Abstract
ΔC°p values of tetra-alkylammonium halide salts Me4NBr, Me4NI, Et4NBr, Et4NI, Pr4 NBr, Pr4NI and Bu4NBr in aqueous solutions at 30°C have been determined by measuring integral heats of solution at 25 and 35°C ΔC°p values which vary from –16.5 to 179 cal deg.–1 mole–1 are in the increasing order of Me4NI < Me4NBr < Et4NBr ≃ Et4NI < Pr4NBr ≃ Pr4NI < Bu4NBr. Results are discussed in terms of the influence of tetra-alkylammonium halide salts on the water structure. Me4NBr and Me4NI break water structure, while all other tetra-alkylammonium bromide and iodide salts enhance or promote water structure. The influence of R4N+ salts in promoting water structure increases greatly with increase in the size of the alkyl group R. The influence of anions (bromide and iodide) does not appear to be significant in modifying the structure of water. Results from this work support the concept of “cation-cation interactions” in explaining the nature of interaction of tetra-alkylammonium halide salts with water.
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