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Scattered isergonic profiles

J J Zimmerman

    Journal of Pharmaceutical Sciences
    |January 1, 1977
    PubMed
    Summary
    This summary is machine-generated.

    Geometric analysis of scatter in isergonic profiles reveals that vertical distances (delta delta H) equal substituent effects (beta delta G). Solvation mechanisms are not supported by these correlations, and experimental error cannot explain the observed scatter.

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    Area of Science:

    • Physical Chemistry
    • Chemical Kinetics
    • Computational Chemistry

    Background:

    • Isergonic profiles are used to analyze reaction kinetics.
    • Scatter in these profiles can obscure underlying chemical mechanisms.
    • Previous approaches have linked scatter to solvation effects via substituent correlations.

    Purpose of the Study:

    • To develop equations for geometric analysis of scatter in isergonic profiles.
    • To differentiate between scatter caused by experimental error and mechanistic factors.
    • To re-evaluate the Hepler approach for implicating solvation mechanisms.

    Main Methods:

    • Geometric analysis of isergonic profiles using vertical (delta delta H), horizontal (delta delta S), and perpendicular (d) distances.
    • Correlation analysis of scatter with various geometric parameters and substituent effects (beta delta G).

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  • Application of the joint confidence region (error contour) approach to quantify uncertainty.

    • Main Results:

    • Vertical distances (delta delta H) were found to be identical to substituent effects (beta delta G).
    • Scatter in the isergonic profiles could not be attributed to experimental error (d > w/2).
    • Solvation effects could not be statistically distinguished from error effects within the observed temperature range.

    Conclusions:

    • The Hepler approach is not warranted for implicating solvation mechanisms based on rho-beta correlations.
    • Precise kinetic data and a higher number of data points (N=4 or 5) are needed to resolve small substituent effects.
    • Distinguishing solvation effects from experimental error in isergonic profiles requires careful analysis of geometric parameters and uncertainty.