J. Surface Sci. Technol., Vol 17, No. 1-2, pp. 1-15, 2001 © 2000 Indian Society for Surface Science and Technology, India Thermodynamics of Micelle Formation and Surface Chemical Behaviour of p-tert — Octylphenoxypolyoxyethylene Ether (TritonX-100) in Aqueous Medium ARINDAM CHATTERJEE*, TANIA DEY’, SHYAMAL K. SANYAL* and SATYA P. MOULIK*,* "Centre for Surface Science, Department of Chemistry, Jadavpur University, Calcutta-700 032, India, E-mail : essju@yahoo.co.uk ’Polymer Science Unit, Indian Association for the Cultivation of Science, Caleutta-700 032, India “Department of Chemical Engineering, Jadavpur University, Caleutta-700 032, India ‘Abstract — The methods of microcalorimetry and tensiometry have been employed for the assessment of the thermodynamics of micellization and surface chemical behaviour of the nonionic surfactant, p-tert-octylphenoxypolyoxyethylene ether (TritonX-100) in aqueous medium. The critical micellar concentration (CMC) obtained at different temperatures by both the methods have been compared. The energetic parameters (Gibbs free energy, enthalpy, entropy and heat capacity) of micellization have been evaluated from the results along with the interfacial adsorption parameters according to physicochemical concepts and relations. The steady state fluorescence quenching method has been employed for the determination of the aggregation number at different temperatures. Keywords : TritonX-100, micellization, microcalorimetry, aggregation number, energetics INTRODUCTION ‘The self-organization of surfactants (amphiphiles) in water to form micelles is a well-studied subject. Micellization is a thermodynamically favourable physicochemical phenomenon and the critical micellar concentration (CMC) of a surfactant is an impor- tant solution property from which thermodynamics of the process can be realized. The evaluation of thermodynamic parameters for nonionic surfactants through CMC is less complex compared to the ionic surfactants because of the absence of electrostatic inter- action including counter-ion binding in the former. However, energetics of self-aggrega- *Author for correspondance2: Chatterjee et al. tion of both types of surfactants are considered to depend on the micellar aggregation number and shape properties. The way the aggregation number influences the energetics of the process has been quantitatively accounted for by Corkill [1] and others [2]. The role of micellar shape in this context has not been so far quantified The enthalpy of micellization can be directly determined by calorimetry and indi- rectly from the temperature dependence of the Gibbs free energy based on van't Hoff’s principle. It is seen in practice that the enthalpies determined by the two methods often disagree with each other [3-7]; as a consequence, the entropies of micellizaion vary. Since the CMC can be method dependent, coupling of the calorimetr'c enthalpy with the Gibbs free energy (obtained by other methods) to evaluate the eniropy of micellization may be unrealistic. Since titration calorimetry can determine both CMC and the enthalpy of micellization, calculation of the latter in terms of the temperature dependence of CMC can be done to compare the agreement/disagreement between the direct and indirect meth- ods for the energetic description. In a recent communication [7], we have presented such an analysis on ionic surfactant systems and have discussed the results from physico- chemical point of view comparing the observations realized from a second method, ie., conductometry. TritonX-100 is a nonionic surfactant whose study is of practical and theoretical interest. It is a water-soluble nonionic surfactant containing polyoxyethelyne (POE) chain as the hydrophilic moiety. Because of the ability to incorporate organic materials within the structure, micellization studies on TX-100 have received considerable attention in both academic and industrial circles [8-10]. But detailed thermodynamic studies of the micellization and interfacial behaviour of TIX-100 are lacking in literature. In this exercise, we have investigated the CMC of TritonX-100 at different tem- peratures by the methods of microcalorimetry and tensiometry to obtain the energetics of self-aggregation by the direct (calorimetry) and indirect (van't Hoff procedure) methods “of evaluation. The interfacial adsorption phenomenon and its energetics have been evalu- ated from the tensiometric data. In the evaluation of the energetic parameters, the role of the micellar aggregation number has been recognized. This has been considered in the present study and consequently, the aggregation numbers of T.