Dynamics and mechanisms of hot chemistry stimulated by recoil methods. Progress report, March 1, 1978--February 28, 1979
The nuclear recoil chemical activation process in cyclobutane-t and subsequent inter- and intra-molecular energy transfer in recoil tritium and recoil chlorine hot reaction systems are analyzed. A stepladder model for intermolecular energy transfer from cyclobutane-t on collision shows average quanta of energy transferred range from 0.5 to 10 kcal/collision in He, N/sub 2/, CO/sub 2/ and cyclobutane bath gases. The recoil energy spectrum of hot chlorine atoms generated via the /sup 37/Cl(n,..gamma..)/sup 38/Cl reaction is also reported. The average recoil energy is found to be 294 eV and the maximum is 528 eV. Average reaction energy is calculated to be relatively independent of composition over the range from 0 to 99% moderation with noble gases in well scavenged systems of moderate reactivity. Geometrical isomerization accompanying the gas phase chlorine atom replacement reaction in 2,3 dichlorohexafluoro-2-butene as a function of moderation has been further investigated. A thermal or near thermal reaction path having a trans/cis product ratio of 1.3 and a high energy process which preferentially forms trans product from both cis and trans reactant are found. Dynamical features associated with the observed high energy inverse isotope effect in the reaction of chlorine atoms with H/sub 2/ and D/sub 2/ have been investigated through a non-Boltzmann rate constant analysis. The origin of this kinetic isotope effect is attributed to the secondary reactive process of collisional dissociation of translationally, vibrationally, and rotationally excited hydrogen chloride product molecules. Investigation of the kinetics and mechanisms of photochemical reactions between sulfur dioxide and aliphatic hydrocarbons has been initiated.
- Research Organization:
- Univ. of Utah, Salt Lake City, UT (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- EY-76-S-02-2190
- OSTI ID:
- 6062537
- Report Number(s):
- COO-2190-19; TRN: 79-018603
- Country of Publication:
- United States
- Language:
- English
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Study of intramolecular energy randomization following nuclear recoil, hot atom substitution
Dynamics and mechanisms of hot chemistry stimulated by recoil methods. Progress report, March 1, 1975--February 29, 1976
Related Subjects
CHLORINATED ALIPHATIC HYDROCARBONS
HOT ATOM CHEMISTRY
CYCLOALKANES
DEUTERIUM
ISOTOPE EFFECTS
RESEARCH PROGRAMS
HYDROCARBONS
PHOTOCHEMICAL REACTIONS
SULFUR DIOXIDE
CHLORINE
CHLORINE 37
ENERGY TRANSFER
NEUTRON REACTIONS
RADICALS
RECOILS
ALKANES
BARYON REACTIONS
CHALCOGENIDES
CHEMICAL REACTIONS
CHEMISTRY
CHLORINE ISOTOPES
ELEMENTS
HADRON REACTIONS
HALOGENATED ALIPHATIC HYDROCARBONS
HALOGENS
HYDROGEN ISOTOPES
ISOTOPES
LIGHT NUCLEI
NONMETALS
NUCLEAR REACTIONS
NUCLEI
NUCLEON REACTIONS
ODD-EVEN NUCLEI
ODD-ODD NUCLEI
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
RADIOCHEMISTRY
STABLE ISOTOPES
SULFUR COMPOUNDS
SULFUR OXIDES
400701* - Radiochemistry & Nuclear Chemistry- Hot-Atom Chemistry