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Volumn 13, Issue , 2007, Pages 485-630

An Examination of Linear Solvation Energy Relationships

Author keywords

HBA basicity; HBD acidity; Linear solvation energy relationships; Solvent effects; Solvent polarity

Indexed keywords

SOLVENTS;

EID: 84983085435     PISSN: None     EISSN: None     Source Type: Book    
DOI: 10.1002/9780470171929.ch6     Document Type: Chapter
Times cited : (877)

References (267)
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    • The reaction studied was the quaternarization of triethylamine by ethyl iodide at 100 °C [N. Menschutkin, Z. Physik. Chem., 6, 41 (1890)]. Menschutkin's first discussion on solvent effects dealt with the reactions between acetic anhydride and alcohols [Z. Physik. Chem., I. 611 (1887)]. The catalytic role of solvents was already recognized in 1862 by Berthelot and Péan de Saint Gilles in their Recherches sur les Affinités [see, e.g., H. G. Grimm, H. Ruf, and H. Wolff.Z. Physik. Chem. BI3.301 (1931)].
    • The reaction studied was the quaternarization of triethylamine by ethyl iodide at 100 °C [N. Menschutkin, Z. Physik. Chem., 6, 41 (1890)]. Menschutkin's first discussion on solvent effects dealt with the reactions between acetic anhydride and alcohols [Z. Physik. Chem., I. 611 (1887)]. The catalytic role of solvents was already recognized in 1862 by Berthelot and Péan de Saint Gilles in their Recherches sur les Affinités [see, e.g., H. G. Grimm, H. Ruf, and H. Wolff.Z. Physik. Chem. BI3.301 (1931)].
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    • See, e.g., Ref 26
    • See, e.g., Ref 26, pp. 239-240.
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    • Laidler, using a different treatment also calculates a somewhat faster increase of
    • Laidler, using a different treatment, also calculates a somewhat faster increase ofK. J. Laidler, Can. J. Chem., 37. 138 (1959).
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    • This is the original procedure used by Kirkwood to develop Equation 14. See also, e.g., M. Jauquet and P. Laszlo, Part I, Chapter IV, Wiley, New York
    • This is the original procedure used by Kirkwood to develop Equation 14. See also, e.g., M. Jauquet and P. Laszlo, in Solutions and Solubilities, Part I, Chapter IV, Wiley, New York, 1974.;.
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    • Ref. 26, Chapter 23.
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    • Self-association of DMSO pure in CCU, e.g.
    • Self-association of DMSO pure and in CCU, e.g., R. H. Figueroa, E. Roig, and H. H. Szmant, Spectrochim. Acta, 22, 587 (1966);.
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    • Figueroa, R.H.1    Roig, E.2    Szmant, H.H.3
  • 35
    • 84983025849 scopus 로고    scopus 로고
    • This technique has been used to determine the dimerization constants of ketones and nitriles in cyclohexane and carbon tetrachloride solutions
    • This technique has been used to determine the dimerization constants of ketones and nitriles in cyclohexane and carbon tetrachloride solutions:.
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    • University of Poitiers (France)
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    • Self-association of N-N.,dimethylformamide, N.,N-dimethylacetamide, and N-methylpyr-rolidone
    • Self-association of N-N, dimethylformamide, N,N-dimethylacetamide, and N-methylpyr-rolidone, T. Yonezawa and I. Morishima, Bull. Chem. Soc Japan, 39, 2346 (1966).
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    • Self-association of ketones, esters, amides, nitriles, nitrocompounds
    • Self-association of ketones, esters, amides, nitriles, and nitrocompounds, H. Saito, Y. Tanaka, S. Nagata, K. Nukada, Can. J. Chem., 51, 2118 (1973).
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    • Saito, H.1    Tanaka, Y.2    Nagata, S.3    Nukada, K.4
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    • Self-association of ρ-fluoronitrobenzene in carbon tetrachloride, Symposium on Linear Free Energy Correlations, Reprints of Papers, Durham, also, cf. Ref. 32
    • Self-association of ρ-fluoronitrobenzene in carbon tetrachloride, R. W. Taft, G. B. Klingensmith, E. Price, and I. R. Fox, Symposium on Linear Free Energy Correlations, Reprints of Papers, Durham, 1964, pp. 275-278; also, cf. Ref. 32.
    • (1964) , pp. 275-278
    • Taft, R.W.1    Klingensmith, G.B.2    Price, E.3    Fox, I.R.4
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    • [C.A. 79. 5767a (1973)] Self-association of aromatic nitrocompounds
    • Self-association of aromatic nitrocompounds, A. A. Leichenko, Y. Y. Maksimov, Zh. Fiz. Khim., 47, 1265 (1973) [C.A. 79. 5767a (1973)].
