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Surfactants Basic

The document discusses the critical micelle concentration (CMC) of surfactants, explaining how surfactants form micelles above a certain concentration, leading to a constant monomer concentration. It describes the structure of micelles, including their hydrophobic cores and polar head groups, and outlines the thermodynamic parameters involved in micellization, such as free energy, enthalpy, and entropy changes. Additionally, it touches on the role of counterions in micelle formation and the impact of temperature on these processes.

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6 views7 pages

Surfactants Basic

The document discusses the critical micelle concentration (CMC) of surfactants, explaining how surfactants form micelles above a certain concentration, leading to a constant monomer concentration. It describes the structure of micelles, including their hydrophobic cores and polar head groups, and outlines the thermodynamic parameters involved in micellization, such as free energy, enthalpy, and entropy changes. Additionally, it touches on the role of counterions in micelle formation and the impact of temperature on these processes.

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tushern93
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© All Rights Reserved
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1.2.1 The critical micelle concentration (CMC) When surfactant is present in a solution at low concentration, its molecules are randomly distributed as individual monomers. As mentioned before, ,one_ characteristic feature of surfactants is their tendency to adsorb at interfaces. Fig. (1.4) shows sos thatthe surface tension desreases. strongly with-increasing concentration of surfactant molecules in the solution, However, at a certain concentration the decline of surface tension is stopped and its value remains almost constant. This indicates that the surface is saturated by a monolayer of surfactants and no more adsorption sites are Surface tenston [Surfactant] Fig. (1.4): Changes in surface tension and organization of amphiphilic molecules with increasing surfactant concentration. ‘Above that concentration the molecules of surfactant present in the bulk will undergo spontancously self-assembly and form well defined aggregates, called micelles, The concentration above which micelle formation becomes appreciable is known as the critical micelle concentration, abbreviated to CMC. All additional surfactant added ‘above the CMC forms or goes into the micelles. This means that the monomer concentration is constant at and above the CMC. Two factors are involved in the spontaneous formation of micelles. First, the hydrophobic effect causes the nonpolar portion of the molecule to be separated from water and sequestered in the interior of Scanned with CamScanner coups determine how closely the the structure. Second, interactions between the head gr C are usually regarded as a 006). In an aqueous d towards the molecules may be packed. Most micelles just above cM 5, 2 spherical association of 50 - 100 surfactant molecules (Tadros solution, the shell of ionic or nonionic polar head groups Is oriente “ i i in Fig. aqueous phase, while the hydrophobic tails aggregate into the core, aS shown in Fig (1.5) (above). . Water Micelle core Qn “@ > Palisade layer Defined number of surfactant monomers Fig.(1.5): The structure of a micelle (above) and reversed micelle (below). The interior of a micelle shows liquid phase properties, such as high mobility of alkyl chains and ability to solubilize water-insoluble molecules. A more polar region consisting of surfactant tails and polar molecules which have penetrated into the micelle interior; this region of a micelle is described as the palisade layer (few carbon atoms deep towards core). The formation of micelle-like aggregates in nonpolar solvents is also possible, although the changes involved in association process must be considerably different from those in aqueous systems. The orientation of the surfactant in the solvent is opposite to that in water, with hydrophobic chains oriented to the bulk and polar heads inside the core. Such a structure is often described as reversed micelle, and is presented in Fig. (1.5) (below). Later, the discussion will be restricted to interfaces involving a liquid phase as in my research, Scanned with CamScanner For more explanation of ionic micelle, a schematic two-dimensional zepreseumasion oF an ionic spherical micelle is shown in Fig. (1.6). In ionic micelles, the surdast potentials are high (Stigter, 1964) and relatively small counterions and the churaed head groups are located in a compact region, known as the Stern layer. which extents from the outer surface of the core to within a few angstroms of the shear surface of the micelle. The compactness of the Stem layer is responsible for the reduction af fie net charge on the micelle, Most of the counterions, are, however, loomed ouside fe shear surface in the Gouy-Chapman electrical double-layer where they wre commiist=is dissociated from the charged aggregate and are able to exchange with ions in the Silk of the solution. Wa (1 6+ Madel of a tvoieal ionic micelle showing the locations of head groups. surfactant trai: Scanned with CamScanner 1.2.2 Structures of micelles in 2 seintion Various miceller shapes are suggested that axe depend on he seocare surfactant, typically the relive size of the head group and el rou. This S ofes described with the critical packing parameter, CPP. defined as: Cpp=VaL where a is the optimal head group ea and V and Lis the volome and eat of he surfactant tail, respectively. Spherical micelles will te formed @ CPR1) 2s shows & Fiz. (17h Lamaiter mice Fig, (1.7): Mstrating the formation of varions structures ia surfactant sctioa with ncresSag surfactant concentration (Bansal etal, 1977} Scanned with CamScanner “Counterion Binding to the Micelles (B=/n): ¢ fraction of counterion bound to a micelle was conductometrically determined as the procedure described and researchers of our laboratory", In this method, the ratio of the pre- and post- micellar slopes (Syand Sp, respectively) of the specific conductance versus concentration plots was the fraction of counter ion dissociated (a) from the micelle!"