Skip to main content
SpringerLink
Log in

Entropy measurements and the kinetic method: A statistically meaningful approach

  • Articles
  • Published:
Journal of the American Society for Mass Spectrometry

Abstract

In the literature, data obtained using the kinetic method have been analyzed to provide both ion affinities and relative entropies for the competitive dissociations involved. In this work, the procedure used to extract this information is shown to be statistically flawed. Using more rigorous statistical procedures, we outline alternative methods of acquiring the same information, including straightforward means of analyzing the uncertainties in the thermodynamic quantities obtained. Fortunately, it is expected that the central values reported in previous work need not be changed, but the uncertainties are much larger than has been previously detailed. The validity of the assumptions involved in the extraction of entropy effects is discussed in some detail.

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. Cooks, R. G.; Kruger, T. L. J. Am. Chem. Soc. 1977, 99, 1279.

    Article  CAS  Google Scholar 

  2. McLuckey, S. A.; Cameron, D.; Cooks, R. G. J. Am. Chem. Soc. 1981, 103, 1313.

    Article  CAS  Google Scholar 

  3. Cooks, R. G.; Koskinen, J. T.; Thomas, P. D. J. Mass Spectrom. 1999, 34, 85.

    Article  CAS  Google Scholar 

  4. Cheng, X.; Wu, Z.; Fenselau, C. J. Am. Chem. Soc. 1993, 115, 4844.

    Article  CAS  Google Scholar 

  5. Wu, Z.; Fenselau, C. Rapid. Commun. Mass Spectrom. 1994, 8, 777.

    Article  CAS  Google Scholar 

  6. Cerda, B. A.; Wesdemiotis, C. J. Am. Chem. Soc. 1996, 118, 11884.

    Article  CAS  Google Scholar 

  7. Cerda, B. A.; Nold, M. J.; Wesdemiotis, C. In Selected Topics in Mass Spectrometry in the Biomolecular Sciences; Caprioli, R. M.; Malorni, A.; Sindona, G., Eds.; Kluwer Academic: Dordrecht, 1997; p 143.

    Google Scholar 

  8. Cerda, B. A.; Hoyau, S.; Ohanessian, G.; Wesdemiotis, C. J. Am. Chem. Soc. 1998, 120, 2437.

    Article  CAS  Google Scholar 

  9. Nold, M. J.; Cerda, B. A.; Wesdemiotis, C. J. Am. Soc. Mass Spectrom. 1999, 10, 1.

    Article  CAS  Google Scholar 

  10. Box, G. E. P.; Hunter, W. G.; Hunter, J. S. Statistics for Experimenters; Wiley: New York, 1978.

    Google Scholar 

  11. Irvin, J. A.; Quickenden, T. I. J. Chem. Ed. 1983, 60, 711.

    Article  Google Scholar 

  12. Krug, R. R.; Hunter, W. G.; Grieger, R. A. J. Phys. Chem. 1976, 80, 2335.

    Article  CAS  Google Scholar 

  13. Krug, R. R.; Hunter, W. G.; Grieger, R. A. J. Phys. Chem. 1976, 80, 2341.

    Article  CAS  Google Scholar 

  14. A short Fortran program for weighted linear regression analysis of such data is available from the author upon request. The program output includes slope, x and y intercepts, and their standard deviations.

  15. Cooks, R. G.; Wong, P. S. H. Acc. Chem. Res. 1998, 31, 379.

    Article  CAS  Google Scholar 

  16. Draper, N. R.; Smith, H. Applied Regression Analysis, 2nd ed.; Wiley: New York, 1966.

    Google Scholar 

  17. Armentrout, P. B. J. Mass Spectrom. 1999, 34, 74.

    Article  CAS  Google Scholar 

  18. Drahos, L.; Vékey, K. J. Mass Spectrom. 1999, 34, 79.

    Article  CAS  Google Scholar 

  19. Ervin, K. M. Int. J. Mass Spectrom. 2000, 195/196, 271.

    Article  Google Scholar 

  20. Armentrout, P. B. In Advances in Gas Phase Ion Chemistry; Adams, N. G.; Babcock, L. M., Eds.; JAI: Greenwich, 1992; vol. 1, pp 83–119.

    Google Scholar 

  21. Rodgers, M. T.; Ervin, K. M.; Armentrout, P. B. J. Chem. Phys. 1997, 106, 4499.

    Article  CAS  Google Scholar 

  22. Rodgers, M. T.; Armentrout, P. B. J. Chem. Phys. 1998, 109, 1787.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Chemistry Department, University of Utah, 315 S. 1400 E. Rm 2020, 84112, Salt Lake City, UT

    P. B. Armentrout

Authors
  1. P. B. Armentrout
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to P. B. Armentrout.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Armentrout, P.B. Entropy measurements and the kinetic method: A statistically meaningful approach. J Am Soc Mass Spectrom 11, 371–379 (2000). https://doi.org/10.1016/S1044-0305(00)00102-1

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1016/S1044-0305(00)00102-1

Keywords

Search

Navigation