摘要:

AbstractThe reaction SO + SO →l S + SO2(2) was studied in the gas phase by using methyl thiirane as a titrant for sulfur atoms. By monitoring the C3H6produced in the reaction\documentclass{article}\pagestyle{empty}\begin{document}$ {\rm S} + {\rm CH}_3\hbox{---} \overline {{\rm CH\hbox{---}CH}_2\hbox{---} {\rm S}} \to {\rm S}_2 + {\rm C}_3 {\rm H}_6 (7) $\end{document}, we determined thatk2≃ 3.5 × 10−15cm3/s at

ISSN:0538-8066    

DOI:10.1002/kin.550151102

出版商:John Wiley&Sons, Inc.    

年代:1983

数据来源: WILEY

摘要:

AbstractThe azoethane‐sensitized thermal reaction of isobutene has been studied at 526–565 K. The initial concentrations of azoethane and isobutene were in the ranges of 1.40–10.5 × 10−4and 6.78–26.6 × 10−4mol/dm3, respectively. From the initial rates of formation of ethane and 2‐methylpentane the heat of formation of the 2‐methyl‐2‐pentyl radical was determined. The result obtained is ±H f0(2‐methyl‐2‐pentyl) = 0.8 ± 2.0 kcal/mol. The entropy of the radical, obtained from statistical mechanical calculations and experimentally, isS0(2‐methyl‐2 pentyl) = 92.8 ± 1.5 cal/mol°K. The results support the high heat of formation of thet‐butyl

ISSN:0538-8066    

DOI:10.1002/kin.550151103

出版商:John Wiley&Sons, Inc.    

年代:1983

数据来源: WILEY

摘要:

AbstractThe reaction mechanism of carbon dioxide with diethanolamine (DEA) is investigated using the stopped‐flow method with optical detection in the ranges of concentration [DEA] = 0.111–8.4 × 10−2Mand [CO2] = 2.94–5.6 × 10−3M. The comparison of the fast time‐dependent light transmission change of a pH indicator with theoretical simulations of integrated rate equations requires a kinetic model in which a simple carbamate formation takes place simultaneously with hydration reactions, whose contributions are far from being negligible. A first‐order reaction relative to DEA is thus found with a rate constant for carbamate formation smaller than usually predicted (110 ± 15M−1s−1at 25°C). The equilibrium constant for the same reaction is also determined giving pKR= 5.3 at 25°C, in satisfactory agreement with

ISSN:0538-8066    

DOI:10.1002/kin.550151104

出版商:John Wiley&Sons, Inc.    

年代:1983

数据来源: WILEY

摘要:

AbstractRelative rate constants for the gas‐phase reactions of OH radicals with a series of cycloalkenes have been determined at 298 ± 2 K using methyl nitrite photolysis in air as a source of OH radicals. Using a rate constant for the reaction of OH radicals with isoprene of 9.60 × 10−11cm3molecule−1s−1, the rate constants obtained were (X 1011cm3molecule−1s−1): cyclopentene 6.39 ± 0.23, cyclohexene 6.43 ± 0.17, cycloheptene 7.08 ± 0.22, 1,3‐cyclohexadiene 15.6 ± 0.5, 1,4 cyclohexadiene 9.48 ± 0.39, bicyclo[2.2.1]‐2‐heptene 4.68 ± 0.39, bicyclo[2.2.1]2,5 heptadiene 11.4 ± 1.0, and bicyclo[2.2.2] 2 octene 3.88 ± 0.19. These data show that the rate constants for the nonconjugated cycloalkenes studied depend on the number of double bonds and the degree of substitution per double bond, and indicate that there are no obvious effects of ring strain energy on these OH radical addition rate constants. A predictive technique for the estimation of OH radical rate constants for alkenes and cycloalkenes

ISSN:0538-8066    

DOI:10.1002/kin.550151105

出版商:John Wiley&Sons, Inc.    

年代:1983

数据来源: WILEY

摘要:

AbstractThe gas‐phase thermal isomerization of hexachlorocyclopropane to hexachloropropene at 208–283°C is first order and unaffected by changes in the surface‐to‐volume ratio or by the addition of iodine, tetrachloroethylene, and oxygen. The first‐order rate constants fit the Arrhenius equation\documentclass{article}\pagestyle{empty}\begin{document}$${\rm log}k({\rm s}^{ - 1}) = (15.74 \pm .022) - (45,660 \pm 526)/4.576T$$\end{document}The reaction was interpreted as an unimolecular process taking place with chlorine atom migration. A comparison of the reactivities of several chlorocyclopropan

ISSN:0538-8066    

DOI:10.1002/kin.550151106

出版商:John Wiley&Sons, Inc.    

年代:1983

数据来源: WILEY

摘要:

AbstractInput data and results are presented for the calculation of a number of third‐order rate constants of atmospheric interest using Troe′s approximate method. A comparison with experimental data indicates that this approach provides a reliable method for predicting unknown rate constants and estimating temperature dependences. These calculations form the basis of the recommendations of the NASA review panel for third‐order rate constants to be used in atmospheric mod

ISSN:0538-8066    

DOI:10.1002/kin.550151107

出版商:John Wiley&Sons, Inc.    

年代:1983

数据来源: WILEY

摘要:

AbstractWe have reinvestigated temperature effects on the rates of hydrolysis of 0.0585Msucrose in 0.57MHCl solutions over the range of 10–40°C using polarimetry as a physical method to follow the reaction while simultaneously analyzing the solutions by HPLC for the disappearance of sucrose and by GLC for the appearance of glucose. When the polarimetric data are corrected for the mutarotation lag, the energy of activation values are the same by all three analytical methods and are temperature‐indepen

ISSN:0538-8066    

DOI:10.1002/kin.550151108

出版商:John Wiley&Sons, Inc.    

年代:1983

数据来源: WILEY

ISSN:0538-8066    

DOI:10.1002/kin.550151109

出版商:John Wiley&Sons, Inc.    

年代:1983

数据来源: WILEY

ISSN:0538-8066    

DOI:10.1002/kin.550151110

出版商:John Wiley&Sons, Inc.    

年代:1983

数据来源: WILEY

ISSN:0538-8066    

DOI:10.1002/kin.550151111

出版商:John Wiley&Sons, Inc.    

年代:1983

数据来源: WILEY