-100 micelles at the stud- ied temperatures have been determined by the method of steady-state fluorescence quench- ing measurements. Although the aggregation number of TX-100 micelles at temperature ~298 K has been reported in the past, its dependence on temperature is hardly found in literature. The shape of TX-100 micelles has been reported to be oblate [11, 12]. We con- sider that the shape remains unchanged over the temperature range selected in this study. So the energetic parameters obtained are not influenced by changes in micellar geometry. EXPERIMENTAL Materials : TritonX-100 (p-tert-octylphenoxypolyoxyethylene ether containing on the average 9.5 oxyethylene units per molecule [8]) was obtained from Sigma, USA. TheThermodynamics of Micelle Formation and Surface Chemical Behaviour 2 pyrene used for the fluorescence measurements was the same purified compound used earlier [13, 14]. The surfactant, cetyl pyridinium chloride (CPC, pure and characterized product, Sigma, USA) was the same sample used in earlier studies [7,15]. Methods : In the tensiometric measurements, the air/solution interfacial tensions were measured with a du Noily Tensiometer (Krliss, Germany) by the platinum ring detach- ment method after appropriate calibration [7, 13, 16-18]. The addition of the concentrated surfactant solution in water was done in installments (with the help of a Hamilton microsyringe) and the measurements were taken after proper mixing and temperature equi- libration. The accuracy of the measurements was within + 0.1 dyne cm-!. The measure- ments were duplicated and the mean values were considered for analysis. The experiments were performed in the temperature range of 288-308 K. The microcalorimetric measurements were taken in an OMEGA Isothermal Titration Calorimeter of Microcal Inc., USA. Aliquots of the concentrated surfactant so- lution of volume 5-15 pL were added in 1.325 mL water taken in the cell from a microsyringe and the heat flow in the cell or out of it during the titration was recorded [6, 7, 14, 15, 19, 20]. The addition of the surfactant solution and the measurements of the heat were done as programmed in the computer. The data treatment was performed with the help of Microcal Origin software. The measurements (repeated at least twice to check reproduéibility) were performed in the temperature range of 288-313 K. The fluorescence measurements were recorded in a Kontron SFM25 fluorimeter, Italy [14]. Measurements at different temperatures (288-313 K) were taken by circulat- ing thermostated water from a thermostatic bath (NESLAB, Coolflow25) around the fluo- rescence cell chamber. The aggregation numbers were determined from steady-state quenching experiments using pyrene (2.0 mol dm-) as probe and CPC (0.4~7.0 umol dm-) as quencher. The probe and the quencher are considered to be located in the same micellar environment and distributed between the aqueous and micellar pseudo phases following Poison’s statistics. The excitation wavelength was 334 nm and emissions were recorded in the range of 350-500 nm to determine the micellar aggregation number. The measurements were duplicated and the mean values were used. RESULTS AND DISCUSSION Critical Micellar Concentration (CMC) of TritonX-100. The CMCs of TritonX-100 at different temperatures have been measured from the change in surface tension and ther- mal behaviour by the tensiometric and microcalorimetric methods. Graphical illustrations of results are presented in Fig. 1 and 2. The point showing the change of course in Fig. 1 represents the CMC point. In Fig. 2, the differential plot in section C indicates CMC at the maximum point. In Fig. 3, the CMC-temperature profiles of TritonX-100 by the two methods are pesented. It is observed that the CMC is method dependent [7]. Al- though there is difference between the CMC values determined by calorimetry and sur- face tension, it is within tolerable limts. In the higher temperature side, the difference4 Chatterjee et al 0. 