Colloids and Surfaces A: Physicochemical and Engineering Aspects 155 (1999) 405 412 www.elsevier.

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A study of micellization parameters and electrostatic interactions in micellar solution of sodium dodecyl sulfate
S.S. Shah a,*, Akhtar Saeed b, Q.M. Sharif b
a b

Department of Chemistry, Quaid -i -Azam Uni6ersity, Islamabad, Pakistan NCE in Physical Chemistry, Uni6ersity of Peshawar, Peshawar, Pakistan Received 5 October 1998; accepted 6 January 1999

Abstract The electrical conductivity of sodium dodecyl sulfate (SDS) in aqueous solution was determined up to a concentration of 10 times the critical micelle concentration. The effects of solution concentration on the various interaction parameters of SDS have been studied. The mass action model was applied to micelle formation to calculate the micellization parameters: micellization constant, Kc; aggregation number, n ; and number of counterions per micelle, m. The micellization parameters also made it possible to evaluate the concentration change of monomeric surfactant ion with total surfactant concentration. The Debye Huckel Onsager equations have been applied to the experimental data for aqueous solution of SDS. An average degree of counterion binding to a micelle (m /n ) and aggregation number (n ) were determined to be 0.72 and 64, respectively. As aggregation number decreases monotonously with increase in concentration, this trend has been employed to calculate the electrical conductivity of the micelle (uM). 1999 Elsevier Science B.V. All rights reserved.
Keywords: Micellization; Aggregation number; Micellar size; Sodium dodecyl sulfate; Ionic conductivity; Ionic strength

1. Introduction The growing interest in surfactants is mainly due to their many applications in chemistry, biology, and pharmacy. Such important roles are related to their ability to form aggregate (micelles) when the surfactant concentration in aqueous solution exceeds critical micelle concentration (CMC) [1]. Sodium dodecyl sulfate(SDS) is the
* Corresponding author. Tel.: + 92-51-829167; fax: + 9251-821397. E -mail address: ssshah@ch-qau.sdnpk.undp.org (S.S. Shah)

ionic surfactant whose micelle formation has been investigated most widely and most profoundly among a number of ionic surfactants [2]. However, an electric conductivity of the micelle itself in aqueous solution still remains unsolved, although the physical and electrostatic pictures [3 5] of the micelles have been presented in great detail. A number of problems remain unsolved as regards the properties of aqueous solutions of surface active substances, despite their theoretical and practical importance. For instance, the three micellization parameters, the micellization con-

0927-7757/99/$ - see front matter 1999 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 7 - 7 7 5 7 ( 9 9 ) 0 0 0 2 1 - 7

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stant, Kc, the micellization aggregation number, n, and the number of counterions per micelle, m, are quite difcult to determine precisely. This is the reason why micelles have been mostly dealt with in a separate phase [6 8]. The purpose of the present work is to investigate the micelle contribution to these properties to some extent. An accurate model of conductivity for micelle solutions should incorporate (i) a means of accounting for the interionic interactions, (ii) an objective denition of the CMC, and (iii) a means of using all of the available conductivity data to test for consistency. Interionic interactions are of great importance for interpreting data for simple electrolytes [9] and must have considerable impact in systems which contain highly charged aggregates. Recently, many kinds of newly synthesized amphiphiles have been in widespread use [10 12] and, therefore, an easy but reliable method to determine these parameters is quite helpful to develop and characterize the properties of aggregates of these amphiphiles. In this study, then, the electrical conductivity change of the SDS solution was analyzed in order to present the picture of micellar solution from which the electrical conductivity of the micelle can be evaluated.

tion into doubly distilled water. Temperature was controlled at 298.2 K. The CMC of the surfactant was determined from the plots of specic conductivity versus concentration of the surfactant solution.

3. Theoretical The following equilibrium can be given for micelle formation of monodisperse ionic micelles [13].
n(n m) n S + m G + = Mn

(1)

where S , G + , Mn are surfactant ion, counterion, and micelle of aggregation number n, and m is number of counterions per micelle, respectively. From Eq. (1) the micellization constant, Kc, is written as Kc = [Mn ]/([Sn][Gm]) (2)

where [S], [G], and [Mn ], are the corresponding molar concentrations, respectively, and the electroneutrality of solution holds: [G] [S] (n m )[Mn ] = 0 (3)

The mass balance for surfactant ion and counterion are respectively expressed as Ct = [S] + n [Mn ] (4) (5)

2. Experimental

Ct = [G] + m [Mn ]

2.1. Materials
SDS, the product of Fluka, was of analytical grade and was used without further purication. Water used was distilled twice from alkaline permanganate solution.

where Ct is the total surfactant concentration. From Eqs. (3)(5), [S] and [G] are written as: [S] = (1 n /m )Ct + (n /m )[G] [G] = (1 m /n )Ct + (m /n )[S] (6) (6a)

2.2. Conductance measurements

The specic conductance of the surfactant (SDS) was measured on a microprocessor conductivity meter (WTW), LF 2000/C model of Wissenchaftlinch Technische Werkstatten (Germany) at 298.2 K. The conductivity was measured stepwise by introducing an aliquot volume of the mother solu-

From the logarithm of Eq. (2), with Eqs. (4) and (6a), one obtains; ln[S] = (m /n ) ln{(1 m /n )Ct + (m /n )[S]} (1/n ) ln Kc + (1/n ) ln{(Ct [S]/n )} (7)

This equation suggests that the concentration of each chemical species can be evaluated at a surfactant concentration in combination with Eqs. (4) and (6a), once the three micellization parameters, Kc, n, and m, are obtained.

