Abstract
Excess molar volumes and relative permittivities at a frequency of 30 kHz were determined precisely for the binary mixtures of 1-alkanols, C n H2n+1OH for n = 1 to 10, with cyclohexane or n-heptane to the mole fraction of 1-alkanol, x, to 0.1 at a temperature of 298.15 K. Apparent dipole moments, μ, of the 1-alkanols were calculated by using the Frohlich equation, and the limiting values, μ0, were determined by extrapolating to infinite dilution. The solvent effect on μ0 was very small. The value of μ0 was largest in methanol and decreased with increasing n. It was found that the alkanols were isolated up to x ≈ 0.003. The threshold of molecular interaction beyond this critical mole fraction was ascertained by means of FT-IR spectra. The dipole moments of the 1-alkanols for n = 1–4 were evaluated by ab initio calculations. The average values of μ0 for the rotational configurations calculated by assuming the Boltzmann distribution agreed excellently with the observed ones. The excess partial molar volumes of 1-alkanols determined at the infinite dilution depended on n as well as the solvent. These results are discussed from the viewpoint of the interactions between the solute and solvent molecules.
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References
C. P. Smith, Dielectric Behavior and Structure (McGraw-Hill, New York, 1955).
R. Tanaka, H. Tsuzuki, K. Okazaki, and T. Kinoshita, Fluid Phase Equilb. 123, 131 (1996).
H. T. French, M. Koshla, and K. N. Marsh, J. Chem. Thermodyn. 20, 1175 (1988).
R. Tanaka and T. Yokoyama, J. Solution Chem. 33, 1061 (2004).
A. J. Treszczanowicz and G. C. Benson, J. Chem. Thermodyn. 9, 1189 (1977).
A. J. Treszczanowicz and G. C. Benson, J. Chem. Thermodyn. 10, 967 (1978).
J. A. Riddick, W. B. Bunger, and T. K. Sakano, Organic Solvents. Physical Properties and Methods of Purification, 4th edn., Techniques of Chemistry, Vol. II [Wiley (interscience), New York, 1986].
R. Mehra, Proc. India Acad. Sci. (Chem. Sci.) 115, 147 (2003).
C. Klofutar and T. Nemec, J. Solution Chem. 25, 1151 (1996).
M. Takenaka, R. Tanaka, and S. Murakami, J. Chem. Thermodyn. 12, 849 (1980).
K. N. Marsh and C. Burfitt, J. Chem. Thermodyn. 7, 955 (1975).
R. Tanaka, O. Kiyohara, P. J. D’Arcy, and G. C. Benson, Can. J. Chem. 53, 2262 (1975).
H. Frohlich, Trans. Faraday Soc. 44, 238 (1948).
J. G. Kirkwood, J. Chem. Phys. 7, 911 (1939).
R. H. Stokes and K. N. Marsh, J. Chem. Thermodyn. 8, 709 (1976).
M. Costas and D. Patterson, J. Chem. Soc., Faraday Trans. 1 81, 635 (1985).
R. Tanaka, B. Luo, G. C. Benson, and B. C.-Y. Lu, Thermochim. Acta 127, 15 (1988).
L. G. Wesson, in Tables of Electric Dipole Moments (Massachusetts Institute of Technology, Technology Press, Cambridge, MA, 1948).
K. L. Ramaswamy, Proc. Ind. Chem. Soc. A4, 108 (1936).
S. W. Peterson and W. H. Rodebush, J. Phys. Chem. 32, 709 (1928).
M. Kubo, Sci. Papers Inst. Phys. Chem. Res. Tokyo 27, 65 (1935).
L. Onsager, J. Am. Chem. Soc. 48, 1486 (1936).
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, N. Rega, P. Salvador, J. J. Dannenberg, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle, and J. A. Pople, Gaussian 98, Revision A.11.4 (Gaussian, Inc., Pittsburgh, PA, 2002).
(a) C. Leem, W. Yang, and R. G. Par, Phys. Rev. B, 37, 758 (1988).
(b) B. Miehlich, A. Savin, H. Stoll, and H. Preuss, Chem. Phys. Lett. 157, 200 (1989).
(c) A. D. Becke, J. Chem. Phys. 98, 5648 (1993).
R. Ditchfield, W. J. Hehre, and J. A. Pople, J. Chem. Phys. 54, 724 (1971).
G. Rauhut and P. Puly, J. Phys. Chem. 99, 3093 (1995).
J. B. Foresman and A. Frisch, Exploring Chemistry with Electronic Structure Methods, 2nd edn. [Gaussian Inc., Pittsburgh, PA, 1996].
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EL-Hefnawy, M., Sameshima, K., Matsushita, T. et al. Apparent Dipole Moments of 1-Alkanols in Cyclohexane and n-Heptane, and Excess Molar Volumes of (1-Alkanol + Cyclohexane or n-Heptane) at 298.15 K. J Solution Chem 34, 43–69 (2005). https://doi.org/10.1007/s10953-005-2072-1
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DOI: https://doi.org/10.1007/s10953-005-2072-1