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Linear solvation energy relationships. A comparison of molar volume and intrinsic molecular volume as measures of the cavity term in reversed phase liquid chromatography

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Summary

Reversed-phase liquid chromatographic capacity factors are well correlated by an equation of the form:

$$logk' = (logk')_0 + mV/100 + s\pi ^* + b\beta + a\alpha $$

wheremV/100 measures the cavity term and π*, β, and α are the solvatochromic parameters that measure solute dipolarity/polarizability, hydrogen bond acceptor basicity, and hydrogen bond donor acidity respectively. Liquid molar volume (molecular weight divided by liquid density at 20°C)\(\bar V\), and computer-calculated intrinsic (van der Waals) molecular volume,\(\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{V} _I \), are compared as measures of the cavity term in a number of correlations.\(\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{V} _I \) leads to more precise correlations as well as to a “cleaner” dissection of the multiple solute/solvent interactions. The opposing exoergic effect of solvent donor/solute acceptor hydrogen bonding, and endoergic cavity term are the main factors influencing HPLC capacity factors.

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References

  1. M. J. Kamlet, R. W. Taft, Acta Chem. Scand.398, 611 (1985).

    Google Scholar 

  2. R. W. Taft, J.-L. M. Abboud, M. J. Kamlet, M. H. Abraham, J. Solution Chem.14, 153 (1985).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    CAS  Google Scholar 

  5. M. J. Kamlet, R. M. Doherty, J.-L. M. Abboud, M. H. Abraham, R. W. Taft, J. Pharm. Sci.75, 338 (1986).

    CAS  Google Scholar 

  6. R. W. Taft, M. H. Abraham, R. M. Doherty, M. J. Kamlet, Nature313, 384 (1985).

    Article  CAS  Google Scholar 

  7. R. W. Taft, M. H. Abraham, G. R. Famini, R. M. Doherty, J.-L. M. Abboud, M. J. Kamlet, J. Pharm. Sci.74, 807 (1985).

    CAS  Google Scholar 

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

    CAS  Google Scholar 

  9. P. C. Sadek, P. W. Carr, R. M. Doherty, M. J. Kamlet, R. W. Taft, M. H. Abraham, Anal. Chem.57, 2971 (1985).

    Article  CAS  Google Scholar 

  10. P. W. Carr, R. M. Doherty, M. J. Kamlet, R. W. Taft, W. Melander, C. Horvath, Submitted for publication to Anal. Chem.

  11. J. E. Haki, A. M. Young, J. Liq. Chromatogr.7, 675 (1984).

    Google Scholar 

  12. A. Bondi, J. Phys. Chem.68, 441 (1964).

    CAS  Google Scholar 

  13. VIKING, developed by Imperial Chemical Industries, PLC.

  14. U. Burkert, N. L. Allinger, “Molecular Mechanics”; ACS Monograph No. 177, American Chemical Society, Washington, D. C., 1982. Part of TRIBBLE, compiled byD. Pensak, E. I. DuPont de Nemours, Inc., Wilmington, DE.

  15. A. Gavezotti, J. Am. Chem. Soc.105, 5220 (1983).

    Google Scholar 

  16. D. E. Leahy, Submitted for publication to J. Pharm. Sci.

  17. R. W. Taft, J.-L. M. Abboud, M. J. Kamler, J. Am. Chem. Soc.103, 1080 (1981).

    Article  CAS  Google Scholar 

  18. T. L. Hafkenscheid, E. Tomlinson, Int. J. Pharmaceut.17, 1 (1983).

    Article  CAS  Google Scholar 

  19. R. S. Pearlman, “Molecular Surface Area and Volume: Their Calculation and Use in Predicting Solubilities and Free Energies of Desolvation”, in The Partition Coefficient: Theory and Measurement,W. Dunn, J. Block, R. S. Peariman, Eds., Pergamon Press, New York, 1986.

    Google Scholar 

  20. T. L. Hafkenscheid, E. Tomlinson, Int. J. Pharmaceut.16, 225 (1983).

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. ICI Pharmaceuticals Division, Mereside, Alderley Park, SK10 4TG, Macclesfield, Cheshire, UK

    D. E. Leahy

  2. Department of Chemistry, University of Minnesota, 55455, Minneapolis, MN, USA

    P. W. Carr

  3. College of Pharmacy, University of Texas, 78712-1074, Austin, TX, USA

    R. S. Pearlman

  4. Department of Chemistry, University of California, 92717, Irvine, CA, USA

    R. W. Taft

  5. White Oak Laboratory, Naval Surface Weapons Center, 20910, Silver Spring, MD, USA

    M. J. Kamlet

Authors
  1. D. E. Leahy
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  2. P. W. Carr
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  3. R. S. Pearlman
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  4. R. W. Taft
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  5. M. J. Kamlet
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Additional information

Publication No. 42 in a series on linear solvation energy relationships.

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Leahy, D.E., Carr, P.W., Pearlman, R.S. et al. Linear solvation energy relationships. A comparison of molar volume and intrinsic molecular volume as measures of the cavity term in reversed phase liquid chromatography. Chromatographia 21, 473–477 (1986). https://doi.org/10.1007/BF02341273

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  • DOI: https://doi.org/10.1007/BF02341273

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