Langmuir 1999, 15, 3279-3282

3279

Langmuir-BET Surface Equation of State in Fluid-Fluid Interfaces

J. Gracia-Fadrique
Departamento de F sica y Q mica Teo rica, Facultad de Qu mica, Universidad Nacional Auto noma de Me xico, Me xico D.F. 04510, Me xico Received September 14, 1998. In Final Form: January 21, 1999
A novel surface equation of state obtained from the BET adsorption isotherm and the Gibbs equation is presented. This equation describes both monolayer and multilayer adsorption. The emphasis of this paper is on monolayers, for which this new equation only contains thermodynamic parameters. In this form, it describes the characteristic behavior of nonionic surfactants, the relation between maximum surface pressure and critical micelle concentration, and the link between the standard free energy of adsorption and the standard free energy of micellization. It also explains and justifies the fundamental work of Rosen regarding the relative effects of structural factors on the surface tension reduction. The deviation of the model from experimental data is explained in terms of the activity coefficient at the critical micelle concentration, which is proportional to the micelle aggregation molecular weight.

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Introduction The Gibbs adsorption isotherm allows us to transform an isotherm to a surface equation of state. The Langmuir isotherm in fluid-fluid interfaces, coupled with the Gibbs equation,1 leads to

of surface tension that show an inflection point.4 The advantage of eq 4 over eq 3 is that an analytical solution can be obtained when the system reaches the saturation condition. In this case,

x2 d ) mRT dx2

( )

f1 x f xcmc f (cmc) f m

(5) (6) (7) (8)

x2 ) 1 + x2 T

(1)

where is the surface coverage ( ) /m), is the Gibbsian surface concentration, m is the maximum or saturation surface concentration, is the surface pressure, R is the gas constant, T is the absolute temperature, x2 is the bulk concentration in mole fraction for the surface-active solute, and is equivalent to the Henry constant in two dimensions. The BET equation and the Gibbs adsorption equation2 give

where (cmc) is the maximum or saturation surface pressure and xcmc is the critical micelle mole fraction. Solving the right-hand side of eq 2 for ) 1

x 2 d mRT dx2

( )

x2 (1 - x2)(1 - x2 + x2)

xcmc (2) (1 - xcmc)(1 - xcmc + xcmc)

Or in an explicit form for we get

)1

(9)

In both cases, the integral form leads to the corresponding surface equation of state:

) mRT ln(1 + x2) x2 ) mRT ln 1 + 1 - x2

Discussion

(3)

1 - xcmc xcmc

(10)

(4)

Substitution of eq 10 in eq 4 leads in a final form to a novel L-B surface equation of state containing only measurable parameters:

By a simple analysis of eq 3, the transformation of the Langmuir isotherm into a surface equation of state is observed. This equation was proposed empirically by Szyszkowski.3 The BET equation is a natural extension of the Langmuir model to the multilayer case; thus, we will call eq 4 the Langmuir-BET (L-B) surface equation of state. This work is devoted to the most common case of monolayer behavior. However, it can be used for systems
(1) Langmuir, I. J. Am. Chem. Soc. 1917, 39, 1848. (2) Brunauer, S.; Emmettand, P. H.; Teller, E. T. J. Am. Chem. Soc. 1938, 60, 309. (3) Von Szyszkowski, B. Z. Phys. Chem. 1908, 64, 385.

) mRT ln 1 +

[ (

1 - xcmc 2 x2 xcmc 1 - x2

(11)

For practical purposes, and for a typical micelle concentration (10-7 < xcmc < 10-3), eq 11 reduces to

) mRT ln 1 +

x2 x2 cmc

(12)

(4) A guila-Herna ndez, J.; Herna ndez, I.; Trejo, A. Int. J. Thermophys. 1995, 16, 45.

10.1021/la981244o CCC: $18.00 1999 American Chemical Society Published on Web 04/01/1999

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Gracia-Fadrique
Table 1. Values of the cmc Predicted with Eq 11 and Experimental Values of the cmc for the System 2-Butoxyethanol + Water14 at Different Temperatures temp (C) 4 25 48 1010m (mol/cm2) 4.76 4.23 3.43 1514 3874 6626 cmc (eq 11) 0.0251 0.0158 0.0124 cmc (exp) 0.0286 0.0163 0.0121

At the critical micelle concentration, eq 11 reduces to

(cmc) ) -mRT ln xcmc

(13)

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This last equation explains the typical behavior of etoxylated nonionic surfactants for which the most hydrophobic members show lower critical micelle concentrations and higher surface pressures and, on the other hand, are more hydrophilic. Surfactants show higher critical micelle concentrations and lower surface pressures (Shick).5-7 A possible mechanism to prove the functionality of eq 13 is to compare the experimental surface pressure at the cmc with the predicted surface pressure when the value of the critical micelle concentration and the maximum surface concentration m are known. In the extensive work of Rosen8-10 on the effectiveness of the surfactants in the surface tension reduction, the value of the maximum surface pressure is compared to the condition for the same surfactant when the surface pressure is 20 mN/m. When the surface pressure is the Rosen pressure ) 20 mN/m, eq 12 becomes

energy of micellization and the maximum surface pressure (cmc):

