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Title: KINETIC THEORY OF HOT-ATOM REACTIONS. II. EVALUATION OF COLLISIONAL ENERGY LOSS. APPLICATION TO REACTIVE MIXTURES

Abstract

S>The kinetic theory of reactions of atoms of high translational energy undergoing moderating collisions was further developed. The nature and lialidity of the assumptions underlying the treatment and the range of applicability of the final expressions are discussed in detail. It is shown that experimental data on the total probability of reaction in which the hot atom is chemically bound can be used to evaluate two fundamental quantities: the reactivity integral, or reaction probability integrated over energy on a logarithmic scale (I); and a measure of average energy transfer in collisions of hot atoms with the reactive species ( alpha ). The treatment involves no variable or arbitrary parameters. As a result sufficient data may be obtained to provide stringent internal consistency tests of the applicability of the model and its assumptions to any given system. Two types of systems are specifically treated: a single reactant moderated by inert gas; and competitive reactions in systems of two reactants. The relative utility of such systems for determination of the basic parameters alpha and I is discussed. Examples of the use of the expressions developed to calculate average logarithmic collisional energy loss ( alpha ) are given. Recent data on interaction ofmore » hot F with CF/sub 4/ and on hot H in mixtures of D/ sub 2/ and CH/sub 4/ are used. The alpha 's derived indicate that moderating collisions in these media are highly inelastic. The hypothesis that CH/sub 4/ is a better moderator than D/sub 2/ was quantitatively confirmed. The implications of the findings for the mechanism of hot-atom processes are briefly discussed. (auth)« less

Authors:
Publication Date:
Research Org.:
Yale Univ., New Haven
Sponsoring Org.:
USDOE
OSTI Identifier:
4129692
NSA Number:
NSA-18-003835
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics (U.S.)
Additional Journal Information:
Journal Volume: Vol: 39; Other Information: Orig. Receipt Date: 31-DEC-64
Country of Publication:
Country unknown/Code not available
Language:
English
Subject:
CHEMISTRY; ATOMS; CARBON FLUORIDES; COLLISIONS; DEUTERIUM; ENERGY; FLUORINATED HYDROCARBONS; FLUORINE; INERT GASES; LOSSES; METHANE; RADIOCHEMISTRY; REACTION KINETICS

Citation Formats

Wolfgang, R. KINETIC THEORY OF HOT-ATOM REACTIONS. II. EVALUATION OF COLLISIONAL ENERGY LOSS. APPLICATION TO REACTIVE MIXTURES. Country unknown/Code not available: N. p., 1963. Web. doi:10.1063/1.1734131.
Wolfgang, R. KINETIC THEORY OF HOT-ATOM REACTIONS. II. EVALUATION OF COLLISIONAL ENERGY LOSS. APPLICATION TO REACTIVE MIXTURES. Country unknown/Code not available. doi:10.1063/1.1734131.
Wolfgang, R. Sun . "KINETIC THEORY OF HOT-ATOM REACTIONS. II. EVALUATION OF COLLISIONAL ENERGY LOSS. APPLICATION TO REACTIVE MIXTURES". Country unknown/Code not available. doi:10.1063/1.1734131.
@article{osti_4129692,
title = {KINETIC THEORY OF HOT-ATOM REACTIONS. II. EVALUATION OF COLLISIONAL ENERGY LOSS. APPLICATION TO REACTIVE MIXTURES},
author = {Wolfgang, R},
abstractNote = {S>The kinetic theory of reactions of atoms of high translational energy undergoing moderating collisions was further developed. The nature and lialidity of the assumptions underlying the treatment and the range of applicability of the final expressions are discussed in detail. It is shown that experimental data on the total probability of reaction in which the hot atom is chemically bound can be used to evaluate two fundamental quantities: the reactivity integral, or reaction probability integrated over energy on a logarithmic scale (I); and a measure of average energy transfer in collisions of hot atoms with the reactive species ( alpha ). The treatment involves no variable or arbitrary parameters. As a result sufficient data may be obtained to provide stringent internal consistency tests of the applicability of the model and its assumptions to any given system. Two types of systems are specifically treated: a single reactant moderated by inert gas; and competitive reactions in systems of two reactants. The relative utility of such systems for determination of the basic parameters alpha and I is discussed. Examples of the use of the expressions developed to calculate average logarithmic collisional energy loss ( alpha ) are given. Recent data on interaction of hot F with CF/sub 4/ and on hot H in mixtures of D/ sub 2/ and CH/sub 4/ are used. The alpha 's derived indicate that moderating collisions in these media are highly inelastic. The hypothesis that CH/sub 4/ is a better moderator than D/sub 2/ was quantitatively confirmed. The implications of the findings for the mechanism of hot-atom processes are briefly discussed. (auth)},
doi = {10.1063/1.1734131},
journal = {Journal of Chemical Physics (U.S.)},
number = ,
volume = Vol: 39,
place = {Country unknown/Code not available},
year = {1963},
month = {12}
}