Abstract
The partial molal heats of solution at infinite dilution, ΔH os , of bolaform salts [Et3N(CH2)nNEt3]Br2 and [allyl3N(CH2)nNallyl3]Br2, have been measured in H2O and D2O at 25°C using a solution calorimeter. The values of ΔH os were endothermic for almost all of the compounds studied. Values of ΔH os were obtained as a function of temperature for several homologs in H2O and D2O. Positive ΔC op values obtained from least-squares analyses of the ΔH os vs T data show an almost linear dependence on the number of methylene groups between the nitrogen centers. Whereas the enthalpy of transfer from H2O to D2O is small and endothermic, relatively large positive heat capacity of transfer data, increasing with increased hydrocarbon content of the salts, were observed. The ability of the bolaform cation to act as a model for cation-cation pairing in R4NX systems is discussed.
Similar content being viewed by others
References
R. L. Kay and D. F. Evans,J. Phys. Chem. 70, 366 (1966).
S. Lindenbaum and G. E. Boyd,J. Phys. Chem. 68, 911 (1964).
W.-Y. Wen and S. Saito,J. Phys. Chem. 68, 2639 (1964).
F. Franks and H. T. Smith,J. Phys. Chem. 68, 3581 (1964).
F. Franks and H. T. Smith,Trans. Faraday Soc. 63, 2586 (1967).
B. E. Conway, R. E. Verrall, and J. E. Desnoyers,Trans. Faraday Soc. 62, 2738 (1966).
W.-Y. Wen and K. Nara,J. Phys. Chem. 71, 3907 (1967);J. Phys. Chem. 72, 1137 (1968).
T. L. Broadwater and D. F. Evans,J. Phys. Chem. 73, 164 (1969).
S. Lindenbaum,J. Phys. Chem. 73, 4334 (1969).
C. V. Krishnan and H. L. Friedman,J. Phys. Chem. 74, 2356 (1970).
T. L. Broadwater and D. F. Evans,J. Phys. Chem. 73, 3985 (1969).
Y.-C. Wu and H. L. Friedman,J. Phys. Chem. 70, 2020 (1966).
H. L. Friedman,J. Phys. Chem. 71, 1723 (1967).
C. V. Krishnan and H. L. Friedman,J. Phys. Chem. 73, 1572 (1969).
C. V. Krishnan and H. L. Friedman,J. Phys. Chem. 73, 3934 (1969).
C. V. Krishnan and H. L. Friedman,J. Phys. Chem. 74, 3900 (1970).
P. R. Philip and J. E. Desnoyers,J. Solution Chem. 1, 353 (1972).
E. M. Arnett and J. J. Campion,J. Am. Chem. Soc. 92, 7097 (1970).
C. Perron and J. E. Desnoyers,J. Chem. Eng. Data (in press).
E. M. Arnett, W. G. Bentrude, J. Burke, and P. M. Duggleby,J. Am. Chem. Soc. 87, 1541 (1965).
R. J. Irving and I. Wadsö,Acta Chem. Scand. 18, 195 (1964).
J. A. Burns and R. E. Verrall, to be published.
H. Ruterjans, H. F. Schreiner, U. Sage, and T. H. Ackermann,J. Phys. Chem. 73, 986 (1969).
B. E. Conway, R. E. Verrall, and J. E. Desnoyers,Z. Physik. Chem. 230, 157 (1965).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Burns, J.A., Verrall, R.E. Thermodynamics of bolaform electrolytes. I. Heat capacities and enthalpies in H2O and D2O. J Solution Chem 2, 489–502 (1973). https://doi.org/10.1007/BF00644876
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00644876