“""®, The fraction of counterion binding ® was determined by subtracting the value of o. from unity B= (1-a)"’. This is the simplest method to get a fairly q@antitative estimation of an important micellar parameter. The shone Gibbs free one] “ avait ohton ( AG‘) Ls ‘¢ thermodynamic state functions such as the standard free-energy change (AG’,), the enthalpy change (AH), and the entropy change (AS",) during the process of lization were important parameters for the basic understanding of the feasibility of the process 2.5K. Thermodynamic parameters: and its inherent constraints etc. For the ionic surfactants of the 1:1 electrolyte type, the standard free energy of micellization was calculated according to the following equation for drug- surfactant system!" on te a's of pgenclo— phask ae sepmation mode well7t AGm = (1 +B) RT InX cue Q) Wl. aay In which, f, the fraction of counterion binding sues at different temperatures and CMC values in mole fraction units were considered. | ~~ ‘The standard enthalpy change of the processes was calculated using the modified van't Hoff equation 26" AH’n =~ (1+) RP alnX cuc/ OT @) as made to calculate AH’, where values at different temperatures and values of In Xcyc vs. T plot w CMC in mole fraction units were considered. When In Xeye vs. T plots are nonlinear, a tangent Ws drawn through the required point i.e. at each temperature of the plot and the slope of the tangent at each temperature was taken as dlnXcyc /67 to calculate AH, 2617, When In Xaye versus T plots are linear, slope of the straight line was taken as equal to 8 InXaaec 07 6 Scanned with CamScanner ‘The values of venay of standard entropy change, AS’,, of micellization were calculated from the following quation AS’ = (AIP ge AG’) T @) 2.5.4, Enthalpy - entropy compensation phenomena Enthalpy — entropy compensation phenomena in micellization of surfactants in the presence of drugs was obtained using the following regression equation!”™”. AH y= Atty + Te BS’ (6) A linear relation between A/f’n and AS®, indicates entropy-enthalpy compensation for a system. The negative intercept of the compensation line is the intrinsic enthalpy gain, AH". and the slope of the compensation line is the compensation temperature, T., According to the working scheme of Lumry and Rajender, the micellization can be described as consisting of two-part processes: @ “chemical” part process i.e. aggregation of the hydrocarbon tails of surfactant molecules to form micelle (12) and “solvation” part process ic. the arrangement of water molecules surrounding the micelles. The latter exhibits the compensation phenomenon. 7, characterizes the solute-solvent interactions i.e. considered as a measure of the compensation part process. AH™,, characterizes the/#6lute-solute interaction i.e. considered as an index of the chemical part process of micellization, The values of AG’, were found to be negative for pure CTAB and drug-CTAB systems. The large negative values of AG’, at different temperatures indicate that drugs supported surfactant micelles formation processes were thermodynamically spontaneous. The negative AG’, values for LFM- CTAB systems were slightly lower than those of pure CTAB whereas the negative AG. values of CFEL-CTAB were found to higher in magnitude compared to those of pure CTAB. Thus CFH supported micellization might be more spontaneous than that of LFM-CTAB system. For both CFH- CTAB and LFM-CTAB systems the value AH? in aqueous medium at 298.15 K were positive, the sign of the values change from positive to negative and the negative values increase with increasing temperature, The AS, values were positive and the values decrease with increase of temperature. The AS’, values of drug-CTAB system were lower in magnitiude compared to those of pure CTAB system at the corresponding temperature. ‘Thus values of AS’, and AH’, indicate that the micellization of this system is entropically controlled at lower temperatures whereas it becomes both entropy and enthalpy controlled at higher temperatures. The negative AH’n, and positive AS", values for drug- CTAB systems indicate that in addition to hydrophobic, electrostatic interactions also play a vital role in the aggregation of drug with CTAB during formation of drug supported CTAB micelles "™, The hydrophobic contribution decreases while the electrostatic interaction increases with rise of temperature, keeping the negative 4G°, values nearly constant over the range of temperature studied. However, the values of AM’, change significantly from positive to negative with gradual rise of temperature, Such a change in the sign of ‘AH’, was also observed for a number of ionic surfactants mein Scanned with CamScanner Wy doophiic gobi MURR eve HHUA TSAR Washer: “IMS erp eyed seal em bir cugfer te call & WANE ) ee inevesting- use. of micolles of omiooe gurs-faekonl Ahab invslvta bork theie edeopbion od sth tein propesti vo Ys for the removal of pallubents dyath meraluc tos and Orga c. rad enofcd Frvn ~ > ALi vons bind to the negahvely chor ged Jursface of mreelles of amipal audactants , ome orsgenni « metenial uz Aowoikkzed in dhe tndevjor of TAR yrrales + > Ke meallar adiition y's foeced thesveghy an ubbrag thechion mmombyane w}}f, puses eemodh, enor, Se Dock the Qssage of Re aneeetles with theile associated mefalle Fons amd GaN, meter af. Scanned with CamScanner

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