288k 50 és 7 4 ewe na * ie g 3 z 3 60 2 a a — 60. = 208K 303K * 0 49. ia «. cue 30. 20 25 3 2 a ° 1 2 a 6 + log log C Fig 1. Tensiometric determination of the CMC of TX-100 at different temperatures. i 33 Tme/min 67 400 San T i A 25: 30 \ 38. °. 8 6 4 = 10.65k mot 04 0 04 os 12 a ey G{AH)dC (arbitrary units) kJ/mol of Triton X-100 ost c 02 00 .enc=0, 345M, T = i c ao 04 08 42 [Tritonx-100/mM Fig 2. Titration of 200 1L aliquots of TX-100 micelles (7.776 mM) into 1.325 mL of water in 30 steps at 293K : (A) heat flow vs time; (B) enthalpy change per mole of TX-100 vs [TX-100]; (C) differential enthalpy change with respect to concentration vs [TX-100]Thermodynamics of Micelle Formation and Surface Chemical Behaviour 5 205 290205300 30510315 Fig 3. Temperature dependent CMC of TX-100 by different methods. widens and the trends vary. With increasing temperature, the polyoxyethylene chain (the polar head group) of TritonX-100 gets desolvated (dehydrated) and self-aggregation oc- curs at lower concentration. The decline is rapid on the higher side of temperature by rapid reduction of hydration. It is known that at ~65°C, TX-100 clouds [10] by way of phase separation. The hump at 308 K is a reality; the experiment has been repeated thrice to witness its existence. A change in solvation and/or molecular organization may be the reason, which is difficult to reconcile at present. The CMC of TX-100, on the average, ranges between 0.20.3 mM at 298 K. In this context the CMC values measured by other workers adopting different methods may be cited. These are 0.27 mM at 298 K by tensiometry [16]; 0.24, 0.26, 0.29 and 0.30 mM at 298, 296, 296 and 298 K respec- tively by spectrophotometry [21-24] and 0,23 mM at 303 K by calorimetry [15]. Thermodynamics of Micelle Formation. The measurement of CMC at different tem- peratures helps evaluation of thermodynamic parameters of the association process. For nonionic surfactants, the following equations are valid [7, 25-27]. AG®, = RT In Xoye (a) dinX eye) AHO RT? ome m ar Q)6 Chatterjee et al. oie asf, = Anon @ and ACpi, = AH) @) Pa tap Where Xaye is the CMC of the surfactant in molefraction unit, AG®,, AH®,, AS®, and ACp®, are the standard Gibbs free energy, enthalpy, entropy and heat capacity respectively. The other terms have their usual significance. The evaluation of the above parameters are relatively simple compared to the ionic surfactants by the absence of counter-ion bind- ing. Since InX¢yyc is not a linear function of T, the AH®, and AS®, have been evaluated by the procedijre of second degree polynomial fitting given below [7, 19, 28-30]. In Xue =a + BT + cT? 6) where a, b and c are fitting constants. By equation (5), dinX oye —— St = b+2cT aT +2¢' (6) Using equations (2) and (6), AH®, = -RT°(b + 2cT) @) The AH?, vs T plot is also not linear; it requires a second-degree polynomial equation (8) for fitting, AH, = A+BT + CT? (8) Thus, 6 ACp?= ies =B+2CT 0) where A, B and C are the required polynomial constants. The thermodynamic parameters obained by processing the tensiometrie CMC data by the above procedure using van't Hoff's rationale are presented in Table 1. It is seen from the table that the micellization of TX-100 is more spontaneous with increasing tem- perature; the process is essentially endothermic which declines with temperature along with corresponding decline in entropy. The change in specific heat is negative and fol- lows the same declining trend as in enthalpy. The above procedure of thermodynamic description of micellization of TX-100 is very frequently done. Direct determination of enthalpy and its combination with AG®, obtained from equation (1) can also produce AS®, and ACp®,. The above two procedures are seldom thoroughly compared which we haveThermodynamics of Micelle Formation and Surface Chemical Behaviour 7 TABLE 1 The CMC and Thermodynamic Parameters* of TX-100 at Different Temperatures from Tensiometric Measurements”. Temp/K — CMC/mM AGo AH? ACP) AS? ‘kJ molt AS mol! Jk) K+ mol ‘K+! mot! 288 0.370 =28:5 25.9 “115 189 293 0.300 29.6 19.9 1.25 169 298 0.278 -30.2 13.5 =1.34 147 303 0.263 -30.9 6.6 1.43 124 308 0.250 -31.6 ~0.86 71.53 100 *AH® is calculated from