Abstract
The enthalpy of dilution of all one-and two-solute aqueous mixtures of a series of compounds were measured from about 0.2 to 2.0 mole-kg−1 at 25°C. The compounds included in the study wereN-methylformamide,N-methylacetamide,N-methylpropionamide,N-butylacetamide, urea, ethylene glycol, pentaerythritol, glucose, and sucrose. The results of the enthalpy measurements were used to calculate the pairwise enthalpy of interaction for each compound with all the other compounds. A simple additivity principle is used to correlate the data. The principle assumes that each functional group on one molecule interacts with every functional group on the other molecule and that each of these interactions has a characteristic effect on the enthalpy that is independent of the positions of the functional groups in the two molecules. The resulting equation gives a rough but useful correlation of the results. Of the six interactions between the CH2, CONH, and CHOH functional groups, the CONH−CONH interaction is the strongest, the CHOH−CHOH interaction is the weakest, and the CH2−CH2 interaction is about equal in magnitude to the rest of the interactions. Thus, the CH2−CH2 and CONH−CONH are not the only interactions making important contributions to the enthalpy of a wide variety of systems.
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References
J. J. Kozak, W. S. Knight, and W. Kauzmann,J. Chem. Phys. 48, 675 (1968).
R. B. Cassel and R. H. WoodJ. Phys. Chem. 78, 2465 (1974).
H. L. Friedman and C. V. Krishnan,J. Solution Chem. 2, 119 (1973).
F. Franks, M. Pedley, and D. S. Reid,J. Chem. Soc. Faraday Trans. I 72, 359 (1976).
M. Roseman and W. P. Jencks,J. Am. Chem. Soc. 97, 631 (1975).
T. H. Lilley and R. P. Scott,J. Chem. Soc. Faraday Trans. 1 72, 184 (1976).
H. Uedaira,Bull. Chem. Soc. Jpn. 45, 3068 (1972).
C. Tanford,The Hydrophobic Effect (John Wiley and Sons, New York, 1973).
E. E. Schrier, M. Pottle, and H. A. Scheraga,J. Am. Chem. Soc. 86, 3444 (1964).
A. Y. Moon, D. C. Poland, and H. A. Scheraga,J. Phys. Chem. 69, 2960 (1965).
D. K. Kunimitsu, A. Y. Woody, E. R. Stimson and H. A. Scheraga,J. Phys. Chem. 72, 856 (1968).
H. Schneider, G. C. Kresheck, and H. A. Scheraga,J. Phys. Chem. 69, 1310 (1965).
G. Nemethy and H. A. Scheraga,J. Phys. Chem. 66, 1773 (1962).
F. Franks and D. S. Reid, inWater, a Comprehensive Treatise, F. Franks, ed. (Plenum Press, New York, 1973), Vol. 2, Chap. 5.
