Effects of Temperature and Emulsifier Concentration on α-Tocopherol Distribution in a Stirred, Fluid, Emulsion. Thermodynamics of α-Tocopherol Transfer between the Oil and Interfacial Regions

The combined linear sweep voltammetry (LSV)/pseudophase kinetic model method was used to obtain the first estimates of the free energies, enthalpy, and entropies of transfer of α-tocopherol (TOC) between the oil and interfacial regions of fluid, opaque, emulsions of n-octane, acidic water, and the nonionic surfactant hexaethyleneglycol mono dodecyl ether (C₁₂E₆) from the temperature dependence of TOC’s partition constant. Determining structure−reactivity relationships for chemical reactions in emulsions is difficult because traditional methods for monitoring reactions are unsuitable and because the partitioning of reactive components between the oil, interfacial, and aqueous regions of opaque emulsions are difficult to measure. The dependence of the observed rate constant, k_obs, for the reaction of an arenediazonium probe, 16-ArN₂⁺, with TOC was determined as a function of C₁₂E₆ volume fraction. The pseudophase kinetic model was used to estimate the interfacial rate constant, k_I, and the partition constants of antioxidants between the oil and interfacial, P_O^I, regions in the emulsion from k_obs versus Φ_I profiles. The thermodynamic parameters of transfer from the oil to the interfacial region at a series of temperatures were respectively obtained from the P_O^I values (ΔG_T^0,O→I), by the van’t Hoff method (ΔH_T^0,O→I), and from the Gibbs equation (ΔS_T^0,O→I). The free energy of transfer is spontaneous, and a large positive entropy of transfer dominates a positive enthalpy of transfer, indicating that the TOC headgroup disrupts the structure of the interfacial region in its immediate vicinity upon transfer from n-octane. The methods described here are applicable to any bimolecular reaction in emulsions in which one of the reactants is restricted to the interfacial region and the rate of its reaction with a second component can be monitored electrochemically.