Abstract
Calorimetrically determined molar enthalpies of solution at infinite dilution in N,N-dimethylformamide and densities of several amides at 25°C are reported. Some of the enthalpies are combined with literature data for enthalpies of vaporization to obtain molar enthalpies of solvation. Relations are found between the enthalpies of solution and the size, and between these enthalpies and the enthalpic pair interaction coefficients of the solute molecules. These relations are quantified by an extension of the random contact point approach. This additivity scheme is also applied to enthalpies of solvation, vaporization and cavity formation. With this approach thermodynamic quantities of solution, solvation, vaporization, and pair interaction of different solutes and solvents are correlated with a single consistent set of group interaction parameters. In addition, the random contact point model provides a simple method to calculate thermodynamics of cavity formation which appear to be as reliable as those of the much more complicated scaled particle theory.
Similar content being viewed by others
References
G. C. Kresheck and I. M. Klotz,Biochemistry 8, 8 (1969).
O. D. Bonner, J. M. Bednarek, and R. Arisman,J. Am. Chem. Soc. 99, 2898 (1977).
H. E. Kent, T. H. Lilley, P. D. Milburn, M. Bloemendal, and G. Somsem,J. Solution Chem. 14, 101 (1985).
M. Bloemendal and G. Somsem,J. Solution Chem. 12, 83 (1983);ibid 13, 281 (1984);J. Chem Thermodyn. 19, 1 (1987).
M. Bloemendal, A. H. Sijpkes and G. Somsem,J. Solution Chem. 15, 81 (1986).
A. Ben-Naim and Y. Marcus,J. Chem. Phys. 81, 2016 (1984). This gives references to earlier studies.
A. Ben-Naim, inSolvation Thermodynamics, (Plenum, New York, 1988, in press).
I. Wadsö,Acta Chem. Scand. 19, 1979 (1965).
P. Starzewski, I. Wadsö, and W. Zielenkiewicz,J. Chem. Thermodyn. 16, 331 (1984).
G. Barone, G. Castronuovo, G. Della Gatta, V. Elia, and A. Ionnone,Fluid Phase Equil. 21, 157 (1985).
H. Reiss, H. L. Frisch, and J. L. Lebowitz,J. Chem. Phys. 31, 369 (1959).
H. Reiss,Adv. Chem. Phy. 9, 1 (1964). This give references to earlier studies.
R. A. Pierotti,J. Phys. Chem. 69, 281 (1965).
N. Desrosiers and J. E. Desnoyers,Can. J. Chem. 54, 3800 (1976).
N. Brückl and J. I. Kim,Z. Phys. Chem. N. F. 126, 133 (1981).
R. W. Balk and G. Somsen,J. Chem. Soc. Faraday Trans. I,82, 933 (1986).
C. de Visser, E. van Netten, and G. Somsen,Electrochim. Acta,21, 97 (1976).
A. C. Rouw and G. Somsen,J. Chem. Soc. Faraday Trans. I. 78, 3397 (1982).
P. Picker, E. Tremblay, and C. Jolicoeur,J. Solution Chem. 3, 377 (1974).
H. C. Zegers and G. Somsen,J. Chem. Thermodyn. 16, 225 (1984).
C. de Visser, W. J. M. Heuvelsland, L. A. Dunn and G. Somsen,J. Chem. Soc. Faraday Trans. I 74, 1159 (1978).
C. de Visser and G. Somsen,J. Solution Chem. 8, 593 (1979).
H. Z. Zegers and G. Somsen,Fluid Phase Equil. 18, 299 (1984).
J. N. Spencer, R. C. Garrett, F. J. Mayer, J. E. Merkle, C. R. Powell, M. T. Tran, and S. K. Berger,Can. J. Chem. 58, 1372 (1980).
J. N. Spencer, S. K. Berger, C. R. Powell, B. D. Henning, G. S. Furman, M. W. Loffredo, E. M. Rydberg, R. A. Neubert, C. E. Shoop, and D. N. Blauch,J. Phys. Chem. 85, 1236 (1981).
G. Della Gatta, G. Barone, and V. Elia,J. Solution Chem. 15, 157 (1986).
J. M. Corkill, J. F. Goodman, and J. R. Tate,Trans. Faraday Soc. 65, 1472 (1969).
J. Konicek and I. Wadsö,Acta Chem. Scand. 25, 1541 (1971).
M. Bloemendal and G. Somson,J. Solution Chem. accepted.
M. Bloemendal and Y. Marcus,AIChE J. 33, in the press (1987).
A. Bondi,J. Phys. Chem. 68, 441 (1964).
R. Gopal and S. A. Rizoi,J. Ind. Chem. Soc. 43, 179 (1966).
F. Kawaizumi, M. Ohno, and Y. Miyahara,Bull. Chem. Soc. Japan 50, 2229 (1977).
A. A. Miroshnichenko,Zh. Prikl. Khim. 52, 2116 (1979).
M. Sukurai and T. Nakagawa,J. Chem. Thermodyn. 16, 171 (1984).
M. Bloemendal and G. Somson,J. Am. Chem. Soc. 107, 3426 (1985).
A. C. Rouw and G. Somsen,J. Chem. Thermodyn. 13, 67 (1981).
K. Suri, J. J. Spitzer, R. H. Wood, E. G. Abel, and P. T. Thompson,J. Solution Chem. 14, 781 (1985).
V. Abate, G. Barone, P. Cacace, G. Castronuovo, and V. Elia,J. Mol. Liq. 27, 59 (1983).
D. Hallen, S. O. Nilsson, W. Rotchild, and I. Wadsö,J. Chem. Thermodyn. 18, 429 (1986).
J. D. Cox and G. Pilcher,Thermochemistry of Organic and Organometallic Compounds, (Academic Press, London, 1970).
F. G. Beilstein,Handbuch der Organische Chemie andErgänzungswerke, Vol. EIV. 2 and Vol. EIV. 4 (Springer Verlag, Berlin, 1975 and 1977).
O. Shuro,Vapour Pressure Data Book, (Publ. Co., Tokyo, 1976).
M. V. Loch and B. F. Sagan,J. Chem. Soc. B 1966, 690 (1966).
C. de Visser, H. J. M. Grunbauer, and G. Somsen,Z. Phys. Chem. N.F. 97, 69 (1975).
P. P. S. Saluja, T. M. Young, R. F. Rodewald, F. H. Fuchs, D. Kohl, and R. Fuchs,J. Am. Chem. Soc. 99, 2949 (1977).
I. Wadsö,Acta Chem. Scand. 20, 544 (1966).
A. C. Rouw and G. Somsen,J. Solution Chem. 10, 533 (1981).
A. J. Easteal and L. A. Woolf,J. Chem. Thermodyn. 15, 195 (1983).
B. A. Cosgrove and J. W. Walkley,Can. J. Chem. 60, 1896 (1982).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Bloemendal, M., Marcus, Y., Booij, M. et al. Enthalpies of solution and solvation of amides in N,N-dimethylformamide: Application of the random contact point approach. J Solution Chem 17, 15–33 (1988). https://doi.org/10.1007/BF00651850
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00651850