A. Ben-Naim and M. Yaacobi,J. Phys. Chem. 78, 170, 175 (1974);79, 1263 (1975);J. Solution Chem. 2, 425 (1973).
D. G. Oakenfull and D. E. Fenwick,Aust. J. Chem. 26, 2649 (1973);27, 2149 (1974);J. Phys. Chem. 78, 1759 (1974).
J. A. Schellman,C. R. Trav. Lab. Carlsberg, Ser. Chim. 29, 223 (1955).
S. J. Gill, J. Hutson, J. R. Clopton, and M. Downing,J. Phys. Chem. 65, 1432 (1961).
I. M. Klotz and J. S. Franzen,J. Am. Chem. Soc. 84, 3461 (1962).
H. Susi, S. N. Timasheff, and J. S. Ardi,J. Biol. Chem. 239, 3051 (1964).
R. H. Stokes,Aust. J. Chem. 20, 2087 (1967).
G. C. Kresheck and I. M. Klotz,Biochemistry 8, 8 (1969).
G. C. Kresheck,J. Phys. Chem. 73, 2441 (1969).
S. J. Gill and L. Noll,J. Phys. Chem. 76, 3065 (1972).
J. J. Savage, Ph.D. Thesis, University of Delaware, June 1976.
P. T. Thompson, D. E. Smith, and R. H. Wood,J. Chem. Eng. Data 19, 386 (1974).
P. R. Stoesser and S. J. Gill,J. Phys. Chem. 71, 564 (1967).
D. Hamilton and R. H. Stokes,J. Solution Chem. 1, 223 (1972).
F. T. Gucker, Jr., and H. B. Pickard,J. Am. Chem. Soc. 62, 1464 (1940).
E. Lange and H.-G. Markgraf,Z. Elektrochem. 54, 73 (1950).
F. T. Gucker, Jr., H. B. Pickerd, and R. W. Planck,J. Am. Chem. Soc. 61, 459 (1939).
E. Lange and K. Mohring,Z. Elektrochem. 57, 660 (1953).
R. B. Cassel and R. H. Wood,J. Phys. Chem. 78, 2460 (1974).
I. Langmuir,Collec. Symp. Monogr. 3, 48 (1925).
E. J. Cohen and J. T. Edsal,Proteins, Amino Acids and Peptides (Reinhold Publishing Co., New York, 1943).
C. Tanford,J. Am. Chem. Soc. 84, 4240 (1962).
H. Schneider, G. C. Kresheck, and H. A. Scheraga,J. Phys. Chem. 69, 1310 (1965).
E. E. Schrier and E. B. Schrier,J. Phys. Chem. 71, 1851 (1967).
C. V. Krishnan and H. L. Friedman,J. Phys. Chem. 73, 1572 (1969);74, 390 (1970);75, 388 (1971).
J. Konicek and I. Wadsö,Acta Chem. Scand. 25, 1541 (1971).
K. Kusano, J. Suurkuusk, and I. Wadsö,J. Chem. Thermodyn. 5, 757 (1973).
C. H. Spink and I. Wadsö,J. Chem. Thermodyn. 7, 561 (1975).
O. Kiyohara, G. Perron, and J. E. Desnoyers,Can. J. Chem. 53, 2591 (1975).
G. M. Wilson and C. H. Deal,Ind. Eng. Chem. Fundam. 1, 20 (1962).
G. A. Ratclif and K. C. Chao,Can. J. Chem. Eng. 47, 148 (1969).
S. Mizushima, T. Sunanouti, S. Nagakura, K. Kuratani, M. Tsuboi, H. Bala, and O. Fujioka,J. Am. Chem. Soc. 72, 3490 (1950).
M. Davies and D. K. Thomas,J. Phys. Chem. 60, 767 (1956).
R. W. Gurney,Ionic Processes in Solution (Dover, New York, 1953).
H. S. Frank inChemical Physics of Ionic Solutions,B. E. Conway and R. G. Barradas, eds. (Wiley New York, 1966);Z. Phys. Chem. (Leipzig) 228, 364 (1965).
P. S. Ramanathan and H. L. Friedman,J. Chem. Phys. 54, 1086 (1971).
M. J. Mastroianni, M. J. Pikal, and S. Lindenbaum,J. Phys. Chem.,76, 3050 (1972).
J. S. Falcone, Jr., and R. H. Wood,J. Solution Chem. 3, 233 (1974).
C. de Visser and G. Somsen,J. Phys. Chem. 78, 1719 (1974);J. Solution Chem. 3, 847 (1974).
J. E. Desnoyers, G. Perron, L. Avédikian, and J.-P. Morel,J. Solution Chem., in press.
W. Dimmling and E. Lange,Z. Elektrochem. 55, 322 (1951).
F. T. Gucker, Jr., H. B. Pickard, and W. L. Ford,J. Am. Chem. Soc. 62, 2698 (1940).
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Savage, J.J., Wood, R.H. Enthalpy of dilution of aqueous mixtures of amides, sugars, urea, ethylene glycol, and pentaerythritol at 25°C: Enthalpy of interaction of the hydrocarbon, amide, and hydroxyl functional groups in dilute aqueous solutions. J Solution Chem 5, 733–750 (1976). https://doi.org/10.1007/BF00643457
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DOI: https://doi.org/10.1007/BF00643457