Journal of Colloid and Interface Science 267 (2003) 151154 www.elsevier.

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Testing the GouyChapman theory by means of surface tension measurements for SDSNaClH2 O mixtures
C. Marcus Persson,a,b, A. Petra Jonsson,a,b Magnus Bergstrm,a,b and Jan Christer Eriksson a,b
a Institute for Surface Chemistry, SE-11486 Stockholm, Sweden b Department of Chemistry, Surface Chemistry, Royal Institute of Technology, Drottning Kristinas vg 51, SE-100 44 Stockholm, Sweden

Received 10 December 2002; accepted 18 July 2003

Abstract Surface tension isotherms were measured for sodium dodecyl sulfate (SDS) at different concentrations of added salt (NaCl). The free energy of the surfactant monolayer was assessed by invoking the GouyChapman theory for the charged head groups, the hydrophobic (Tanford) free energy of transfer of the hydrocarbon chain, and the hydrocarbon chain congurational free energy according to Gruens calculations and nally macroscopic contact terms. In particular, the effect of an increased salt concentration in bulk was examined. Theoretical predictions compare well with the experimental ndings, and good agreement was found with respect to both the variation of free energy of the monolayer and the surface pressure behavior. Thus, at least for a liquid-expanded monolayer of SDS, the GouyChapman model yields a satisfactory account of the electrostatic contribution to the thermodynamic properties at different salt concentrations of NaCl. 2003 Elsevier Inc. All rights reserved.
Keywords: Surface tension; Surface pressure; Ionic surfactant; SDS; GouyChapman

1. Introduction In various ways the GouyChapman theory of charged interfaces, assuming a smeared-out surface charge and neglecting ionion correlation and volume effects, has been shown to hold for 1:1 salts. A main reason is presumably that the size and ionion correlation effects approximate cancel [1]. The intuitive model of an adsorbed surfactant layer at the airwater interface as being composed of a hydrocarbon part, liquid-like in its properties, and a polar part of which the head groups mix with the adjacent solution has recently been veried through sum frequency generation spectroscopy and ellipsometric measurements [2,3]. Thus, we are justied in adhering to the molecular model of a surfactantladen 1/v interface presented by Eriksson and Ljunggren [4] for which the free energy of the electrostatic double layer is calculated according to the GouyChapman model. In the present study we compare the prediction of the molecular theory as to the effect of added salt (NaCl) with the corresponding experimental results.
* Corresponding author.

2. Material and methods Sodium dodecyl sulfate (SDS) was purchased from Sigma and repeatedly recrystallized in ethanol. Sodium chloride was obtained from Merck (Suprapur) and used as received. Surface tension was measured with a Krss K12 tensiometer, employing the Wilhelmy plate method. The water used in the experiments was obtained from a Millipore RiOs-8 and Milli-Q Plus 185 purication system and nally ltered through a 0.2-m Millipak lter.

3. Theory We consider a liquid-expanded monolayer in which the hydrocarbon part of the monolayer behaves as a liquid hydrocarbon and adhere largely to the approach taken in [4]. The following lm free energy contributions are taken into account: the one caused by the hydrophobic effect, the congurational free energy of the hydrocarbon chains, the changes in the macroscopic tensions, and the free energy of the electrostatic double layer. The free energy gain in transferring a hydrocarbon chain from the bulk solution at mole fraction x2 to the interface has

E-mail address: marcus.persson@surfchem.kth.se (C.M. Persson). 0021-9797/$ see front matter 2003 Elsevier Inc. All rights reserved. doi:10.1016/S0021-9797(03)00761-6

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been quantied by Tanford [5] and is for a straight saturated C12 hydrocarbon chain given by Tan /kT = 19.96 ln x2 , (1)

According to the above scheme, the surface pressure is determined by = (conf + el ), (9)

where k is the Boltzmann constant and T the absolute temperature (295 K). The attachment of the hydrocarbon chains, packed to the bulk-phase densities, to the polar groups residing in water imposes constraints on their congurational degrees of freedom. This free energy contribution, gconf , as calculated by Gruen [6] and Szleifer et al. [7] relative to bulk hydrocarbon agrees well with experimental results [4] for a dodecyl chain. Thus we can use the numerical t [4] gconf /kT = 3.126301 1.155336L + 0.1827336L2 0.01407631L3 + 0.0004774232L4, (2) where L is the thickness of the interface, determined by L = V /a2 , V being the molar volume of the hydrocarbon chain (351 3 /molecule) and a2 being the average molecular area. As a condensed monolayer is formed some changes in the macroscopic surface tensions will occur. gm is the change in macroscopic surface energies and is given by gm = hv a2 + hw a2 , (3)

i.e., of the sum of the congurational and electrostatic component of the surface pressure where conf = dgconf dL dL da2 .
T , all

