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Title: RECOIL TRITIUM REACTIONS: METHYL CHLORIDE

Abstract

Recoil tritium reactions with CH/sub 3/Cl give three importart hot products HT, CH/sub 2/TCl, and CH/sub 3/T, in the approxiraate ratios 2.7: 1.0:0.8 at 1 atmosphere pressure. When I/sub 2/ is used as the radical scavenger, CH/sub 2/TI is observed in yields comparable to that of CH/sub 2/TCl. Variation of the gas pressure during irradiation shows that the yields of CH/sub 2/TCl and CH/sub 2/TI are pressure dependert in a manner consistent with the reaction CH/sub 2/TCl* yields CH/sub 2/T + Cl. Measurements in the liquid phase indicate that approximately half of the original molecules formed by substitution of T for H decompose at 1 atm. gas pressure before de-excitation can occur. The relative ease of replacement of H by T per C--H bond is about 0.78 to 1 for CH/sub 3/Cl vs cyclo-C/sub 4/H/sub 8/. The pressure-dependent reactions demonstrate the presence of a long-lived excited molecule and indicate that most of the observed CH/sub 2/T radicals are formed through a two-step mechanism. Steric inhibition of hot substitution reactions by Cl substituents is a small effect at most. (auth)

Authors:
; ;
Publication Date:
Research Org.:
Univ. of Kansas, Lawrence, KS (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
4055322
NSA Number:
NSA-18-017893
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society (U.S.)
Additional Journal Information:
Journal Volume: Vol: 86; Other Information: Orig. Receipt Date: 31-DEC-64
Country of Publication:
Country unknown/Code not available
Language:
English
Subject:
CHEMISTRY; BUTANE; CHEMICAL REACTIONS; CHLORIDES; COMPOUNDS; CONFIGURATION; CYCLOALKANES; DECOMPOSITION; DIAGRAMS; EFFICIENCY; ENERGY LEVELS; EXCITATION; FREE RADICALS; GASES; HYDROGEN; IODINE; LABELLED COMPOUNDS; LIFETIME; LIQUIDS; MEASURED VALUES; METHYL RADICALS; MOLECULES; ORGANIC CHLORINE COMPOUNDS; ORGANIC IODINE COMPOUNDS; PRESSURE; RADIATION CHEMISTRY; RADIOLYSIS; RECOILS; TABLES; TRITIUM; VARIATIONS

Citation Formats

Tang, Y, Lee, E K.C., and Rowland, F S. RECOIL TRITIUM REACTIONS: METHYL CHLORIDE. Country unknown/Code not available: N. p., 1964. Web. doi:10.1021/ja01061a002.
Tang, Y, Lee, E K.C., & Rowland, F S. RECOIL TRITIUM REACTIONS: METHYL CHLORIDE. Country unknown/Code not available. https://doi.org/10.1021/ja01061a002
Tang, Y, Lee, E K.C., and Rowland, F S. 1964. "RECOIL TRITIUM REACTIONS: METHYL CHLORIDE". Country unknown/Code not available. https://doi.org/10.1021/ja01061a002.
@article{osti_4055322,
title = {RECOIL TRITIUM REACTIONS: METHYL CHLORIDE},
author = {Tang, Y and Lee, E K.C. and Rowland, F S},
abstractNote = {Recoil tritium reactions with CH/sub 3/Cl give three importart hot products HT, CH/sub 2/TCl, and CH/sub 3/T, in the approxiraate ratios 2.7: 1.0:0.8 at 1 atmosphere pressure. When I/sub 2/ is used as the radical scavenger, CH/sub 2/TI is observed in yields comparable to that of CH/sub 2/TCl. Variation of the gas pressure during irradiation shows that the yields of CH/sub 2/TCl and CH/sub 2/TI are pressure dependert in a manner consistent with the reaction CH/sub 2/TCl* yields CH/sub 2/T + Cl. Measurements in the liquid phase indicate that approximately half of the original molecules formed by substitution of T for H decompose at 1 atm. gas pressure before de-excitation can occur. The relative ease of replacement of H by T per C--H bond is about 0.78 to 1 for CH/sub 3/Cl vs cyclo-C/sub 4/H/sub 8/. The pressure-dependent reactions demonstrate the presence of a long-lived excited molecule and indicate that most of the observed CH/sub 2/T radicals are formed through a two-step mechanism. Steric inhibition of hot substitution reactions by Cl substituents is a small effect at most. (auth)},
doi = {10.1021/ja01061a002},
url = {https://www.osti.gov/biblio/4055322}, journal = {Journal of the American Chemical Society (U.S.)},
number = ,
volume = Vol: 86,
place = {Country unknown/Code not available},
year = {Wed Apr 01 00:00:00 EST 1964},
month = {Wed Apr 01 00:00:00 EST 1964}
}