the van't Hoff equation SCMC of 0.27 mM at 296K has been reported in ref. 16 00 4 42 5 a 5 2B 4 126 . “167 = eee oo 02 04 06 08 10 12 14 (1X10 / mt Fig 4. Microcalorimetric determination of AH®, of TX-100 at different temperatures. (a) 288K : titration of 200 ul aliquots of TX-100 micelles (7.776 mM) into 1.325 mL of water in 30 steps; (b) 293K ; titration of 200 pL aliquots of TX-100 micelles (7.776mM) into 1.325 mL. of water in 30 steps; (c) 298K : titration of 200 UL aliquots of TX-100 micelles (7.776mM) into 1.325 mL. of water in 30 steps; (d) 303K : titration of 200 ul aliquots of TX-100 micelles (7.776mM) into 1.325 mL of water in 30 steps; (e) 308K : titration of 200 uL aliquots of TX-100 micelles (7.776mM) into 1.325 mL of water in 30 steps; (f) 313K : titration of 240 pL. aliquots of TX-100 micelles (7.776mM) into 1.325 mL of water in 30 steps. JSST-28 Chatterjee et al. recently done on ionic surfactants and herein do on TX-100. In Fig. 4, the microcalori- metric runs on differential heats of dilution of TX-100 at six different temperatures 288, 293, 298, 303, 308 and 313 K are presented. The CMC and the enthalpy of micellization have been evaluated from the results as indicated in Fig, 2 and recently described [7, 14, 15, 19]. The calorimetrically found sets of results are presented in Table 2. In this table, thermodynamic parameters obtained by processing the CMC data by the van't Hoff method are also shown. It is observed that the AH®,, AS®, and ACp®, appreciably differ. The comparison of microcalorimetric results obtained by the above two procedures (Table 2) has revealed that the direct results of microcalorimetry are lower than those realized by the method of van't Hoff (Table 1). TABLE 2 The CMC and Thermodynamic Parameters of TX-100 at Different Temperatures from Microcalorimetric Measurements". Temp/K CMC/mM — AG®, AH? fet mol ACp) IK mol! AS° IK molt ‘ki mol! van't Cal vant Cal. van't Cal Hoff Hoff Hoff 288 0425-282 161 129° 374 478 154 143 293 0345 229.2141 10.6 408 462 148 136 298 0325 298 120 893 4420-445 140 130 303 0315 30497 6.04 476 428 132 120 308 0320 «30.973 3.64 —510 412 124 n2 313 0.270 318 4.6 2.40 =545-395 116 109 CMC of 0.23 mM at 303K has been reported in ref. 15 There are reports [3—7] on the disagreement between the van't Hoff and calorimet- ric enthalpies of micellization. The effect of micellar aggregation number on the free en- ergy change for the process may affect the other derived energ#tic parameters. It may be argued that the temperature effect on CMC automatically takes care of the aggregation number related component (if any), and the AH®, described from the polynomial fitting in terms of equation 2 or 8 is the true value. The AG®, is of course different and can be obtained from the equation of Corkill et al. [1] based on mass action principle. AGi< Rafa inks v0 iG i where n is the aggregation number of the surfactant and f (n) is given by the equation i,Thermodynamics of Micelle Formation and Surface Chemical Behaviour 9 n° (2n—1) ee n(2n—1) GN ey D +(n De we To evaluate AG‘, by equation 11, we have determined the average aggregation number ¥ by the fluorescence quenching method in the following way at a total [TX-100] of 1 mmol dm™ (nearly ten times the CMC). The relationship of 1 to the pyrene fluorescence in the absence (I,) and presence of the quencher CPC (1) is given by the rela- ay (12) it = Ha (S]-eme where [S] is the total surfactant concentration in the system (1 mmol dm in this study). We have obtained n values at different temperatures by plotting In (Iy/1) vs [Q] and multiplying the slopes with {[S]-CMC} at the respective temperatures. The 7 val- ues obtained are 117, 124, 135, 131, 140 and 159 at the temperatures 288, 293, 298, 303, 308 and 313 K respectively. They are found to increase with temperature which is expected. Using these 1 values in equation 11, the AG®, has been found to increase to the extents of 0.35-0.45 kJ mol-! which is only minor with respect to the AGS, realized oth- erwise. The thermodynamic parameters documented in the Tables | and 2 are, therefore, valid and discussion based on their magnitudes and signs would be realistic. The AH®, of micellization of TX-100 obtained by the calorimetric and van't Hoff methods are both