(cmc) ) -mGmic

(19)

The standard free energy of adsorption is defined as

-Gads ) RT ln

()
x2

(20)

x2f0

The limiting value at infinite dilution predicted by eq 11 is then

20 ) mRT ln

x2 cmc + x)20 x2 cmc

()
x2

2 ) mRT xcmc x2f0

(21)

(14)

In the vicinity of the critical micelle concentration

Kronberg et al.13 have suggested that the standard free energies of adsorption and micellization are related by a constant. Combining eqs 19, 21, and 22, we obtain a general relation for the standard free energies of adsorption and micellization.

x2 cmc + x)20 x)20

Thus, eqs 14 and 15 can be expressed as

(15)

2Gmic - Gads ) RT ln mRT

(22)

20 ) mRT ln

[ ]
x)20 x2 cmc

(16)

The difference between eq 13 and eq 16 is

cmc - ( ) 20) ) mRT ln

[ ]
xcmc x)20

(17)

This equation is the same as that deduced by Rosen and accounts for the effectiveness of the reduction in the surface tension.11 It is important to point out that this reduction is found under the condition proposed in eq 16; eq 17 is valid only near the saturation conditions, and eq 18 confirms the condition of the surface pressure value being around 20 mN/m or higher. For nonionic surfactants the standard free energy of micellization is given by12

Gmic ) RT ln xcmc

(18)

Equation 11 has been tested with our own experimental data, previously published14 for the system 2-butoxyethanol + water at several temperatures (4, 25, 48 C). Table 1 shows the experimental value of the cmc obtained from the abrupt change in the slope of the surface pressure versus ln(x) plot. The results show a good agreement with the values predicted by eq 11. m and are adjusted parameters from the experimental data. However, the last example is a particular case that fulfills eq 11. For characteristic cmc values (10-7 to 10-3 mole fraction) and surface saturation concentrations (24) 10-10 gmol/cm2, 25 C), eq 11 leads to nonrealistic surface pressures values. So, lets call systems L-B those ones that obey eq 11. The departure from this behavior is very closely related to the structure of the chemical potential involved. Both eqs 3 and 4 are deduced using the ideal chemical potential. Ross15 has pointed out the need for considering the activity coefficients for the solute and the solvent in the bulk and surface phase for a complete description of the adsorbed solutes. This lack of information for many systems can be avoided by the use of the symmetric convention for the activity coefficient in the cmc region. Under the symmetrically normalized convention

Then, eq 13 provides a direct relation of the standard free

(5) Schick, M. J. J. Colloid Sci. 1962, 17, 801. (6) Schick, M. J.; Atlas, S. M.; Eirich, R. J. Phys. Chem. 1962, 66, 1326. (7) Meguro, K.; Takasawa, Y.; Kawahashi, N.; Tabata, Y.; Ueno, M. J. Colloid Interface Sci. 1981, 83, 50. (8) Rosen, M. J. J. Am. Oil Chem. Soc. 1972, 49, 293. (9) Rosen, M. J. J. Am. Oil Chem. Soc. 1974, 51, 461. (10) Rosen, M. J. J. Colloid Interface Sci. 1976, 56, 320. (11) Rosen, M. J. Surfactants and Interfacial Phenomena, 2nd ed; John Wiley & Sons: New York, 1989; Chapter 5, p 217, eq 5.1. (12) Molyneux, P.; Rhodes, C. T.; Swarbrick, J. Trans. Faraday Soc. 1965, 61, 1043.

i f 1 as xi f 1

(23)

and the BET equation may be expressed in terms of the activity coefficient of the surface-active solute in the bulk
(13) Kronberg, B.; Lindstro m, M.; Stenius, P. Competitive Adsorption of an Anionic and a Nonionic Surfactants on Polystyrene Latex in Phenomena in Mixed Surfactant Systems; Scamehorn, V. F., Ed.; ACS Symposium Series No. 311; American Chemical Society: Washington, DC, 1986; Chapter 17. (14) Elizalde, F.; Gracia, J.; Costas, M. J. Phys. Chem. 1988, 92, 1032. (15) Ross, S. Colloids Surf. 1983, 7, 121.

Langmuir-BET Surface Equation of State

Langmuir, Vol. 15, No. 9, 1999 3281

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Figure 1. Natural logarithm of the activity coefficient at the cmc (cmc) as a function of the ethylene oxide content (EO) for polyoxyethylene hexadecanols21 (b), dodecanols5 (9), nonylphenols22 (1), and octylphenols23 (2).

