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Apparent molal heat capacities of transfer from H2O to D2O of tetraalkylammonium bromides

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Abstract

The volumetric specific heats (in J-K−1-cm−3) of tetraalkylammonium bromides (R 4 NBr) have been measured at 25°C in the concentration range 0.02 to 0.4 aquamolal in H 2 O and D 2 O with a differential flow microcalorimeter. The apparent molal heat capacities φc, calculated from the specific heats and known densities, were fitted with the equation φc=φ oc +Acm1/2+Bcm whereA c is the Debye-Hückel limiting slope andB c is an adjustable parameter.

The standard heat capacity of transfer ΔC optr =φ oc (D 2 O-φ oc (H 2 O) of R 4 NBr is positive forR equal ton-propyl andn-butyl and negative for methyl and ethyl. Except for Me 4 NBr in H 2 O, allB c are negative and become more so as the size of the cation increases;B c is usually more negative in D 2 O. These results can be interpreted with a two-state model for water and show that a positive ΔC optr is evidence that the solute is an overall structure maker, while a negative value indicates a net structure breaker. The negativeB c is consistent with the existence of strong solute-solute structural (mostly hydrophobic-hydrophobic and hydrophobic-hydrophilic) interactions in the solution.

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  1. Department of Chemistry, Université de Sherbrooke, Sherbrooke, Québec, Canada

    P. R. Philip & J. E. Desnoyers

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  1. P. R. Philip
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Philip, P.R., Desnoyers, J.E. Apparent molal heat capacities of transfer from H2O to D2O of tetraalkylammonium bromides. J Solution Chem 1, 353–367 (1972). https://doi.org/10.1007/BF00715993

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  • DOI: https://doi.org/10.1007/BF00715993

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