positive: the latter is more positive than the former. The AHS, values obtained by the van't Hoff method using the tensiometric CMC values are even more endothermic. The AH®, values normally obtained by both van't Hoff and calorimetric methods for ionic surfactants are negative [7, 19, 31]. This shows radical difference be- tween the ionic and nonionic surfactants with respect to micellization. Ionic (electrostatic) interaction in case of former is a major difference compared to the nonionics, The release of water molecules by the disruption of hydrophobic hydration of amphiphile tail dur- ing its transfer to the micelle involves absorption of heat and associated disorder in the system, Simultancously, there occurs reorganization and restructuring of the released water molecules with associated exothermic heat change. This makes the resultant AH®, less endothermic compared to the van't Hoff result where the second exothermic process does “pot influence the enthalpy of the n(monomer) <—* micelle equilibrium, obtained from “the temperature dependence of CMC. It may be mentioned that the two processes have a basic difference; the calorimetry is an integral process whereas the van't Hoff treatment is a differential process [4]. The AS®, are all positive, a state of disorder results by way of micellization. Like the ae \AH®,, the AS®, decreases with temperature; the increased thermal energy10 Chatterjee et al. AS°,,/ J.C molt 110 120 130, 140 150 16 20 r T T T Tor a AH? kdmot™ (aH? Jey kd: mor? 1000 -12002C— 140180 BOL (aS, )5y/ 3K *mor™ Fig 5. Compensation plots of AH®, and AS®, obtained from different methods, at higher temperature decreases hydrophobic hydration and consequently the magnitudes of both AH? and AS®,. The AS®, by van't Hoff method is obviously higher than AS? by calorimetry. In Fig, 5, the compensation plot between AH®, and AS®, is illustrated. The compensation temperatures (Tr...) obtained are 306.6 and 258.4K, Like other micellar systems, the ACp®, are all negative [6, 7, 19]; this is because of relatively less ordered final state (micellar state) than the initial hydrophobically hy- drated (more ordered) state of the monomer. With increasing temperature, the magnitude of ACp?, expectedly increases. The coupled dependence of (AH®,)../(AHY,),s, (AS%,).4/(AS®,)ya, and (ACp?,)../ (ACp%,),x, are presented in Fig. 6. The profiles are all nicely linear. The AH®, , AS®, and ACp?, profiles with temperature by both the methods are also linear, They are not shown to save space. In Table 3, the difference of the thermodynamic parameters for example, [(AH®,),_,Thermodynamics of Micelle Formation and Surface Chemical Behaviour BT (QH® ea! Kd.mol™ paisa Sse Stee sang reacdal ta! 1B ry * Cor. Coaff=0.9927 3 4 ay 4 Se = 6 5 160 £ Corr, Coeff =0.9928 eed & 2 04 4 = % 1204 T i i ae % 110 4120 430 440 2 2 Tea = 044 (08% eat LK mot & 2 054 Seale CaaS 3 8 04s 048 04M 042-040-038 (SCP yea! IK mot" Fig 6. Correlation of AH®. 9,» ASE, and ACp?, between van't Hoff and calorimetric methods. TABLE 3 The Difference between the Thermodynamic Parameters Realized by the Calorimetric and van't Hoff Methods for TX-100 at Different Temperatures. Temp/K A(AH®) AS mol! A(A8°.) AK mol! A(ACp9) K+ mot! 288 3.20 =I 104 293 3.49 11.9 54 298 -3.08 ~10.3 3 303 3.68 12.1 4B 308 3.62 Sills -98 313 Seal ~7.08 -15012 Chatterjee et al. - (AH?,),,;] or A(AH®.) are presented for the studied temperatures. Both A(AH®,) and A(AS),) slightly vary with temperatuer; there are large variations at the highest tempera- ture studied, i.e., at 313K. This temperature has a sizable say on the thermodynamics of the micellization process of TX-100. Recognizing the exothermic reorganization of wa- ter structure following micellar entry of the monomers, the A(AH®,) and A(AS®.) corre- spond to this effect per mole of monomer unit. The values obviously decrease with in- creasing temperature and the change at 313K is more compared to other lower tempera- tures. The A(AS9,) are also negative and the values decrease with increasing temperature with a comparative large change at 313K. The A(ACp®,) are initially negative and de- crease in magnitude, and at 308 and 313 K the values are positive. This is in accord- ance with the balance between the breakdown of the