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  • Tenside 2004

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    Tenside 2004

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    PHYSICAL CHEMISTRY Prshan hac lish Porth and Dhomesh Vrode, Sti Adsorption Characteristics and Micelle Formation of Two Cationic Surfactants and their Mixtures in Aqueous Solution [Adsorption characteristics and micellization of two cationic su factants vi. tetradecytrimethylammonium bromide (CTAB!) {and tetradecyhriphenyiphosphonium bromide (CyTPBY) were ‘examined from surface tension and electrical conductivity meas urements, The ertical micelle concentrations (CMCS), the de sree of counterion binding to micelles, (), the area/molecule at the air-water interface and the thermodynamic parameters of ‘micelizaton (AG, AH". and As.) were evaluated at several temperatures (25780°C). The mixtures of the two surfactants were also examined over the entire mole raction range (0-1) in water and aqueous NaCI solutions (0.01, 0.05 and 0.1 M) by surface tension measurements and the obtained results were analyzed using Rubingh’s regular solution theory. These mixed surfactant systems in water showed a near ideal behavior with [values close to zero but shits towards nonideality in presence fof NaCl. The results are discussed in terms of polar head group (its size and hydrophobicity), effect of ionic strength and tem- perature. ‘Adsorptionseigenschaften und Mizelbildung von rwei katio- nischen Tensiden und ihren Mischungen in wisstigen Lisun- gen. Die Adsorptionseigenschaften und die Mizellbidung der Beiden ationischen Tenside Tetradecytsimethylammionivm- bbromid (C;.TAB1) und Tetradecyltiphenylphosphoniumbromid (CuatPB) wurden mit Hife von Grenalichenspannungs- und Lettdhigkeitsmessungen untersucht. Die kritischen Mizell dungskonzentrationen (CMCs), der Grad der Gegenionenbin dung an die Mizellen (i), die Fiche/MolekUl an der Lut- Was ser-Grenaflache und die thermodynamischen Parameter der Mizellbildung (4, AH®, und AS,,) wurden far verschiedene Temperaturen (250°C) bestimmt. Mischungen der beiden Tenside wurden dber den gesamten Molenbruchbereich (0-1) sowohl in Wasser als auch in wassrigen NaCl-Losungen (0,0 (0.05 und 0,1 M) mit Hife von Grenalichenspannungsmessun- igen untersucht, Die Ergebnisse wurden mitels Rubingh’s requ far solution theory analysiet. Dabei zeigen diese Mischsysteme in Wasser nahezu ideales erhalten mit frWerten nahe Null In "NaCl-Lasung verschob sich dieses Verhalten jedoch hin zur [Nchtidealitt. Die Ergebnisse werden im Hinblick aut die polare Kopigruppe (Graf und Hydrophobie), den Efflekt der lonen- stirke und die Temperaturdiskuter. 1 Introduction Sueface active agents are unique substances; their molecules due to the presence of distinct hydrophilic and hydrophobic ‘moieties behave peculiarly in solution. The two basic fea tures viz. adsorption from solution and micelle formation shown by surfactants are responsible for their functional properties viz. wetting, emulsifying, solubilizing, dispersing, foaming and rheology control ete. which are widely em ployed in almost all chemical industries [1~2). Though not examined so extensively as anionic and nonionic susfac tants, cationic surfactants offer some additional advantages ‘over other classes of surfactants [36]. Cationic surfactants besides their surface activity show antibacterial properties and are used as cationic softeners, lubricants, retarding agents, antistatic agents and in some cases consumer use. Cationic surfactants belonging to qua ternary salts are well known compounds and have been ‘examined for their surface and solution behavior using 3 variety of methods viz, surface tension (7, 8}, conductance [9-11], viscosity (12, 13), dye solubilization (14), sound velo- «ity (10, 15, 16}, fluorescence (17), small angle neutron scat tering [18~ 20) and light scattering [21 ‘Mixtures of surfactants of various fypes in aqueous sol tion [22-30] often show superior properties to that of asin gle surfactant system. Treatments based on regular solution theory [3134] use CMCs to caleulate the interaction. para ‘mete, fi, to obtain information on the magnitude of interac tions between surfactants in a mixed micelle, A negative va ue of indicates synergism in mixed micelle formation, a positive value indicates antagonism and if =O then mixed ‘micelle formation is ideal. The larger the value of the stronger is the mixing nonideslity and the corresponding sy nergismn, Mixed micelles composed of mixtures of surfac fants of similar structure are nearly ideal [35 36), However, mixed micelles containing ionic and nonionic or anionic and cationic surfactants show negative deviations from ide- ality [22—24 Tn this paper, we present the results obtained on aggre