ISSN:0538-8066    

DOI:10.1002/kin.550020302

出版商:John Wiley&Sons, Inc.    

年代:1970

数据来源: WILEY

摘要:

AbstractA method for constructing potential energy surfaces previously proposed by the author has been extended to hydrogen transfer reactions between halide, oxygen, and carbon atoms. A qualitative relation was found between the repulsive energy and the number of anti‐bonding electrons. In general, the calculated kinetic isotope effect is in satisfactory agreement with observed values and the contributions by H‐atom tunneling to the rate of reaction is smaller than that obtained from other surfa

ISSN:0538-8066    

DOI:10.1002/kin.550020303

出版商:John Wiley&Sons, Inc.    

年代:1970

数据来源: WILEY

摘要:

AbstractO(1D), produced from the photolysis of N2O at 2139 Å, reacts with N2O in accord with:\documentclass{article}\pagestyle{empty}\begin{document} $$ \begin{array}{*{20}c} {(2)} & {{\rm O}(^1 D) + N_2 {\rm O} \to {\rm N}_2 + {\rm O}_2 } \\ \end{array} $$ \end{document}\documentclass{article}\pagestyle{empty}\begin{document} $$ \begin{array}{*{20}c} {(3)} & { \to 2{\rm NO}} \\ \end{array} $$ \end{document}We have used the method of chemical difference to obtain an accurate measure ofk2/k3= 0.59 ± 0.01. Furthermore, the quantum yield of production of O(3P), either on direct photolysis or on deactivation of O(1D) by N2O, is less than 0.02 and probably zer

ISSN:0538-8066    

DOI:10.1002/kin.550020304

出版商:John Wiley&Sons, Inc.    

年代:1970

数据来源: WILEY

摘要:

AbstractNitrogen quantum yields are reported for the photolysis of C2F5NNC2F5at 3660 Å over the pressure range 2–10 cm from 25° to 150°c. The Stern–Volmer plots obtained are discussed and compared with those obtained with azoethane and azois

ISSN:0538-8066    

DOI:10.1002/kin.550020305

出版商:John Wiley&Sons, Inc.    

年代:1970

数据来源: WILEY

摘要:

AbstractThe kinetics of the decomposition of benzotrifluoride was studied from 720°c to 859°c in a flow system with and without carrier gas. Consideration of the product distribution made possible the study of the decomposition into CF3and C6H5radicals, which appeared to be truly homogeneous in character. The first‐order rate constant of the CC bond fission, logk(sec−1) = (17.9 ± 0.5) (99.7 ± 2.5)/θ, did not change with change of initial concentration, pressure of the carrier gas, or contact time. The Arrhenius parameters have been related to the appropriate thermodynamic data. Assumption of 0 kcal/mole for the activation energy of the reverse combination reaction yielded DH 298°(C6H5CF3) = 103.6 ± 2.5 kcal/mole and ΔH f298°(C6H5) = 77.1 ± 3.0 kcal/mole.Applicability of the simple first‐order formula to calculation of the rate constant h

ISSN:0538-8066    

DOI:10.1002/kin.550020306

出版商:John Wiley&Sons, Inc.    

年代:1970

数据来源: WILEY

摘要:

AbstractCombination reactions of the methyl radical have been studied by following the decay of the absorbance of the methyl radical during the course of the reaction by means of kinetic spectroscopy. The limiting values of the second‐order rate constants at high pressure were determined for two reactions at room temperature:\documentclass{article}\pagestyle{empty}\begin{document}$ \begin{array}{*{20}c} {{\rm CH}_{\rm 3} + {\rm CH}_{\rm 3} ( + {\rm M}) \to {\rm CH}_{\rm 3} {\rm CH}_{\rm 3} ( + {\rm M}):k_1 = (2.6 \pm 0.3) \times 10^{10} 1{\rm mole}^{ - {\rm 1}} \sec ^{ - 1} } \\ {{\rm CH}_{\rm 3} + {\rm NO }( + {\rm M}) \to {\rm CH}_{\rm 3} {\rm NO }( + {\rm M}):k_2 = (2.4 \pm 0.2) \times 10^9 1{\rm mole}^{ - {\rm 1}} \sec ^{ - 1} } \\ \end{array} $\end{document}The extinction coefficient of the methyl radical was found to have a maximum value of (1.02 ± 0.06) X 1041 mole−1cm−1at 216.4 nm. Integration of the extinction coefficient over the absorption band of the methyl radical gave an oscillator strength of 1.0

ISSN:0538-8066    

DOI:10.1002/kin.550020307

出版商:John Wiley&Sons, Inc.    

年代:1970

数据来源: WILEY

摘要:

AbstractA simple electrostatic model of point dipoles is used which permits direct calculation of the activation energies for the addition of the molecules H2O, H2S, H3N, and H3P to olefins. These calculated values agree with the known experimental data to within ±2 kcal/mole on the average. It was found that the best fit could be obtained with a polar transition state that corresponded to a reduction in bond order from 1 to ½ for the bond‐breaking coordinates and an increase in bond order from 0 to 0.18 for the bond‐forming coordinates. The replacement of a hydrogen atom of the species H2O, H2S, H3N, or H3P by a polarizable methyl group is expected to stabilize the charge on the central atoms. The following stabilization energies for the pairs H2OCH3OH, H2SCH3SH, H3NCH3NH2, H3PCH3PH2were calculated: −4.8 kcal/mole, −0.7 kcal/mole, −1.9 kcal/mole, −0.8 kc

ISSN:0538-8066    

DOI:10.1002/kin.550020308

出版商:John Wiley&Sons, Inc.    

年代:1970

数据来源: WILEY

摘要:

AbstractThe reaction of trifluoromethyl radicals with ammonia in the gas phase has been studied in the temperature range 30‐352°. Product formation is not explicable simply in terms of the reactions:\documentclass{article}\pagestyle{empty}\begin{document}$\begin{array}{*{20}c} {{\rm CF}_{\rm 3} + {\rm NH}_{\rm 3} \to {\rm CF}_3 {\rm H} + {\rm NH}_2 } \\ {2{\rm CF}_3 \to {\rm C}_2 {\rm F}_6 } \\\end{array}$\end{document}and curvature of the Arrhenius plot at high and low temperatures suggests that there are additional sources of fluorofo

ISSN:0538-8066    

DOI:10.1002/kin.550020309

出版商:John Wiley&Sons, Inc.    

年代:1970

数据来源: WILEY

ISSN:0538-8066    

DOI:10.1002/kin.550020301

出版商:John Wiley&Sons, Inc.    

年代:1970

数据来源: WILEY