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    • Leichenko, A.A.1    Maksimov, Y.Y.2
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    • 3 and Mel at 20°C
    • 3 and Mel at 20°C.
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    • P:Ref. 27;.
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    • This scale has been included as an extension of Kosower's Z parameters [E. M. Kosower, J. Am. Chem. Soc, 80, 3253 (1958)]
    • S, S. Brownstein, Can. J. Chem., 38, 1590 (1960). This scale has been included as an extension of Kosower's Z parameters [E. M. Kosower, J. Am. Chem. Soc, 80, 3253 (1958)].
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    • 3N and EtBr in benzene-acetone solutions [data from A. von Hemptine and A. Bekaert, Z. Physik. Chem., 28, 255(1895)
    • 3N and EtBr in benzene-acetone solutions [data from A. von Hemptine and A. Bekaert, Z. Physik. Chem., 28, 255(1895).
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    • The short-lived clustering of benzene and other highly polarizable molecules around polar solutes likely through a dipole-induced dipole mechanism is also known:
    • The short-lived clustering of benzene and other highly polarizable molecules around polar solutes, likely through a dipole-induced dipole mechanism is also known: R. D. Bertrand, R. D. Compton; and J. G. Verkade, J. Am. Chem. Soc, 92, 2702 ,(1970);.
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    • Bertrand, R.D.1    Compton, R.D.2    Verkade, J.G.3
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    • For a recent survey of solvent effects on spectroscopic properties, see, e.g., Ref. 9a
    • For a recent survey of solvent effects on spectroscopic properties, see, e.g., Ref. 9a;.
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    • concerning the use limitations of the dielectric functions to correlate infrared shifts see e.g.
    • concerning the use and limitations of the dielectric functions to correlate infrared shifts, see, e.g., W. D. Horrocks, Jr., and R. M. Mann, Spectrochim. Acta, 19, 1375 (1963);.
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    • and references cited therein
    • P. Laszlo and J. I. Musher, J. Chem. Phys., 41, 3906 (1964) and references cited therein.
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    • 84983069094 scopus 로고    scopus 로고
    • Although most of the information available on this system comes from Ref. 34c we have used the values given by Abraham and Abraham (19)
    • Although most of the information available on this system comes from Ref. 34c we have used the values given by Abraham and Abraham (19).
  • 95
    • 84983072759 scopus 로고    scopus 로고
    • this connection, see Ref. 20a
    • In this connection, see Ref. 20a.
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    • Part II, O. Sinanoglu, Ed. Academic, New York, Chapter 5, and references herein
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    • See also Ref. 43a, The formal extension to fluorescence spectra has been carried out by Mataga Kaifu Koizumi [N.Mataga Kaifu Y.Koizumi M.
    • The formal extension to fluorescence spectra has been carried out by Mataga, Kaifu, and Koizumi [N. Mataga, Y. Kaifu, and M. Koizumi, Bull. Chem. Soc. Japan, 29, 465 (1956)];See also Ref. 43a.
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    • We are not considering here the contribution from dispersion forces as discussed in Refs. 58a and 58A and by Longuet-Higgins and Pople [H. C. Longuet-Higgins and J. A. Pople, J. Chem. Phys., 27, 192 (1957)]. These forces will introduce a red shift (relative to the gas phase) even in the case of nonpolar solutes in nonpolar solvents, For an exhaustive study on the use of dielectricre fractive index functions to correlate solvent effects see e.g
    • For an exhaustive study on the use of dielectric and refractive index functions to correlate solvent effects, see, e.g., F. W. Fowler, A. R. Katritzky, and R. J. D. Rutherford, J. Chem. Soc. (B), 460 (1971). We are not considering here the contribution from dispersion forces as discussed in Refs. 58a and 58A and by Longuet-Higgins and Pople [H. C. Longuet-Higgins and J. A. Pople, J. Chem. Phys., 27, 192 (1957)]. These forces will introduce a red shift (relative to the gas phase) even in the case of nonpolar solutes in nonpolar solvents.
    • (1971) J. Chem. Soc. (B) , pp. 460
    • Fowler, F.W.1    Katritzky, A.R.2    Rutherford, R.J.D.3
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    • For a recent application of this technique to the uv-visible and fluorescence spectra of azulene and cyclopenta [efjheptalene, see H.Yamaguchi Ikeda T.Mametsuka H.