initial non-specific hydration of the nonpolar part of the monomer and the reorganization of the solute following the micellization process; thé latter exceeds the former at temperature 308 K and above. Al- though both A(AH,) and A(AS2,) vary nonlinearly with temperature, the A(ACp®,) var- ies linearly (curves not shown). The A(AH?,) and A(AS®,) also show a linear correlation with a compensation temperature (TP...) Of 283 K. These thermodynamic informations about the water structure reformation are of significant importance for the micellization of TX-100. Interfacial adsorption of TX-100. The adsorption parameters of TX-100 at the air-water interface have been evaluated from the tensiometric results using the following relations [13, 16-18]. __ Re a oe 2.303RT © CMC Figg © ce 108 Awnin = ni (ay where Uyjge % Cy Amin and N are the surface excess of TX-100 at CMC, the two dimen- sional surface pressure of the amphiphile molecules at the interface, the bulk concentra- tion of TX-100, the minimum head group area of the amphiphile molecule and the Ayogadro number respectively. The = vs logC plots to derive the slope (dz/dlogC) at different temperatures are illustrated in Fig. 7. The T,,., and A,,, values obtained at temperatures 288, 293, 298, 303 and 308 K are presented in Table 4. With increasing temperature, the [’,,,, has mildly increased except at 308K which shows a reasonable decline. The A, values have con- sequently decreased and finally increased. The increased adsorption with rise in tempera- ture results from greater instability of TX-100 in the bulk. The hydration of TX-100 molecules is known to decrease with increasing temperature and at 338K (65°C) phase separation or clouding occurs [10]. This phenomenon leads to transfer more molecules of TX-100 to the interface from the bulk with rise in temperature. Por a better understanding, the thermodynamics of interfacial adsorption have been examined. The relations used for this are given below [13, 16-18].Thermodynamics of Micelle Formation and Surface Chemical Behaviour 13 7 154 [Zax 6 . ie ze cme = 20: = 0. 5 ‘e asf é ° as 30 454 [Peax] 451 [503K] \ \ 5 cnc owe Lb» a € 18 4 1 ° 60 as 30 a5 loge loge Fig 7. & vs logC profiles for TX-100 at different temperatures. (15) (16) and AS%, = a7 where the new terms AG®,, AH%, and AS®, are the standard Gibbs free energy, standard enthalpy and standard entropy of adsorption respectively. The results are presented in Table 4. The AG®, shows increased spontaneity with temperature in accordance with T,,,., values. The adsorption pr cess is exothermic which declines with temperature; the AH, at 308K is quite smail. This suggests that the ad- sorption of the amphiphile molecules at the interface occurs with lower state of organi- zation. This is supported by the AS®, which starts from negative sign at 288K and changes sign at 293K and remains so with significant rise in magnitude meaning that the process of interfacial adsorption ends up with lowering of compact amphiphile organi-14 Chatterjee et al. zation. The AH®, and AS®, finally compensate each other with a compensation tempera- ture (Toomp) 0F298.4K. comp! TABLE 4 Interfacial Adsorption Parameters of TX-100 at Different Temperatures Obtained from Tensiometric Measurements. Temp/ CMC/mM AG, x 10 A,,,/nm? AG, ant, AS), Kk iki mol/mol m? fkI mol"! IK! mot! K+ mot! 288-0370. 28.5 2.46 0.676 46.7 53.9 24.9 293 0300 -29.5 248 0.671 46.7 418 16.7 298 = 0.278 «= -30.2 251 0.660 ~47.0 28.9 60.8 303 (0.263 -30.9 2.56 0.648 47.2 14.9 106 308 0250-315 2.48 0.670 48.0 =0.045 156 CONCLUSIONS The CMC of TX-100 by microcalorimetry is higher than that by tensiometry. The AH®, obtained directly from calorimetry differs from that obtained indirectly by the van't Hoff method. The latter is more endothermic than the former. This difference has been accounted for due to the altered organization of water structure resulting from the trans- fer of monomer from the solution phase into the micelle. The altered aggregation of the TX-100 micelle minorly contributes to the thermodynamics of the self-aggregation proc- ess. The TX-100 monomers get dehydrated and favourably get adsorbed at the air/water interface with rise in temperature. 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