Classification of calorimetric titration plots for alkyltrimethylammonium and alkylpyridinium cationic surfactants in aqueous solutions

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Abstract
Calorimetric titration plots for deaggregation of micelles formed by alkylpyridinium and alkyltrimethylammonium surfactants are classified into three types, A, B and C, depending on the shape of the plot of the enthalpy of dilution as a function of surfactant concentration. For Type A plots the recorded heat of injection q changes sharply between two parts of the titration curve over which the recorded heats are effectively independent of the composition of the solution in the sample cell. For Type B plots, the change is less sharp and both parts of the plot show dependences of heat q on solution composition, a pattern accounted for in terms of solute–solute interactions. Type C plots are complicated, in that no sharp change in q is recorded, the complexity of the plots being accounted for in terms of micelle–monomer equilibria over a range of surfactant concentrations and related enthalpies of deaggregation.

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