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The value of degree of counterion binding to micelle (m /n ) is evaluated from the ratio of slopes in the conductivity, K, versus concentration, C, above and below the CMC. The micellization constant can be derived from the denition of the CMC. 1/Kc = 2n (n + m )(CMC)n + m (8)

4. Results and discussion The changes of specic and equivalent conductivities with total surfactant concentration are shown in Fig. 1. From the kink point, the CMC was determined as 8.1 mol m 3. The values of specic conductivities below and above the CMC are also given in Tables 1 and 2, respectively. The concentrations of [Na + ] and [DS ] were separately determined up to 10 times the CMC at 298.2 K. The concentration changes of the two ions with total surfactant concentration have been already analyzed by the mass action model, hence for the present study, the values of surfactant ion concen-

On the other hand, the molar conductivity of a micelle, uM, with charge (n m ) can be given from the equivalent conductivity [14] as uM = 0.820(n m )2/rp = h (n m )2 (9)

where r is a micellar radius and p is solvent viscosity.

Fig. 1. Specic and equivalent conductivity of SDS at 298.2 K.

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Table 1 Specic conductivity (K ), ionic strength (I ) with total surfactant concentration (Ct) and the corresponding ionic conductivity (u ) changes (premicellar phase at 298.2 K) Ct (mol m3) 0.609 1.190 1.744 2.272 2.777 3.260 3.723 4.166 4.591 5.000 5.392 5.769 6.132 6.481 K (103 S m1) 0.401 0.796 1.14 1.50 1.80 2.10 2.38 2.65 2.88 3.12 3.32 3.53 3.71 3.90
I (mol1/2 m3/2) 0.780 1.090 1.320 1.507 1.666 1.805 1.929 2.041 2.142 2.236 2.322 2.401 2.476 2.545 uNa+ (104 S m2 mol1) 49.21 48.85 48.60 48.38 48.20 48.04 47.90 47.77 47.65 47.55 47.45 47.36 47.27 47.19 uDS (104 S m2 mol1) 20.97 20.76 20.61 20.48 20.37 20.28 20.20 20.12 20.05 19.99 19.93 19.88 19.83 19.78

tration [DS ] have been read off from Fig.3 of ref. [14]. Then, Eqs. (4) and (6a) were used to calculate the concentration of micelle [Mn ] and concentration of counterion [Na + ], respectively. The most reliable values for the parameters were found to be n = 64, m = 46.7 and log Kc = 230 [5]. These parameters values could perfectly reproduce the concentration changes of the two ions with SDS concentration up to 10 times the CMC. These changes are summarized in Table 2. SDS perfectly dissociates itself in an aqueous solution below the CMC and the ionic conductivity of Na + can be given by the following equation [15]: uNa + = (50.10 1.141
I )/104 (S m2 mol 1) (10)

known, it is possible to obtain the contribution of each chemical species to the equivalent conductance (L) above the CMC.

L = uNa + [Na + ] + uDS [DS ] + uM[Mn ]

(12)

As L = uNa + + uDS is below the CMC, uDS is easily evaluated, and can be expressed as uDS = (21.49 0.674
I )/104 (S m2 mol 1) (11)

The limiting ionic conductivity of surfactant ion uo DS (21.49) is obtained by linear regression analysis [16]. The changes of ionic conductivity of surfactant ion uDS with surfactant concentration above and below the CMC are shown in Fig. 2. Now that concentration changes of Na + , DS and micelle with surfactant concentration are

Fig. 2. Ionic conductivity of surfactant ion (uDS ) versus square root concentration of SDS.

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Table 2 Specic conductivity (K ), concentration changes of counterion [Na+], surfactant ion [DS], micelle [Mn ] and ionic strength (I ) with total surfactant concentration (Ct) and the corresponding ionic conductivity (u ) changes (micellar phase at 298.2 K) Ct (mol m3) 14.07 21.58 24.90 30.82 38.28 42.50 47.95 53.95 58.85 62.94 67.93 71.93 76.16 80.23 K (103 S m1) 6.10 7.60 8.15 9.53 11.36 12.29 13.53 14.79 15.83 16.68 17.64 18.49 19.22 19.67 [Na+] (mol m3) 8.92 10.45 11.12 12.43 14.00 15.04 16.25 17.61 18.83 19.84 21.07 22.13 23.25 24.32 [DS] (mol m3) 7.01 6.33 6.02 5.62 5.01 4.87 4.51 4.15 4.00 3.88 3.71 3.69 3.65 3.61 [Mn ] (mol m3) 0.110 0.238 0.295 0.393 0.519 0.587 0.678 0.778 0.857 0.922 1.003 1.066 1.132 1.197 I (mol m3) 24.38 43.80 52.70 67.66 86.80 97.53 111.52 126.91 139.00 149.00 162.00 171.87 182.30 192.49 uNa+ (104 S m2 mol1) 44.46 42.55 41.82 40.72 39.47 38.84 38.05 37.25 36.65 36.17 35.57 35.14 34.69 34.26 uDS (104 S m2 mol1) 18.16 17.02 16.59 15.94 15.21 14.83 14.37 13.89 13.54 13.26 12.91 12.65 12.38 12.13 uM (S m2 mol1) 0.374 0.235 0.214 0.214 0.195 0.195 0.176 0.158 0.158 0.142 0.142 0.124 0.109 0.095

