Micelle formation conductometric determination of the CMC (critical micellication concentration) of a surfactant

Theory: Surfactants constitute the most important group of detergent components. Generally, these are water-soluble surface-active agents comprised of a hydrophobic portion, usually a long alkyl chain, attached to hydrophilic or water solubility enhancing functional groups. Surfactants can be categorized according to the charge present in the hydrophilic portion of the molecule (after dissociation in aqueous solution): nonionic surfactants, ampholytic surfactants, cationic surfactants anionic surfactants

Sodium dodecylsulfate (SDS)

All surfactants possess the common property of lowering surface tension when added to water in small amounts. The characteristic discontinuity in the plots of surface tension against surfactant concentration can be experimentally determined. The corresponding surfactant concentration at this discontinuity corresponds to the critical micelle concentration. Another method to determine the CMC is to be seen in conductivity measurements, which also show characteristic plots and discontinuities of specific conductivity versus surfactant concentration. At surfactant concentrations below the CMC, the surfactant molecules are loosely integrated into the water structure. In the region of the CMC, the surfactant-water structure is changed in such a way that the surfactant molecules begin to build up their own structures. Due to the limited solubility of surfactants in water, aggregates are formed in which the hydrophobic or hydrophilic sections of the surfactant are stuck together. The micelle may be represented as a globular cylindrical or ellipsoidal cluster of individual surfactant molecules in equilibrium with its monomers. The reverse orientation of the hydrophilic and hydrophobic portion of the surfactant in a

hydrocarbon medium leads to reversed micelles. Planar bilayers or small unilamellar vesicles are also formed. The extraordinary variety of the phase behavior of surfactants in solution can further be broadened by the inclusion of additives or cosurfactants. The micelle formation process can be described by the following equation: m * S <=> Sm

where m is the average association number S the concentration of monomeric surfactant and Sm the concentration of micelles.

The surfactants are of widespread importance in the detergent industry, in emulsification, lubrication, catalysis, tertiary oil recovery, and in drug delivery. In biochemistry, the practical as well as theoretical importance of surfactants may be illustrated with the following examples: Surfactants have allowed the investigation of molecular properties of membrane proteins and lipoproteins, acting as solubilizing agents and as probes for hydrophobic binding sites. In high performance liquid chromatography, common techniques such as ionexchange HPLC, reversed-phase HPLC and size exclusion-HPLC may require surfactants to solubilize membrane proteins. Ionpair HPLC requires surfactants as reagents in order to achieve the separation conditions (ionpairing).

Experimental part: The conductivity of an aqueous sodium dodecylsulfate (SDS)- solution is measured in dependence on concentration. Chemicals: 0.1 M SDS solution, NaCl solution, MgCl2 solution Procedure : 1) Add to 100 ml water 0.1 M SDS-solution in steps of 0.5 ml (in summary 15 ml), after that 10 ml SDS- solution in 5 ml steps. After each adding the solution has to be thoroughly stirred and conductivity () is measured. 2) Add to 100 ml NaCl- solution (5 .10-3 M, 5 . 10-2 M, 1 . 10-2 M) the same steps as given in 1). 3) = f(c) is measured as given in 2) for a 0.1 M SDS-solution in 1 . 10-3 CaCl2.

Discussion: 1) Plot vs. the volume added and determine the cmc (in Mol/l) of SDS from the point of intersection of both straight lines. 2) Discuss the influence of concentration and valency of the electrolyte on the cmc of SDS.