Skip to main content
SpringerLink
Log in

Linear solvation energy relations

  • Published:
Journal of Solution Chemistry Aims and scope Submit manuscript

Abstract

Solvents have been parameterized by scales of dipolarity/polarizability π*, hydrogen-bond donor (HBD) strength α, and hydrogen-bond acceptor strength β. Linear dependence (LSER's) on these solvent parameters are used to correlate and predict a wide variety of solvent effects, as well as to provide an analysis in terms of knowledge and theoretical concepts of molecular structural effects. Some recent applications utilizing this approach are presented. Included are analyses of solvent effects on (a) the free energies of transfer of tetraalkylammonium halide ion pairs and dissociated ions, (b) rates of nucleophilic substitution reactions, (c) the contrast in solvent effects of water (HBD) and dimethyl sulfoxide (non-HBD) on the acidities of m- and p-substituted phenols, (d) partition coefficients of non-HBD solutes between solvent bilayers, and (e) family relationships between proton transfer (and non-protonic Lewis acid) basicities and corresponding β values for monomer HBA. A comprehensive summary of LSER with references is given.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. V. A. Plam,Fundamentals of the Quantitative Theory of Organic Reactions, in Russian (Khimiya, Leníngrad, 1967).

    Google Scholar 

  2. M. J. Kamlet, J. L. M. Abboud, and R. W. Taft,Prog. Phys. Org. Chem. 13, 485 (1981).

    Google Scholar 

  3. M. J. Kamlet and R. W. Taft,J. Am. Chem. Soc. 98, 377 (1976).

    Google Scholar 

  4. R. W. Taft and M. J. Kamlet,J. Am. Chem. Soc. 98, 2886 (1976).

    Google Scholar 

  5. R. W. Taft,Prog. Phys. Org. Chem. 14, 247–350 (1983),

    Google Scholar 

  6. W. F. Reynolds, P. Das, D. W. MacIntyre, R. D. Topsom, S. Marriott, E. von Nagy-Felsobuki, Nagy-Felsobuki, and R. W. Taft,J. Am. Chem. Soc. 105, 378 (1983).

    Google Scholar 

  7. S. Marriott, W. F. Reynolds, R. W. Taft, and R. D. Topsom,J. Org. Chem. 49, 959 (1984).

    Google Scholar 

  8. For a recent summary of the solvatochromic parameters see M. J. Kamlet, J. L. M. Abboud, M. H. Abraham, and R. W. Taft,J. Org. Chem. 48, 2877 (1983).

    Google Scholar 

  9. M. J. Kamlet, P. W. Carr, R. W. Taft, and M. H. Abraham,J. Am. Chem. Soc. 103, 6062 (1984),

    Google Scholar 

  10. M. J. Kamlet, R. W. Taft, P. W. Carr, and M. H. Abraham,J. Chem. Soc., Faraday Trans. 1 78, 1869 (1982);

    Google Scholar 

  11. M. J. Kamlet, M. H. Abraham, R. M. Doherty, and R. W. Taft,J. Am. Chem. Soc. 106, 464 (1984).

    Google Scholar 

  12. R. W. Taft, M. H. Abraham, G. R. Famini, R. M. Doherty, J. L. M. Abboud, and M. J. Kamlet,J. Med. Chem., submitted.

  13. R. W. Taft, M. H. Abraham, R. M. Doherty, and M. J. Kamlet,J. Am. Chem. Soc., in press.

  14. M. J. Kamlet, R. W. Taft, and J. L. M. Abbound,J. Am. Chem. Soc. 99, 6027 (1977).

    Google Scholar 

  15. J. L. M. Abboud, J. J. Kamlet, and R. W. Taft,J. Am. Chem. Soc. 99, 8325 (1977). (b) J. L. M. Abboud and R. w. Taft,J. Phys. Chem. 83, 412 (1979).

    Google Scholar 

  16. J. L. M. Abboud, R. W. Taft, and M. J. Kamlet,J. Chem. Res., 98 (1984).

  17. R. W. Taft and M. J. Kamlet,Inorg. Chem. 22, 250 (1983); (b) J. L. M. Abboud, G. Guiheneuf, M. Essfar, R. W. Taft, and M. J. Kamlet,J. Phys. Chem. 88, (1984), in press.

