OPEN AND CYCLIC MULTIMERS IN ALCOHOL-SOLUTIONS - A QUANTITATIVE MODEL FOR THE ASSOCIATION AND THE PERMITTIVITY

When plotted versus concentration in an inert solvent, the dielectric Kirkwood g factor of most normal alcohols exhibits a minimum lower than unity followed by a rise up to values larger than unity in the neat alcohol. This behaviour is interpreted by the fact that H-bond association favours cyclic multimers at low concentrations and open multimers at high concentrations. A quantitative model using chain statistics and predicting this behaviour is summarized. A comparison is made between the results of this model and literature data on n-hexan-1-ol diluted in cyclohexane at 25 and 55-degrees-C. From the fitted values of the dissociation constants at these two temperatures it is deduced that the enthalpy for the destruction-formation of a hydrogen bond in this alcohol is about 20 kJ mol-1.