density for various surfactant compositions: 50 °C,
regular solution interaction parameter of -5.0. The figure 0.03 M NaCI.
indicates that sulfonate monomer concentration increases
by 1 order of magnitude above the cmc as compared to 2 of alcohol adsorption differ substantially among these
orders of magnitude above cmc for 50 % sulfonate system systems. Thus, the data indicate that the eight ethoxyl
(Figure lOb). Thus, an increase in sulfonate adsorption groups are insufficient to mask or even partially mask the
with concentration should be expected to occur in this alumina surface and the synergism for mixture adsorption
system, but at a reduced rate. Since adsorption of the mainly arises from the hydrophobic interaction of the sur-
nonionic surfactant is dependent on the generation of a factants at the alumina-water interface as well as in the
hydrophobic microdomain by the sulfonate species, the bulk solution.
reduced sulfonate adsorption rate leads to a slow increase
of adsorption of the nonionic C12EOs- Conclusions
Figure 11 compares the zeta potential of alumina for Resultsobtained with mixtures of a nonionic/anionic
various surfactant compositions as a function of the sul- surfactant system have shown more complex behavior
fonate adsorption density. Results indicate that a single comparedto thoseof singlesurfactant systems. Ethox-
curve is adequate for fitting the data, although the levels ylated alcohol itself showed only trace adsorption on
Coadaorptionof Surfactant Mixtures Langmuir, Vol. 8, No.4, 1992 1069
alumina, but it was clear that the adsorption can be markedly the hydrophobicinteraction amongthe hydro-
enhancedby ordersof magnitudeby the introduction of carbonchainsof the adsorbednonionicand ionic surfac-
the anionic sulfonate. It is suggestedthat the initial tant moleculesand.thus increasetheir adsorptionmark-
electrostaticadsorptionof sulfonateprovidesa sufficient edly.
number of hydrophobic sites for hemimicellar type ad.
sorption of ethoxylated alcohol to occur. Such a mech- Acknowledgment. Financialsupport of the National
anismis analogousto the surfacenucleationphenomenon, ScienceFoundation (CTS-89-21570).
Departmentof En-
wherethe primary adsorbingspeciesacts as a catalytic ergy, Unilever Research.and BP America is gratefully
agent for the adsorption of the secondaryspecies. The
inclusionof nonionicsurfactantin the adsorbedlayer can acknowledged.
beexpectedto reducethe electrostaticrepulsionbetween Registry No. CuE., 3055-98-9;
Al,o3.1344-28-1;CeHl,c.H.-
the sulfonate head groups in the layer and enhance SO3Na.6149-o3-7.