    Google Scholar 

  18. B. Frange, J. L. M. Abboud, C. Benamou, and L. Bellon,J. Org. Chem. 47, 4553 (1982).

    Google Scholar 

  19. R. W. Taft and M. J. Kamlet, unpublished results.

  20. J. L. M. Abboud, K. Sraidi, G. Guiheneuf, M. J. Kamlet, and R. W. Taft, in preparation.

  21. J. L. M. Abboud, R. W. Taft, and M. J. Kamlet,J. Chem. Res. 98 (1984).

  22. R. W. Taft, unpublished results,

  23. J. Bromilow, J. L. M. Abboud, C. B. Lebrilla, R. W. Taft, G. Scorrano, and V. Lucchini,J. Am. Chem. Soc. 103, 5448 (1981);

    Google Scholar 

  24. J. f. Gal, M. Berthelot, and R. W. Taft, unpublished results.

  25. B. Chawla, M. Fujio, L. Simanyi, S. K. Pollack, C. Lebrilla, C. W. Fong, H. G. Grant, M. J. Kamlet, and R. W. Taft,J. Am. Chem. Soc. to be submitted.

  26. B. Chawla, S. K. Pollack, C. B. Lebrilla, M. J. Kamlet, and R. W. Taft,J. Am. Chem. Soc. 103, 6924 (1981) and unpublished results.

    Google Scholar 

  27. J. Bromilow, R. T. C. Brownlee, V. O. Lopez, and R. W. Taft,J. Org. Chem. 44, 4766 (1979).

    Google Scholar 

  28. C. G. Swain, M. S. Swain, A. L. Powell, and S. Alumni,J. Am. Chem. Soc. 105, 502 (1983).

    Google Scholar 

  29. R. W. Taft, J. L. M. Abboud, and M. J. Kamlet,J. Org. Chem. 46, 2001 (1984).

    Google Scholar 

  30. M. H. Abraham, R. W. Taft, and M. J. Kamlet,J. Org. Chem. 46, 3053 (1981).

    Google Scholar 

  31. M. H. Abraham, R. W. Taft, and M. J. Kamlet, unpublished results.

  32. P. Kebarle,Annu. Rev. Phys. Chem. 28, 445 (1977).

    Google Scholar 

  33. C. Hansch, and A. Leo,Substituent Constants for Correlation Analysis in Chemistry and Biology, (Wiley-Interscience, New York, 1979).

    Google Scholar 

  34. R. W. Taft, M. H. Abraham, R. M. Doherty, and M. J. Kamlet,Nature, accepted for publication.

  35. M. Fujio, R. T. McIver, Jr., and R. W. Taft,J. Am. Chem. Soc. 103, 4017 (1981).

    Google Scholar 

  36. M. Mishima, R. T. McIver, Jr., R. W. Taft, F. G. Bordwell, and W. N. Olmstead,J. Am. Chem. Soc. 106, 2717 (1984).

    Google Scholar 

References cited in table AI Solvatochromic Comparison Method (SCM) series

  1. M. J. Kamlet and R. W. Taft,J. Am. Chem. Soc. 98, 377 (1976).

    Google Scholar 

  2. R. W. Taft and M. J. Kamlet,J. Am. Chem. Soc. 98, 2886 (1976).

    Google Scholar 

  3. T. Yokoyama, R. W. Taft, and M. J. Kamlet,J. Am. Chem. Soc. 98, 3233 (1976).

    Google Scholar 

  4. M. J. Kamlet, E. G. Kayser, M. E. Jones, J.-L. M. Abboud, J. W. Eastes, and R. W. Taft,J. Phys. Chem. 82, 2477 (1978).

    Google Scholar 

  5. M. J. Kamlet, R. W. Taft, and J.-L. M. Abboud,J. Am. Chem. Soc. 99, 6027 (1977).

    Google Scholar 

  6. J.-L. M. Abboud, M. J. Kamlet, and R. W. Taft,J. Am. Chem. Soc. 99, 8325 (1977).

    Google Scholar 

  7. B. Chawla, S. K. Pollack, C. B. Lebrilla, M. J. Kamlet, and R. W. Taft,J. Am. Chem. Soc. 103, 6924 (1981).

    Google Scholar 

  8. B. Chawla, M. Fujio, L. Simanyi, S. K. Pollack, C. Lebrilla, C. W. Forn, H. G. Grant, M. J. Kamlet, and R. W. Taft,J. Am. Chem. Soc. to be submitted.

