ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The kinetics of the gas-phase thermal isomerization between trans- and cis-1,2-bis(trifluoromethyl)-1,2,3,3-tetrafluorocyclopropane as well as their decomposition to trans- and cis-perfluoro-2-butene, respectively, and CF2, was studied in the temperature range of 473-533°K, with an initial pressure of reactant of 1.5 to 7.0 Torr. Some runs were also made with the addition of SF6 as an inert gas up to a total pressure of 100 Torr. The reactions are first order and homogeneous. The rate constants for the geometrical isomerization fit the following Arrhenius relations: \documentclass{article}\pagestyle{empty}\begin{document}$$ {{\log {k}_{{trans}\to {cis}}}\mathord{\left/{\vphantom {{\log {k}_{{trans}\to {cis}}}{(\sec ^{ - 1})}}}\right.\kern-\nulldelimiterspace}{(\sec ^{ - 1})}}{ = }{{{(15}{.15}\pm{0}{.16)-(44,487}\pm{ 374)}}\mathord{\left/ {\vphantom {{{(15}{.15} \pm{0}{.16) - (44,487 }\pm { 374)}}{4.576{ }T}}} \right.\kern-\nulldelimiterspace} {4.576{ }T}} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {{\log {k}_{{trans}\to {cis}}}\mathord{\left/{\vphantom {{\log {k}_{{trans}\to {cis}}}{(\sec ^{ - 1})}}}\right.\kern-\nulldelimiterspace} {(\sec ^{ - 1})}}{ = }{{{(15}{.35} \pm {0}{.19) - (43,419 } \pm { 428)}} \mathord{\left/ {\vphantom {{{(15}{.35} \pm {0}{.19) - (43,419 } \pm { 428)}} {4.576{ }T}}} \right. \kern-\nulldelimiterspace} {4.576{ }T}} $$\end{document} and the corresponding equations for the decomposition of the trans and cis-cyclopropane are \documentclass{article}\pagestyle{empty}\begin{document}$$ {{\log {k}_{{trans}}} \mathord{\left/ {\vphantom {{\log {k}_{{trans}}} {(\sec ^{ - 1})}}} \right. \kern-\nulldelimiterspace} {(\sec ^{ - 1})}}{ = }{{{(15}{.14} \pm {0}{.28) - (46,700} \pm { 652)}} \mathord{\left/ {\vphantom {{{(15}{.14} \pm {0}{.28) - (46,700 } \pm { 652)}} {4.576{ }T}}} \right. \kern-\nulldelimiterspace} {4.576{ }T}} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {{\log {k}_{{cis}}} \mathord{\left/ {\vphantom {{\log {k}_{{cis}} } {(\sec ^{ - 1})}}} \right. \kern-\nulldelimiterspace} {(\sec ^{ - 1})}}{ = }{{{(15}{.39} \pm {0}{.26) - (46,639} \pm { 598)}} \mathord{\left/ {\vphantom {{{(15}{.39} \pm {0}{.26) -(46,639 } \pm { 598)}} {4.576{ }T}}} \right. \kern-\nulldelimiterspace} {4.576{ }T}} $$\end{document}.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550111208
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