    • For a recent application of this technique to the uv-visible and fluorescence spectra of azulene and cyclopenta [efjheptalene, see H. Yamaguchi, T. Ikeda, and H. Mametsuka, Bull. Chem. Soc. Japan, 49, 1762 (1976).
    • (1976) Bull. Chem. Soc. Japan , vol.49 , pp. 1762
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    • Ref. 49, Ref.34A;
    • Ref. 34A;E. M. Kosower, J. Am. Chem. Soc, 80, 3262 (1958); Ref. 49.
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    • Kosower, E.M.1
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    • The effects of band everlap (usually with higher intensity, higher energy bands), of hidden underlying lower intensity bands, and of changing band shape with changing solvent, all of which we include in the term spectral anomalies, can cause shifts in Vmax of as much as 0.4-0.5 kK. We have attempted to minimize such complications by taking as the midpoint between the two positions on the spectral envelope where OD (optical density) = 0.90 ODmax. We consider that for "well-behaved" spectra, combined uncertainities in i>max due to usual spectral anomalies and experimental precision limits in measuring the spectra are about O.lOkK
    • The effects of band everlap (usually with higher intensity, higher energy bands), of hidden underlying lower intensity bands, and of changing band shape with changing solvent, all of which we include in the term spectral anomalies, can cause shifts in Vmax of as much as 0.4-0.5 kK. We have attempted to minimize such complications by taking as the midpoint between the two positions on the spectral envelope where OD (optical density) = 0.90 ODmax. We consider that for "well-behaved" spectra, combined uncertainities in i>max due to usual spectral anomalies and experimental precision limits in measuring the spectra are about O.lOkK.
  • 150
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    • Other polar materials have been studied: e.g., ethers, amines, lactones, acid anhydrides, coumarines and cyanine dyes. Detailed references are given by R. Foster, in Organic Charge-Transfer Complexes, Academic, London-New York
    • Other polar materials have been studied: e.g., ethers, amines, lactones, acid anhydrides, coumarines and cyanine dyes. Detailed references are given by R. Foster, in Organic Charge-Transfer Complexes, Academic, London-New York, 1969, p. 108.
    • (1969) , pp. 108
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    • J. W. Emsley, J. Feeney, and L. H. Sutcliffe, Eds., Pergamon, Oxford-New York, Chapter 1
    • R. Foster and C. A. Fyfe, in Progress in Nuclear Magnetic Resonance Spectroscopy, J. W. Emsley, J. Feeney, and L. H. Sutcliffe, Eds., Pergamon, Oxford-New York, 1969; Vol. 4; Chapter 1;.
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    • Ref. 84;Ref. 38
    • Ref. 84;Ref. 38.
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    • As shown in Table 20, for example
    • As shown in Table 20, for example.
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    • Ref. 83, p. 21;R. S. Mulliken, 74, 811 (1952)
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    • W. H. Freeman, San Francisco, For a discussion of HBA properties of the benzene 7r-system, see
    • For a discussion of HBA properties of the benzene 7r-system, see G. C. Pimentel and A. L. McClellan, The Hydrogen Bond, W. H. Freeman, San Francisco, 1960, pp. 22-24;.
    • (1960) The Hydrogen Bond , pp. 22-24
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    • For examples of hydrogen bonding by methylene chloride, see
    • For examples of hydrogen bonding by methylene chloride, see, e.g., E. F. Meyer and F. A. Baiocchi, J. Am. Chem. Soc, 99, 6206 (1977).
    • (1977) J. Am. Chem. Soc , vol.99 , pp. 6206
    • Meyer, E.F.1    Baiocchi, F.A.2
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    • ref. 20a
    • In ref. 20a, p. 1681.
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    • Ref. 27
    • Ref. 27, p. 265.
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    • and references cited therein
    • W. Adkock and T. C. Khor, J. Am. Chem. Soc, 100, 7799 (1978) and references cited therein.
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    • Ref. 49
    • Ref. 49, p. 301;.
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    • Unpublished results of T. N. Hall and M. J. Kamlet
    • Unpublished results of T. N. Hall and M. J. Kamlet.
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    • University of California, Irvine
    • J. W. Rakskys, Jr., PhD. Thesis, University of California, Irvine, 1967.
    • (1967) PhD. Thesis
    • Rakskys, J.W.1


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