Figure 2. Natural logarithm of the critical micelle concentration (cmc) (2), the aggregation number (b), and the activity coefficient at the cmc (cmc) (9) for nonylphenol ethoxylates, at 25 C.22
Table 2. Group Contribution of the cmc and cmc to the Standard Free Energy of Micellization5,21,22,23 (eq 31) homologous series C16Ei (25 C) C12Ei (55 C) NF (25 C) p.t. OF (25 C) Gmic (cal/mol) RT ln xcmc RT ln cmc RT ln xcmc RT ln cmc RT ln xcmc RT ln cmc RT ln xcmc RT ln cmc HPHOB (cal/mol) -652 +540 -812 +630 -550 +350 -550 +385 HPHIL (cal/mol) +33 -166 +15 -80 +27 -56 +53 -222

phase 2 and the activity coefficient for solute at the surface phase as

) (1 - x2)(1 - x2 + 2x2) mm
In the vicinity of the cmc

2x2

(24)

2 f cmc f m f m
and eq 24 at the cmc is now

cmcxcmc (1 - x2)(1 - x2 + cmcxcmc)

Solving eq 25 for we get

)1

(25)

1 1 - xcmc cmc xcmc

(26)

Figure 1 shows a linear behavior of the logarithm of the activity coefficient versus the ethylene oxide content for several homologous series. The negative contribution to the activity coefficient is common for every one, and the aggregation number of the micelle is proportional to the activity coefficient at the cmc (Figure 2). The same empirical equation for the logarithm of the cmc versus ethylene oxide content has been proposed for the classical behavior of nonionic surfactants. Hsiao et al.19 have proposed that the critical micelle concentration and the ethylene oxide chain length for a homologous series should be related by the equation.

and the L-B equation (eq 11), in terms of the activity coefficient, is

ln xcmc ) A +Bn

(29)

) mRT ln 1 +

1 1 - xcmc 2 x2 cmc xcmc 1 - x2

(27)

but 1 - xcmc = 1, and eq 27 at the cmc is reduced to

where A and B are empirical constants for a given homologous series of fixed hydrophobic content and n is the ethylene oxide chain length. Equation 29 may be expressed in terms of hydrophilic-hydrophobic contribution groups to the standard free energy of micellization20

(cmc) ) -mRT ln(cmcxcmc)

(28)

Gmic ) RT ln xcmc ) mHPHOB + nHPHIL (30)

If we write eq 30 in terms of the activity of the solute at
(19) Hsiao, L.; Dunnin, H. N.; Lorenz, P. B. J. Phys. Chem. 1956, 60, 657. (20) Rosen, M. J. Surfactants and Interfacial Phenomena, 2nd ed.; John Wiley & Sons: New York, 1989; p 151. (21) Elworthg, P. H.; MacFarlene, C. B. J. Pharm. Pharmacol. 1962, 14, 100. (22) Shick, M. J. J. Colloid Interface Sci. 1965, 20, 464. (23) Crook, E. H. J. Phys. Chem. 1963, 67, 1987. (24) Crook, E. H. J. Phys. Chem. 1964, 68, 3592.

It is necessary to emphasize that eq 27 is accurate in the vicinity of the cmc, although for many systems only the calculation of one constant () is enough for a total description.16-18 Selected values from the literature for (cmc), xcmc, and m allow us to calculate cmc with eq 28.
(16) Van hunsel, J.; Joos, P. Langmuir 1987, 3, 1069. (17) Lucassen-Reynders, E. H.; Van den Tempel, M. Proceedings of the 4th International Congress on Surface Active Substances (Brussels, 1964); Gordon & Breach, New York, 1964; Vol. II, p 779. (18) Van Hunsel, J.; Joss, P. J. Colloid Interface Sci. 1989, 129, 286.

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the cmc acmc instead of only the mole fraction, then

Gmic ) RT ln acmc ) RT ln cmcx cmc

(31)

From Figure 2, we can appreciate the opposite values for the slope (HPHIL) and the intercept (mHPHOB) for the cmc and cmc. Table 2 shows this contribution for different group contributions of several homologous series. As is expected for cmc, ethylene oxide groups show a positive contribution to the free energy of micellization (unfavorable to the micelle formation) and the CH2 groups show a negative contribution to the free energy of micellization (favorable to the micelle formation). On the other hand, for cmc, the ethylene oxide groups show a negative contribution to the free energy of

micellization (favorable to the micelle formation) and the CH2 groups show a positive contribution to the free energy of micellization (favorable to the micelle formation). This activity coefficient behavior suggests a reduction in the hydrophobic character as a result of the association process, where the coupling of the hydrocarbon tails decreases the hydrophobic effect and the neighboring of the ethylene tails promotes a higher water structuring. It seems that this mechanism, together with the number or degree of association of the micelle, plays an important role in avoiding the segregation of the surfactant.

LA981244O

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