Linear Solvation Energy Relationships (LSER) series

  1. M. J. Kamlet, and R. W. Taft,J. Chem. Soc., Perkin Trans. 2 337, (1979).

  2. M. J. Kamlet, M. E. Jones, R. W. Taft, and J.-L. M. Abboud,J. Chem. Soc., Perkin Trans. 2, 342 (1979).

    Google Scholar 

  3. M. J. Kamlet and R. W. Taft,J. Chem. Soc., Perkin Trans. 2, 349 (1979).

    Google Scholar 

  4. R. W. Taft and J. J. Kamlet,J. Chem. Soc., Perkin Trans. 2, 1723 (1979).

    Google Scholar 

  5. M. J. Kamlet, A. Solomonovici, and R. W. Taft,J. Am. Chem. Soc. 101, 3734 (1979).

    Google Scholar 

  6. M. J. Kamlet, T. N. Hall, J. Boykin, and R. W. Taft,J. Org. Chem. 44, 2577 (1979).

    Google Scholar 

  7. R. W. Taft, N. J. Pienta, M. J. Kamlet, and E. M. Arnett,J. Org. Chem. 46, 661 (1981).

    Google Scholar 

  8. R. W. Taft and M. J. Kamlet,Org. Magn. Reson. 14, 485 (1980).

    Google Scholar 

  9. M. J. Kamlet, R. W. Taft, P. W. Carr, and M. H. Abraham,J. Chem. Soc., Faraday Trans. 1 78, 1689 (1982).

    Google Scholar 

  10. M. J. Kamlet, C. Dickinson, and R. W. Taft,Chem. Phys. Lett. 77, 69 (1981).

    Google Scholar 

  11. M. J. Kamlet, C. Dickinson, and R. W. Taft,J. Chem. Soc. Perkin Orans. 2, 353 (1981).

    Google Scholar 

  12. R. W. Taft, J.-L.M. Abboud, and M. J. Kamlet,J. Am. Chem. Soc. 103, 1080 (1981).

    Google Scholar 

  13. M. J. Kamlet, P. W. Carr, R. W. Taft, and M. H. Abraham,J. Am. Chem. Soc. 103, 6062 (1981).

    Google Scholar 

  14. R. W. Taft, T. Gramstad, and M. J. Kamlet,J. Org. Chem. 47, 4557 (1982).

    Google Scholar 

  15. M. H. Abraham, R. W. Taft, and M. J. Kamlet,J. Org. Chem. 46, 3053 (1981).

    Google Scholar 

  16. M. J. Lamlet, C. Dickinson, T. Gramstad, and R. W. Taft,J. Org. Chem. 47, 4971 (1982).

    Google Scholar 

  17. M. J. Lamlet and R. W. Taft,Pol. J. Chem. 55, 1337 (1981).

    Google Scholar 

  18. J.-L. M. Abboud, R. W. Taft, and M. J. Kamlet,Bull. Chem. Soc. Jpn. 55, 603 (1982).

    Google Scholar 

  19. M. J. Abraham, M. J. Kamlet, and R. W. Taft,J. Chem. Soc., Perkin Trans. 2, 923 (1982).

    Google Scholar 

  20. M. J. Kamlet and R. W. Taft,J. Org. Chem. 47, 1734 (1982).

    Google Scholar 

  21. J.-L. M. Abboud, R. W. Taft, and M. J. Kamlet,J. Phys. Chem. 88, (1984), in press.

  22. R. W. Taft and M. J. Kamlet,Inorg. Chem. 22, 250 (1983).

    Google Scholar 

  23. M. J. Kamlet, J.-L. M. Abboud, M. H. Abraham, and R. W. Taft,J. Org. Chem. 48, 2877 (1983).

    Google Scholar 

  24. C. M. Fong, M. J. Kamlet, and R. W. Taft,J. Org. Chem. 48, 832 (1983).

    Google Scholar 

  25. T. Yokoyama, R. W. Taft, and M. J. Kamlet,Aust. J. Chem. 36, 701 (1983).

    Google Scholar 

  26. Blank entry.

  27. J.-L. M. Abboud, R. W. Taft, and M. J. Kamlet,J. Chem. Res., 98 (1984).

  28. R. W. Taft, J.-L. M. Abboud, and M. J. Kamlet,J. Org. Chem. 49, 2001 (1984).

    Google Scholar 

  29. R. W. Taft, M. H. Abraham, R. M. Doherty, and M. J. Kamlet,J. Am. Chem. Soc. accepted.

  30. M. J. Kamlet, J. F. Gal, P. C. Maria, and R. W. Taft,J. Chem. Soc., submitted for publication.

  31. R. W. Taft, M. H. Abraham, R. M. Doherty, and M. J. Kamlet,Nature, accepted.

Solubility Properties in Polymers and Biological Media (SPPBM) series

