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 reaction between NO2 and CF2CCl2 has been investigated in the temperature range from 50 to 80°C. The reaction is homogeneous. Three products are formed: O2NCF2CCl2NO2 and equimolecular amounts of CINO and of O2NCF2C(O)Cl. The rate of consumption of the reactants is independent of the total pressure, the reaction products, and added inert gases and can be represented by a second-order reaction: \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d[{\rm NO}_{\rm 2}]}}{{dt}} = - 2\frac{{d[{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2}]}}{{dt}} = k[{\rm NO}_{\rm 2}][{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2}] $$\end{document}However, the distribution of the products is influenced by the pressure of the present gases, which favor the formation of the dinitro-compound in a specific way. The effect of CF2CCl2 is the greatest. In the absence of added gases, the ratio of O2NCF2CCl2NO2 to that of O2NCF2C(O)Cl is proportional to (CF2CCl2 + γP products).The experimental results can be explaned by the following mechanism: P and X represent the products and the added gases: \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d[{\rm NO}_{\rm 2}]}}{{dt}} = - 2\frac{{d[{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2}]}}{{dt}} = k_1 [{\rm NO}_{\rm 2}][{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2}] $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = 3.16 \pm 0.5 \times 10^6 \exp ( - 10500 \pm 1000{\rm cal/}RT){\rm M}^{{\rm - 1}} {\rm s}^{{\rm - 1}} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm \gamma }_{{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2} } :{\rm \gamma }_P :{\rm \gamma }_{{\rm C}_{\rm 2} {\rm F}_{\rm 5} {\rm CI}} :{\rm \gamma }_{{\rm CCL}_{\rm 3} } :{\rm \gamma }_{{\rm CF}_{\rm 4} } :{\rm \gamma }_{{\rm N}_{\rm 2} } = 1:0.22:0.15:0.14:0.054:0.015 $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm \gamma }_{{\rm NO}_{\rm 2} } 〈 0.01 $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_3 = 1.4 \pm 0.3 \times 10^8 {\rm s}^{{\rm - 1}} $$\end{document}
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550180810