gation behavior of tetradecyltrimethylammoniuim bromide (CuTABr) and tetradecyltriphenylphosphonium bromide {CucTPB:) in water across a range of temperatures (25~ 40°C) by clectrical conductivity measurements. The critical imicelle concentrations (CMCs) and the degree of counter ion dissociation of micelles (f) were obtained at each tern perature. From the CMC values as a function of tempera- ture, the corresponding thermodynamic parameters of mi- cellization were algo evaluated. The CMCs were also determined at 30°C from surface tension measurements for single surfactants and at various mole fractions in mixed systems of C,,TABr and C,,TPBr in water and aqueous salt (NaCl) solutions 2 Experimental 21 Materials The cationic surfactants tetradecylrimethylammonium bro- mide (C),TABr) and tetradecyltriphenylphosphoniumn bro ride (C).TPBe) were highly pure samples from Lanchaster, England and were used as supplied, Their purities were ascertained by surface tension measurements; surface ten sion —log concentration plot did not show any minimum. Te ple distiled water from an all Pyrex glass apparatus was used for the preparation of solutions, NaCl used was AnalaR grade, Prashant Bahadur et al. Adsorption characteristics and micelle formation of two cationic surfactants 2.2 Methods 221 Surface terson ‘The surface tension of single and mixed surfactants in water and aqueous salt solutions was determined. by Using the drop mumber method. All measurements were carried out at 30°C. The CMC values were determined at sharp break points in surface tension against logarithm fof concentration curves for individual and mixed surfac- tants 222 Conductance Conductometric measurements were made with a digital conductivity meter (Phillips, India) using a dip-type cell in the temperature range 25—40°C. All measurements were done in a jacketed vessel, which was maintained at the 3p propriate temperature (20:1 °C), The errors in the conduc- tance measurements were within £0.5%, The conductance Was measured after thorough mixing and temperature equ Iibrium at each dilution. 33 Results and Discussion ‘The surface tension (7) for surfactants C\yTABE and CyaTPBr were measured for a range of concentrations above ie etc rg, sng nr toe eon ne 830 (ey curas (a caer | Fal tt rt Figure 2, ots pei cndcty vrs concenttion of CTAB n Vite at iter empeate (@) 25°C (a) 50°C) 39°C (A) AO a eae [ae [ven | a | Table 1 tera Popes of Coon Suaants in Water at SDC and below the eritical micelle concentration (CMC): the EMC was determined from the log C plots (Figure I). ‘These plots show a decrease in surface tension, which is fol lowed by almost a constant value with a further increase in concentration of surfactants after the CMC, The CMCs of Surfactants determined in this way are recorded in Table whieh is in close agreement with the CMC data reported in Iiterature (37). ‘The area occupied by the surfactant molecules in A’, at the airwater interface at saturation monolayer was st rmated using the surface tension (y) data at temperature T and the Gibbs adsorption isotherm 1 (ar "apr (atte) ° where Tis surface excess, R is the universal gas constant, C fs the concentration ofthe surfactant and n is taken as 2 be Cause of the ionie nature ofthe surfactants. The values of area/molecule obtained are recorded in Table 1. (Cy TABr and Cy,TPBr have the same hydrophobic chain length but differ only in polar head group size. Despite of having very bulky polar head group, CysTPBr has quite low value of CMC (0.6 mM) as compared t0 Cy,TABr (398 mM) Which can be explained on the basis that the presence of three phenyl groups in the polar head group region of CutPBr which may impart additional hydrophobicity and helps it to undergo micelle formation more favorably. For cationie surfactants with the same head group area but dif ferent chain length of counter ion, the area values remain ‘essentially the same. Since the area per molecule at the in- terface is primarily influenced by head group size 2 larger value of area pet molecule for CyeTPBr (622 A) than {CysTABr (51.1 A) can be anticipated ‘Conductivity measurements were performed in order to evaluate the CMC and the degree of counterion dissociation (G0). This known that the specific conductivity is linearly cor related tothe surfactant concentration in both the premicel- Jar and in the postmicellar regions, in the manner that the slope in the premicellar region is greater than that in the postmicellar region. The intersection point between the two Straight lines gives the CMC while the ratio between the slopes of the postmicellar region to that in the premicellar region gives the degree of counter ion dissociation, Conduc tance data for solutions of Cy.TABr and C,

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