4. Gibbs surface tension equation Assuming the surfactant and the salt to be fully dissociated results in the following conditions: cDS = cSDS , cNa+ = cSDS + cNaCl = ctot . (10) (11)

Furthermore assuming the activity factors to be given by the DebyeHckel limiting law yields the following expressions for the chemical potential of SDS: SDS = DS + Na+
2 = 0 + RT ln f + RT ln cDS + RT ln cNa+ . SDS

where hv is the surface tension of the hydrocarbonvapor interface formed and hw the surface tension value of the hydrocarbonwater interface. We next invoke the approximation 0 = hv + hw , (4)

(12) Hence,
2 dSDS = RT d ln f + d ln cSDS + d ln(cSDS + cNaCl ) ,

where 0 is the surface tension value of water at zero SDS concentration. The free energy due to a layer of surfactant ions and its counterions is calculated by the GouyChapman theory, which is based on the PoissonBoltzmann approximation assuming a smeared-out surface charge. Accordingly, we have gel = 2kT ln S + S 2 + 1 2kT (S 2 + 1) 1 , (5) S

where ln f = 1.17 ctot . Accordingly, using Eq. (11), dcSDS 2 . d ln f = 1.17 ctot Finally, we obtain dSDS = RT

(13)

(14)

2cSDS + cNaCl 1.17cSDS d ln cSDS . (15) cSDS + cNaCl ctot

where S, the reduced charge parameter, is dened by S= 2 , 8RT 0 r c (6)

Insofar as NaCl remains negligible and the changes in NaCl are minor the Gibbs surface tension equation is simply (constant T ) d = SDS dSDS . (16) Thus the surface excess, DS (SDS = DS ) is readily obtained from Eqs. (15) and (16). However, DS accounts for the amount adsorbed in the m monolayer (DS ) plus a small negative contribution due to the exclusion of DS ions from the diffuse part of the double layer. Taking this small contribution into account transforms Eq. (16) for the salt-free case into
m DS = SDS (1 x),

where is the surface charge density, R the ideal gas constant, r the relative dielectric constant for the solution, 0 the (vacuum) permissivity constant, and c the total salt concentration in the bulk. The net free energy change per DS ion in the monolayer becomes = g DS = a2 , (7)

where DS is the chemical potential of the dodecyl sulfate ion. The surface tension, , is also given by the derivative = dg da2 .
T , all

(17) in the diffuse part of the double

where x, the fraction of DS layer, is given by [8] 1 1+x = 1x S S2 + 1 1 .

(8)

(18)

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153

Fig. 1. Surface tension isotherms for SDS at different concentrations of NaCl. From right to left, 0, 10, 30, 50, 100, and 300 mM.

Fig. 2. The surface pressure isotherms for SDS in 0 (upper thick line) and 30 mM NaCl (lower thick line). The thin lines are calculated according to the model (the upper for 0 mM and the lower for 30 mM NaCl).

This effect becomes smaller and smaller as the salt concentration is increased. The reason is that the extent of the diffuse double layer decreases while also the concentration of DS in the bulk decreases for a given adsorbed amount. At 30 mM NaCl concentration the effect is negligible. The change in the activity factor with SDS concentration also decreases as the background concentration of NaCl is increased. This is due to the fact that the change in total ion concentration becomes smaller and smaller.