  1. SPPBM-1, M. H. Abraham, M. J. Kamlet, R. W. Taft, and P. K. Weathersby,J. Am. Chem. Soc. 105, 6797 (1983).

    Google Scholar 

  2. SPPBM-4, M. J. Kamlet, M. H. Abraham, R. M. Doherty, and R. W. Taft,J. Am. Chem. Soc. 106, 464 (1984).

    Google Scholar 

  3. SPPBM-5, R. W. Taft, M. H. Abraham, G. R. Famini, R. M. Doherty, and M. J. Kamlet,J. Med. Chem., submitted.

References cited in table AIII

  1. K. J. Shea, Y. Okahata, and T. K. Dougherty,Macromolecules 17, 296 (1984).

    Google Scholar 

  2. S. Y. Khorshev, V. L. Tsvetkova, and A. N. Egorochkin,J. Organomet. Chem. 264, 169 (1984).

    Google Scholar 

  3. O. W. Kolling,Anal. Chem. 56, 430 (1984).

    Google Scholar 

  4. E. Bienvenue, R. Msika, and J.-E. Dubois,J. Chim. phys. 77, 803 (1980).

    Google Scholar 

  5. B. Marcandalli, E. Bubini-Paglia, and L. Pellicaiardi-Di Liddo,Gazz. Chim. Ital. 111, 187 (1981).

    Google Scholar 

  6. C. W. Fong and H. G. Grant,Org. Magn. Reson. 14, 147 (1980).

    Google Scholar 

  7. R. Romeo, D. Minniti, and S. Lanza,Inorg. Chem. 19, 3663 (1980).

    Google Scholar 

  8. O. Kolling,Anal. Chem. 52, 987 (1980).

    Google Scholar 

  9. C. Dell'Erba, G. Guanti, G. Garbarino, M. Novi, and G. Poluzzi Corallo,Tetrahedron 37, 795 (1981).

    Google Scholar 

  10. O. Kolling,Anal. Chem. 53, 54 (1981).

    Google Scholar 

  11. P. Beak, J. B. Covington, and J. M. White,J. Org. Chem. 45, 1347 (1980).

    Google Scholar 

  12. H. Mustroph and J. Epperlein,J. für prakt. Chem. 322 305 (1980).

    Google Scholar 

  13. O. Kolling,Anal. Chem. 51, 1324 (1979).

    Google Scholar 

  14. G. Jones, W. R. Jackson, S. Kanoktanaporn, and A. M. Halpern,Optics Commun. 33, 315 (1980).

    Google Scholar 

  15. L. Abate, M. L. Longo, E. Maccarone, and M. Torre,Gazz. Chim. Ital. 110, 527 (1980).

    Google Scholar 

  16. B. Frange, J.-L. M. Abboud, C. Benamou, and L. Bellon,J. Org. Chem. 47, 4553 (1982).

    Google Scholar 

  17. A. Peloso, J. Chem. Soc., Dalton Trans. 2141 (1982).

  18. K. M. Kadish and D. Chang,Inorg. Chem. 21, 3614 (1982).

    Google Scholar 

  19. E. Ciuffarin, M. Isola, and P. Leoni,Tetrahedron Lett. 22, 2131 (1981).

    Google Scholar 

  20. O. Kolling,Anal. Chem. 55, 143 (1983).

    Google Scholar 

  21. D. R. Terrell and F. Evers,J. Polymer Sci. 20, 2529 (1982).

    Google Scholar 

  22. J. D. Pipkin and V. J. Stella,J. Am. Chem. Soc. 104, 6672 (1982).

    Google Scholar 

  23. E. Padros, A. Morros, J. Manosa, and M. Dunach,Eup. J. Biochem. 127, 117 (1982).

    Google Scholar 

  24. A. Marty and P. Viallet,J. Photochem. 20, 213 (1982).

    Google Scholar 

  25. M. S. A. Abd-El-Mottaleb,Z. Naturforsch. 37A, 1353 (1982).

    Google Scholar 

  26. D. M. Manuta and A. J. Lees,Inorg. Chem. 22, 3825 (1983).

    Google Scholar 

  27. V. Y. Fain, L. Y. Kliot, Y. V. Ivanov, and B. E. Zaitsev,Organ. Reactivity 20, 467 (1093).

    Google Scholar 

  28. R. Roussel, M. Oteyza de Guerrero, P. Spegt, and J. C. Galin,J. Heterocyclic Chem.

  29. P. C. Tway and L. J. Cline Love,Chem. Phys. Lett. 87, 204 (1982).

    Google Scholar 

  30. A. Marty and P. Viallet,C. R. Acad. Sc. Paris 296, 343 (1983).

    Google Scholar 

  31. K. S. Schanze, T. F. Mattox, and D. G. Whitten,J. Org. Chem. 48, 2808 (1983).

    Google Scholar 

