The dynamics of some reactions which produce hydrogen fluorides
The dynamics of some reactions which produce hydrogen fluorides
Using the arrested relaxation variant of the infrared chemiluminescence technique, experimental studies have been made of the following reactions: F+CH4, F+C2H6, F+CH20, F+SiHC13, F+HBr andF4HI. These experiments yielded estimates of the relative rate constants into the excited vibrational states of the HF product of reaction, and of the rotational distributions in these vibrational manifolds.Information theory has been used in an attempt to compact the vibrational distributions of the reactions, and frequently this has allowed the identification of a single informative observable pertaining to the disposal of energy to this degree of freedom.For the reactions F+CH4, F4-C2 H6, F+CH2O, the analysis has permitted an insight into the role in the reaction dynamics of the internal degrees of freedom of the radical leaving group; for the reaction F+HI it allowed the discovery of two channels (distinguishable by the amount of energy apparently available to the reaction products) by which HF may be produced, although it was not possible using information theory to characterise these reaction pathways. Where appropriate, an information-theoretic analysis of the disposal of energy to the rotational degrees of freedom of the HF product has been attempted, but it has not been possible to identify the pertinent information observables.The classical trajectory method has been applied to the reactions F+HBr and F+HI in an attempt to explain the experimental results in terms of single potential surfaces, calculated semi-empirically by the London-Eyring-Polanyi-Sato method. Using the empirical findings of an earlier study of the reaction F+HCl -HF+Cl, some predictions have been made of the energy disposal and branching in the reaction H+C1F --> HF+Cl or HC1+F. Information theory has been used to demonstrate that the energy disposal alone is incapable of accounting for the calculated branching ratio. Finally, the systems H+F2 and D+F2 have been used to compare the findings of classical and quantum mechanics for the dynamics of atom-molecule reactions, and to gain insight into the effect of isotopic substitution on the energy distributions of these reactions. It is reported that, while the gross features of the dynamics are correctly predicted by a classical calculation, the finer aspects are not so, and that the effect of the increased mass of D over H, is a significant one, which may be explained classically.
University of Southampton
1979
Naylor, John Charles
(1979)
The dynamics of some reactions which produce hydrogen fluorides.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
Using the arrested relaxation variant of the infrared chemiluminescence technique, experimental studies have been made of the following reactions: F+CH4, F+C2H6, F+CH20, F+SiHC13, F+HBr andF4HI. These experiments yielded estimates of the relative rate constants into the excited vibrational states of the HF product of reaction, and of the rotational distributions in these vibrational manifolds.Information theory has been used in an attempt to compact the vibrational distributions of the reactions, and frequently this has allowed the identification of a single informative observable pertaining to the disposal of energy to this degree of freedom.For the reactions F+CH4, F4-C2 H6, F+CH2O, the analysis has permitted an insight into the role in the reaction dynamics of the internal degrees of freedom of the radical leaving group; for the reaction F+HI it allowed the discovery of two channels (distinguishable by the amount of energy apparently available to the reaction products) by which HF may be produced, although it was not possible using information theory to characterise these reaction pathways. Where appropriate, an information-theoretic analysis of the disposal of energy to the rotational degrees of freedom of the HF product has been attempted, but it has not been possible to identify the pertinent information observables.The classical trajectory method has been applied to the reactions F+HBr and F+HI in an attempt to explain the experimental results in terms of single potential surfaces, calculated semi-empirically by the London-Eyring-Polanyi-Sato method. Using the empirical findings of an earlier study of the reaction F+HCl -HF+Cl, some predictions have been made of the energy disposal and branching in the reaction H+C1F --> HF+Cl or HC1+F. Information theory has been used to demonstrate that the energy disposal alone is incapable of accounting for the calculated branching ratio. Finally, the systems H+F2 and D+F2 have been used to compare the findings of classical and quantum mechanics for the dynamics of atom-molecule reactions, and to gain insight into the effect of isotopic substitution on the energy distributions of these reactions. It is reported that, while the gross features of the dynamics are correctly predicted by a classical calculation, the finer aspects are not so, and that the effect of the increased mass of D over H, is a significant one, which may be explained classically.
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Published date: 1979
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Local EPrints ID: 462574
URI: http://eprints.soton.ac.uk/id/eprint/462574
PURE UUID: 76b051fc-6e49-4436-bd7d-722959b3efa6
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Date deposited: 04 Jul 2022 19:24
Last modified: 04 Jul 2022 19:24
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Author:
John Charles Naylor
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