摘要:

AbstractThe photolysis of 2‐methylcyclohexanone has been studied in the gas phase at 313 nm, mainly at 100°C, over a range of pressures. The Hg(63P1) photosensitized decomposition has also been investigated at 100°C. Under conditions of high excitation and/or little collisional quenching the major products are carbon monoxide and the hydrocarbons: 1‐hexene,trans‐andcis‐2‐hexene and methylcyclopentane, with minor aldehyde formation. The various product ratios are presented in tabular form. At lower excitation energies, and with increased collisional deactivation,trans‐ andcis‐5‐heptenal become important products, and thetrans/cisaldehyde ratio is seen to be slightly pressure dependent when all the systems are compared. Similarly, there is a small pressure dependence for the Σ hexenes/methylcyclopentane ratio. From experiments at 250°C the temperature dependence of this ratio was established, and for thermalized hexane‐1,5‐diyl an activation energy difference (Ed−Ec) = −1.3 kcal mol−1has been determined for the disproportionation and combination of the biradical. The mechanism for the photolysis is discussed in terms of triplet state photochemistry and biradical intermediates as developed, in particular, by Frey and coworkers,

ISSN:0538-8066    

DOI:10.1002/kin.550200502

出版商:John Wiley&Sons, Inc.    

年代:1988

数据来源: WILEY

摘要:

AbstractThe hexacyanoferrate(III)‐thallium(I) reaction in aqueous acetic acid containing large concentrations of hydrochloric acid is considerably accelerated both by hydrogen and chloride ions as well as increasing acetic acid in the medium. The experimental results obey the rate law (1) where β1to β6\documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{rcl} {{\rm (1)}} & {- \frac{{{\rm d[Fe(CN)}_{\rm 6} ^{{\rm 3 -}}]}}{{dt}} = \frac{{\{\beta _4 k_a [{\rm H}^ +] + \beta _5 k_b [{\rm H}^ +]^2 \} \beta _2 [{\rm Cl}^ -]^2 [{\rm Fe(CN)}_{\rm 6} ^{{\rm 3 -}}]_T [Tl^ +]_T}}{{\{1 + \beta _4 [{\rm H}^ +] + \beta _5 [{\rm H}^ +]^2 + \beta _6 [{\rm H}^ +]^3 \} \{1 + \beta _1 [{\rm Cl}^ -] + \beta _2 [{\rm Cl}^ -]^2 + \beta _2 [{\rm Cl}^ -]^3 \}}}}\end{array}$$\end{document}are the cumulative stability constants of the species TlCl, TlCl 2−, TlCl 32−, HFe(CN) 62−, H2Fe(CN) 6−and H3Fe(CN)6respectively andkaandkbare the rate constants associated with the mono‐ and di‐protonated oxidant species. The main active species are

ISSN:0538-8066    

DOI:10.1002/kin.550200503

出版商:John Wiley&Sons, Inc.    

年代:1988

数据来源: WILEY

摘要:

AbstractThe thermal isomerization of azulene was studied in shock waves over the range 1300–1900 K. Monitoring azulene and naphthalene light absorptions in the UV, a complete conversion azulene → naphthalene was observed. After correction for some falloff effects, a limiting high pressure rate constantkx= 1012.93exp(−263 kJ mol−1/RT) s−1was derived. Based on thiskx, specific rate constantsk(E) for photoexcitation experiments were co

ISSN:0538-8066    

DOI:10.1002/kin.550200504

出版商:John Wiley&Sons, Inc.    

年代:1988

数据来源: WILEY

摘要:

AbstractRate constants for the reactions of oxirane with alkanethiols in the presence of basic catalyst were studied at the temperature range of 20–50°C. A mechanism of these reactions has been proposed and appropriate kinetic equation has been present

ISSN:0538-8066    

DOI:10.1002/kin.550200505

出版商:John Wiley&Sons, Inc.    

年代:1988

数据来源: WILEY

摘要:

AbstractThe chlorinations of dimethylamine, diethylamine, methylethanolamine, ethylethanolamine and diethanolamine by N‐chlorosuccinimide have been found to be equilibrium reactions of order one with respect to both N‐chlorosuccinimide and amine in the forward direction and of order one with respect to succinimide and the resulting N‐chloramine in the other. These results are explained by postulating a mechanism in which the rate controlling step consists in direct exchange of positive chlorine between the N‐chlorosuccinimide and th

ISSN:0538-8066    

DOI:10.1002/kin.550200506

出版商:John Wiley&Sons, Inc.    

年代:1988

数据来源: WILEY

ISSN:0538-8066    

DOI:10.1002/kin.550200501

出版商:John Wiley&Sons, Inc.    

年代:1988

数据来源: WILEY