The Influence of Phase, Temperature and Bromine Concentration on Bromine Production in the Decomposition of CCI ₃ Br by γ-Rays ^1a,b

Journal Article · Fri Sep 01 04:00:00 EDT 1961 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja01478a002· OSTI ID:4837890

Firestone, Richard F.; Willard, John E.

The production of Br/sub 2/ by the radiolysis of CCl/sub 3/Br with Co/ sup 60/ gamma rays was studied in the solid, liquid, and gas phases and as a function of temperature and bromine concentration. In the solid state at - 121 deg and below, the value of G(Br/sub 2/) is 0.12 molecule produced/100 ev, independent of temperature. From 78 to 98 deg G(Br/sub 2/) increases with temperature to about 3.5 with an apparent activation energy of about 2 kcal/mole. Although this activation energy suggests a diffusion controlled process, there is no change in G(Br/sub 2/) or its temperature dependence on crossing solid phase transitions at -35.5 and -13.5 deg or in going from the solid to the liquid state at the melting point - 5.6 deg . Preliminary experiments indicate that there is no marked difference in yield in the gas phase as compared to the liquid phase at the boiling point. At bromine concentrations above about 0.01 M, G(Br/ sub 2/) is independent of bromine concentration at all temperatures in both the solid and the liquid. Below 0.01 M and at temperatures of 20 deg and above, however, G(Br/sub 2/) decreases with increasing concentration. The bromine- sensitive reaction appears to have an activation energy of about 3 kcal/mole, slightly higher than the bromine insensitive reaction. The presence of oxygen raises G(- CCl/sub 3/Br) several-fold, the production of Cl/sub 2/ (a minor radiolysis product) being increased by a larger factor than Br/sub 2/ production.

• Research Organization: Univ. of Wisconsin, Madison
• Sponsoring Organization: USDOE
• NSA Number: NSA-15-030726
• OSTI ID: 4837890
• Journal Information: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 17 Vol. 83; ISSN 0002-7863
• Publisher: American Chemical Society (ACS)
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

BOILING
BROMINE
CHEMISTRY
CHLORINE
COBALT 60
CONTROL
DECOMPOSITION
DIFFUSION
GAMMA RADIATION
GASES
HALOGENATED HYDROCARBONS
LIQUIDS
MELTING
ORGANIC COMPOUNDS
OXYGEN
PRODUCTION
SOLIDS
TEMPERATURE