5. Results and discussion The surface tension isotherms measured at different NaCl concentrations are displayed in Fig. 1. The decrease in SDS concentration for a given adsorption density as the salt concentration of NaCl is increased is clearly seen. This is due to the decrease in the free energy of forming a charged monolayer as the ionic strength of the solution is increased as evident from Eq. (5). The surface pressure isotherms of SDS at different bulk concentrations of NaCl, 0 and 30 mM, are displayed in Fig. 2. These results verify that the simple GouyChapman model of the interface combined with the Gruen expression for the congurational contribution account well for the observed surface pressure isotherms especially at higher salt concentrations of NaCl. The less good agreement in the absence of salt could be due to trace amounts of impurities (dodecanol). This effect is expected to be less severe as the salt concentration is increased since the surface activity of SDS increases signicantly. Another possibility is that DS , which is the coion in the salt-free case, is large and hydrophobic in contrast to Cl , which acts as coion at higher salt concentrations. The change in free energy due to an increase in the salt concentration at a constant molecular area is readily calculated from (assuming all other free energy contributions remain the same when changing the salt concentration) g 0 = gel 19.96kT + gconf + gcontact + pg , DS (19)
Fig. 3. The free energy according to Eq. (19) (lled symbols, theory, putting pg = 0) and Eq. (20) (unlled symbols, experiment). The circles are for a molecular area of 50 2 and the squares for a molecular area of 40 2 .

where gconf + gcontact presumably are independent of the salt concentration and pg is a constant independent of the adsorption density. It includes the free energy changes upon transferring the polar group from the bulk to the interface apart from purely electrostatic contributions. The corresponding change, dominated by the change in gel , in the electrostatic free energy can also be computed from the experimental data by employing Eq. (7). In this way we obtain g 0 = a2 + ln f xDS . DS (20)

The surface tension values at a constant molecular area (40 and 50 2 ) and the corresponding SDS mole fraction were inserted in Eq. (20). Because the salt concentration increases signicantly we used the experimentally determined values of the activity factor obtained from [9]. The theoretical values, obtained from the GouyChapman theory, and the experimentally determined ones are shown in Fig. 3 for two molecular areas, 40 and 50 2 . We note that the difference between the experimental and the theoretical points, pg , is nearly constant for a given molecular area as well as comparing the two molecular areas (0.85kT ). This supports the use of Eq. (19), which is based upon adding various free energy contributions. For instance, the fact that a given ad-

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sorption density of SDS occurs at lower SDS concentrations when the salt concentration is raised is readily explained by the decrease in free energy of forming a charged monolayer as predicted by the GouyChapman theory. For the SDS/NaCl monolayer case this theoretical approach works well, especially when considering that no adjustable parameters but the head group constant pg are involved. However, to generalize our ndings one would need to study additional charged monolayers systems. It might well turn out that all that is needed to fully capture the behavior of other similar monolayer systems would be to invoke other values for the head group constant pg encompassing different counterions.

mately giving rise to an approximate surface pressure equal to 2kT /a2 for large values of the S parameter. Apart from a small (constant) head group contribution, the monolayer free energy itself is also reproduced by the model used here for different salt concentrations as well as at different packing densities. Acknowledgment This work was supported by the Competence Centre for Surfactants Based on Natural Products, SNAP. References

6. Conclusions To conclude, we have veried that the GouyChapman theory of the electrical double-layer that was developed almost a century ago provides a next-to-quantitative account of the electrostatics of monolayers of SDS in the liquidexpanded range. The inherent features of an evenly distributed, smeared-out surface charge and volumeless counterand coions may well seem unrealistic, yet the model covers two important entropic effects, viz. the lateral and the vertical mixing of the counterions with the solvent, ulti[1] R. Kjellander, S. Marcelja, J. Phys. Chem. 90 (1986) 1230. [2] S.R. Goates, D.A. Schoeld, C.D. Bain, Langmuir 15 (1999) 1400. [3] G.R. Bell, S. Manning-Benson, C.D. Bain, J. Phys. Chem. B 102 (1998) 218. [4] J.C. Eriksson, S. Ljunggren, Colloids Surf. 38 (1989) 179. [5] C. Tanford, The Hydrophobic Effect, 2nd ed., Wiley, New York, 1980. [6] D.W.R. Gruen, E.H.B. Lacey, in: K.L. Mittal, B. Lindman (Eds.), Surfactants in Solution, Vol. 1, Plenum, New York, 1984. [7] I. Szleifer, A. Benshaul, W.M. Gelbart, J. Phys. Chem. 94 (1990) 5081. [8] J.C. Eriksson, Finn. Chem. Lett. 105 (1982). [9] Handbook of Chemistry and Physics, 78th ed., CRC Press, Boca Raton, FL, 19971998.