Proton Affinities of Primary Alkanols: An Appraisal of the Kinetic Method

Journal of Physical Chemistry A

Volumn 103, Issue 6, 1999, Pages 705-709

  Holmes, John L ^a   Aubry, Christiane ^a   Mayer, Paul M ^a  

^a UNIVERSITY OF OTTAWA   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000502141     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp984094z     Document Type: Article

References (28)

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15. -4% of the ions will have sufficient energy to dissociate on the metastable time scale. In the present experiment, typically 1-10% of the adduct ions entering the third field-free region were metastable therein.
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18. 14 suite of programs, on an SGI Octane workstation, at the HF/6-31G(d) level of theory.
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21. Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. J. Phys. Chem. Ref. Data 1998, 17 (Suppl. 1).
22. Hunter, E. P.; Lias, S. G. Proton Affinity Evaluation. In NIST Chemistry WebBook, NIST Standard Reference Database Number 69; Mallard, W. G., Linstrom, P. J., Eds.; National Institute of Standards and Technology: Gaithersburg, MD, 1998.
23. Gauld, J.; Holmes, J. L.; Radom, L. Acta Chem. Scand. 1997, 51, 641-645.
24. Anomalous behavior among n-alkyl species has been reported in solution studies where the acidities of n-alkanoic acids and H-alkylamines show an inversion from the ethyl to hexyl homologues. This does not appear to be the case here where only the butyl species appears anomalous. It is worth noting that the gas-phase acidities of the homologous alkanols show no such effect. Similar experiments in this laboratory with homologous amines and nitriles failed to show any discontinuities with increasing alkyl group size.
25. 21 have found that the relative rate constants for branching reactions can be related to the relative activation energies by a In-linear relationship. They noted that the relationship was not universally applicable, however, nor is it validation of eq 1, which incorporates temperature as one of the principal variables.
26. Craig, S. L.; Zhong, M.; Choo, B.; Brauman, J. I. J. Phys. Chem. A 1997, 101, 19-24.
27. For examples, see: (a) Luo, Y.-R.; An, Y.; Holmes, J. L. J. Mass Spectrum. 1994, 29, 579. (b) Holmes, J. L.; Lossing, F. P. Org. Mass Spectrom. 1991, 26, 537-541.
28. For examples, see: (a) Luo, Y.-R.; An, Y.; Holmes, J. L. J. Mass Spectrum. 1994, 29, 579. (b) Holmes, J. L.; Lossing, F. P. Org. Mass Spectrom. 1991, 26, 537-541.