Abstract
The partial molal heats of solution ΔH os and the partial molal heat capacities of solution ΔC op of the bolaform salts [Et3N(CH2)nNEt3]Br2 and [allyl3N(CH2)nNallyl3]Br2 have been obtained at infinite dilution in dimethylsulfoxide (DMSO). A comparison of these data with the results of previous thermodynamic studies of the same solutes in aqueous solvents has been carried out. The observed differences have been interpreted in terms of solute-induced solvent structural effects occurring in aqueous solvent media. Partial molal heat capacities of the bolaform salts at infinite dilution in DMSO, H2O, and D2O have been calculated from ΔC op data and previously reported values of the heat capacities of the crystalline state. The data clearly show that the structure-promoting capabilities of these salts in aqueous solvents increase with increasing hydrocarbon content. A comparison of contributions to partial molal heat capacities of methylene groups in the bolaform and R4N+ series of salts reveals that similarities exist between the solvation effects of CH2 groups in the normal alkyl chain of the R4N+ cations and in the bridging alkyl chain of the bolaform cation.
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This paper was taken from the work submitted by John A. Burns to the College of Graduate Studies of the University of Saskatchewan, Saskatoon, Canada, in partial fulfillment of the requirements for the Degree of Doctor of Philosophy.
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Burns, J.A., Verrall, R.E. Thermodynamics of bolaform electrolytes. IV. Enthalpies and partial molal heat capacities in H2O, D2O, and dimethylsulfoxide. J Solution Chem 4, 369–381 (1975). https://doi.org/10.1007/BF00645570
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DOI: https://doi.org/10.1007/BF00645570