Abstract
Apparent molar volumes Vφ and heat capacities Cp,φ of NaCl, KCl, KNO3, AgNO3, KI, NaBPh4 and Ph4PCl have been measured in acetonitrile (AN)-water mixtures up to xAN=0.25 by flow densitometry and flow microcalorimetry. Limited data have also been obtained for NaF, LiCl and KBr up to x AN =0.15. Single ion volumes and heat capacities of transfer were obtained using the assumption ΔtXφ(PH4P+) = ΔtXφ(BPh4-) where X=V or C p and ΔtXφ is the change in Xφ for a species on transfer from H2O to AN-H2O mixtures. Volumes and heat capacities for simple salts show relatively little dependence on solvent composition. However, ΔtXφ for simple ions show more pronounced variations, exhibiting at least one extremum. These extrema are similar to but much less pronounced than those derived previously for ions in t-butanol-water mixtures. Surprisingly little correlation is found between the present data and other thermodynamic transfer functions. This is attributed to the predominance of ion-solvent over solvent-solvent interactions in AN-H2O solutions. ΔtVφ and ΔtCp,φ for the silver ion differ markedly from those of the alkali metal ions as a result of the well-known specific interaction between Ag+ and AN.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Y. Marcus,Ion-Solvation (Wiley, New York, 1985).
B. G. Cox and W. E. Waghorne,Chem. Soc. Rev. 381 (1980).
Y. Marcus,Rev. Anal. Chem. 5, 53 (1981).
B. G. Cox, A. J. Parker, and W. E. Waghorne,J. Phys. Chem. 78, 1731 (1974). (1974).
B. G. Cox, R. Natarajan, and W. E. Waghorne,J. Chem. Soc. Faraday Trans. I 75, 86 (1979).
E. De Valera, D. Feakins, and W. E. Waghorne,J. Chem. Soc. Faraday Trans. I 79, 1061 (1983).
Y. P. Handa and G. C. Benson,J. Solution Chem. 10, 291 (1981).
G. C. Benson, P. J. D'Arcy, and Y. P. Handa,Thermochim. Acta 46, 295 (1981).
R. Diguet,Chemical Reactivity in Liquids (Plenum, New York, 1988) p. 105.
A. J. Parker, B. W. Clare, and R. P. Smith,Hydrometallurgy 4, 233 (1979).
A. J. Parker,Pure Appl. Chem. 53, 1437 (1981).
B. W. Clare, P. Singh, P. Mangano, A. J. Parker, and D. M. Muir,Austral. J. Chem. 36, 1687 (1983).
P. Singh, I. D. MacLeod, and A. J. Parker,Austral. J. Chem. 36, 1675 (1983).
M. H. Abraham and Y. Marcus,J. Chem. Soc. Faraday Trans. I 82, 3255 (1986).
G. T. Hefter, J.-P. E. Grolier, and A. H. Roux,J. Solution Chem. 18, 229 (1989).
E. Wilhelm, J.-P. E. Grolier, and M. H. Karbalai Ghassemi,Ber. Bunsenges. Phys. Chem. 81, 925 (1977).
J.-P. E. Grolier, E. Wilhelm, and M. H. Hamedi,Ber. Bunsenges. Phys. Chem. 82, 1282 (1978).
L. Avedikian, G. Perron, and J. E. Desnoyers,J. Solution Chem. 4, 331 (1975).
G. S. Kell,J. Chem. Eng. Data 12, 66 (1967).
H. F. Stimson,Am. J. Phys. 23, 614 (1955).
C. Treiner,Can. J. Chem. 55, 682 (1977).
F. J. Millero,Chem. Rev. 71, 147 (1971).
C. Jolicoeur, P. R. Philip, G. Perron, P. A. Leduc, and J. E. Desnoyers,Can. J. Chem. 50, 3167 (1972).
O. Enea, P. P. Singh, E. M. Woolley, K. G. McCurdy, and L. G. Hepler,J. Chem. Thermodyn. 9, 731 (1977).
J. E. Desnoyers, C. De Visser, G. Perron, and P. Picker,J. Solution Chem. 5, 605 (1976).
G. C. Allred and E. M. Woolley,J. Chem. Thermodyn. 13, 147 (1981).
M. R. J. Dack, K. J. Bird, and A. J. Parker,Austral. J. Chem. 28, 955 (1978).
R. Zana, G. Perron, and J. E. Desnoyers,J. Solution Chem. 8, 729 (1979).
C. De Visser, W. J. M. Heuvelsland, L. A. Dunn, and G. Somsen,J. Chem. Soc. Faraday Trans. I. 74, 1159 (1978).
J. I. Kim,Bull. Soc. Chim. Belg. 95, 435 (1986); and references cited therein.
J. I. Lankford and C. M. Criss,J. Solution Chem. 16, 753 (1987).
K. M. Kale and R. Zana,J. Solution Chem. 6, 733 (1977).
G. T. Hefter and P. J. McLay,J. Solution Chem. 17, 535 (1988).
L. G. Hepler,J. Phys. Chem. 61, 1426 (1957).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Hefter, G.T., Grolier, J.P.E., Roux, A.H. et al. Apparent molar heat capacities and volumes of electrolytes and ions in acetonitrile-water mixtures. J Solution Chem 19, 207–223 (1990). https://doi.org/10.1007/BF00650455
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00650455