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where Eqs. (10) and (11) were applied to the solutions above the CMC and the contribution of charged micelle was taken into account to calculate the ionic strength. For evaluation of ionic strength, we have applied a 3D model [17] as this model includes the contribution of all charged species in the solution. 1 m 1 1 2 2 + I = % Ci Z 2 i = (Ci + C m ) + lCnn (1 i ) 2 2 2i = 1 (13) where Ci is the total surfactant concentration, C + m is the concentration of counterion, Cn is the concentration of micelle, n is aggregation number, l is a shielding factor to account for the fact that the micelles contribute to the ionic strength and i is the counterion binding parameter equivalent to m /n. In the 3D model, the contribution of the micelles is more signicant over the other species in the solution than the previous models [17], yielding only smaller ionic strengths. This is because the micelle contributions are taken to be zero in previous models. When micelle contributions to conductivity and the interionic interactions are included in the 3D model, the ionic strength above the CMC increases to a level much higher than that for an equal concentration of 1:1 electrolytes. This increase is due to the signicant contributions of the micelles which are treated as an [n (1 i )]:1 electrolyte (see Eq. (13)). The ionic strength values with surfactant concentration are shown in Fig. 3. The Einstein Stokes equation (Eq. (14)) can be applied to the relation between the ionic conductivity of micelle with the charge Z of 17.3 and its radius r, when a moving particle is larger in size compared with the surrounding solvent molecules. uM = Z F 2/6yNpr (14)

Fig. 3. Ionic strength (I ) of surfactant solution versus the total concentration of SDS.

where F is Faradays constant, N is Avogadros number, and p is the viscosity coefcient of solvent. The radius of the micelle, calculated from the values of ionic conductivities of micelles given in Table 2, is found to be between 0.10 and 0.14 nm. This is a too small value to be accepted. On the other hand, the radius of micelle was evalu-

ated to be 2.53 nm from its diffusion coefcient [18]. This radius is longer than the full length of DS ion, and the 2.07 nm evaluated by Tanford [1]. This anamolous behavior can be explained by the fact that micelles move about with many solvent molecules and with counterions around them in the form of ionic atmosphere. In micelle formation, the monomer packing depends on geometric parameters such as micelle radius, r, chain monomer volume, 6, maximum length that the chain can assume(critical chain length), and the interfacial area per monomer, a (see Fig. 4). For spherical micelles, simple geometry is used to calculate micelle radius [19] by following the equations N = 4yr 3/36 a = 4yr 2/n (15) (16)

Tanford [1] has related the monomer chain , 3) to the number of carbon atoms, nc, volume (in A of the alkyl chain, as in Eq. (17).

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Fig. 4. Schematic representation of an idealized spherical micelle.

Fig. 5. Ionic conductivity of micelle (uM) versus surfactant concentration.

,3 6 = 27.4 + 26.9nc A

(17)

, 3 in Eq. (17) gives r = Substitution of 6 = 350 A , for n = 64. As aggregation number (n ) 17.11 A decreases monotonously with concentration, we get different values of r for aggregation number n = 7060. The aggregation number of SDS has been read off from Fig. 2 of ref. [14], up to a concentration of 80 mol m 3. The higher ionic conductivity of the micelle can be explained by the fact that high specic conductivity of the metal is due to free electrons moving about metal atoms, which suggests some hints on higher conductivity of the ionic micelle. In other words, some counterions can move freely from one micelle to the other through the overlapping of diffuse double layers around the micelle when two micelles come close together. Interionic interactions reduce the molar conductivities by an amount which depends on the size, charge and limiting conductivity of the individual ions, as well as the effective ionic strength. These interactions are generally due to hydrodynamic and electrostatic effects. In this report, we have investigated the interaction parameters of SDS solution in general and ionic conductivity of the micelle (uM) in particular. As aggregation number decreases monotonously with increase in concentration, this trend has been applied to calculate the electrical conductivity of the micelle (uM). The values of electrical conducitivity of the micelle (uM) with surfactant concentration are shown in Fig. 5.

From the graph it is clear that uM values decrease monotonously with concentration of SDS, similar to the aggregation number (n ). These minor but contributing factors will help us to investigate further into the interionic interactions and the micelle formation of other surfactant solutions.

Acknowledgements The laboratory facilities provided to one of us (QMS) by Prof. Dr M. Saleem, Chairman, Department of Chemistry and the nancial grant of the Quaid-i-Azam University, Islamabad are gratefully acknowledged.

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