  32. W. Abraham, M. Kupfer, and G. Kreysig,J. prakt. Chem. 324, 753 (1982).

    Google Scholar 

  33. M. Kupfer and W. Abraham,J. prakt. Chem. 325, 95 (1983).

    Google Scholar 

  34. W. Abraham, M. Kupfer, K. Buck, and D. Kreysig,Z. Naturforsch. 36A, 1213 (1981).

    Google Scholar 

  35. T. Zhu, C. H. Su, B. K. Lemke, L. J. Wilson, and K. M. Kadish,Inorg. Chem. 22, 2527 (1983).

    Google Scholar 

  36. R. Fuchs and W. K. Stephenson,J. Am. Chem. Soc. 103, 5159 (1983).

    Google Scholar 

  37. J. D. Pipkin and V. J. Stella,Int. J. Pharmaceutics 14, 263 (1983).

    Google Scholar 

  38. A. K. Yatsimirsky, A. D. Ryabov, V. P. Zogorodnikov, I. K. Sakodinskaya, O. I. Kavetskaya, and I. V. Berezin,Inorg. Chem. Acta 48, 163 (1981).

    Google Scholar 

  39. W. A. Pryor, G. J. Gleicher, and D. F. Church,J. Org. Chem. 48, 4198 (1983).

    Google Scholar 

  40. J. C. Curtis, B. P. Sullivan, and T. J. Meyer,Inorg. Chem. 22, 224 (1983).

    Google Scholar 

  41. A. Uri and A. Tuulmets,Organ. Reactivity 20, 578 (1983).

    Google Scholar 

  42. J. A. Connor and C. Overton,Inorg. Chim. Acta 65, L1 (1982).

    Google Scholar 

  43. C. Czongar, R. Socher, and G. Tamaschewski,J. prakt. Chem. 324, 246 (1982).

    Google Scholar 

  44. M. Kupfer and W. Abraham,Monatsh. Chem. 114, 513 (1983).

    Google Scholar 

  45. P. Nicolet and C. Laurance,J. chim. phys. in press.

  46. K. Hamanoue, K. Nakajima, M. Amano, T. Hidaka, T. Nakayama, and H. Teranishi,Polymer Photochem. 3, 407 (1983).

    Google Scholar 

  47. B. Marcandelli, L. Pellicciardi-Di Liddo, C. Di Fede, and I. R. Bellobono,J. Chem. Soc., Perkin Trans. 2, 589 (1984).

    Google Scholar 

  48. J. F. Coetzee and A. Hussam,J. Solution Chem. 11, 395 (1982).

    Google Scholar 

  49. S. Ueji, M. Nakamura, M. Kitadani, and A. Sera,Bull. Chem. Soc. Japan 55, 1665 (1982).

    Google Scholar 

  50. E. Maccarone, G. Perrini, and M. Torre,Gazz. Chim. Ital. 112, 25 (1982).

    Google Scholar 

  51. T. C. Werner and D. B. Lyon,J. Phys. Chem. 86, 933 (1982).

    Google Scholar 

  52. I. Lee, T. S. Uhm, D. D. Sung, and G. Yeom,Daehon Hwahok Hwoejee 27, 1 (1983).

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, University of California, 92717, Irvine, CA

    Robert W. Taft

  2. Department de Chimie, Universite Cadi Ayyad, Marrakech, Morocco

    Jose-Luis M. Abboud

  3. White Oak Laboratory, Naval Surface Weapons Center, 20910, Silver Springs, MD

    Mortimer J. Kamlet

  4. Department of Chemistry, University of Surrey, GU2 5XH, Guildford, Surrey, UK

    Michael H. Abraham

Authors
  1. Robert W. Taft
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jose-Luis M. Abboud
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Mortimer J. Kamlet
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Michael H. Abraham
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

Session lecture, Ninth International Conference on Non-Aqueous Solutions, Pittsburgh, PA, August 1984.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Taft, R.W., Abboud, JL.M., Kamlet, M.J. et al. Linear solvation energy relations. J Solution Chem 14, 153–186 (1985). https://doi.org/10.1007/BF00647061

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00647061

Key words

Search

Navigation