摘要:

AbstractA kinetic model is presented to describe the high temperature (1800 K

ISSN:0538-8066    

DOI:10.1002/kin.550260302

出版商:John Wiley&Sons, Inc.    

年代:1994

数据来源: WILEY

摘要:

AbstractStructure–reactivity correlations are developed and used to test a biradical mechanism for gas‐phase thermal Diels‐Alder reactions of cyclohexa‐1,3‐diene with substituted ethenes and reverse reactions. © 1994 John Wiley

ISSN:0538-8066    

DOI:10.1002/kin.550260303

出版商:John Wiley&Sons, Inc.    

年代:1994

数据来源: WILEY

摘要:

AbstractThe kinetics of hydrogen peroxide decomposition has been investigated in the presence of Wofatit KPS (4% DVB, 40–80 μm) resin in the form of mono (mea), di (dea), triethanolamine (tea), ethylenediamine (eda), andN,N′‐diethylethylenediamine (deeda)‐ Mn(II) complexes. The rate constantk(per g dry resin) was evaluated over the temperature range 25–40°C. The reaction was first‐order with respect to [H2O2]. The rate constant,k, with the three ethanolamines decreased in the following order mea>dea>tea which is the same order of basicity. Also,kvalue with deeda is lower than eda as a result of steric hindrance. The peroxo metal complex which formed at the beginning of the reaction, was found to contain the catalytic active species. The rate of reaction was proportional to [Mn‐complex], [H2O2] and [H+]−1. The activation parameters were calculated and a probable reaction mechanism is proposed. © 1994 Jo

ISSN:0538-8066    

DOI:10.1002/kin.550260304

出版商:John Wiley&Sons, Inc.    

年代:1994

数据来源: WILEY

摘要:

AbstractComplex dynamical behavior has been observed in the oxidation of hydroxylamine by bromate in acidic sulfate medium. The reaction shows clock type kinetics in closed conditions and an aperiodic oscillations if gaseous products are removed from the system with a constant flow‐rate. The reduction kinetics of bromate ions with excess hydroxylamine has been studied in the presence of allyl alcohol. The observed pseudo‐first‐order rate constantkobshas been found to follow the expression\documentclass{article}\pagestyle{empty}\begin{document}$$ k_{{\rm obs}} = \frac{{kK_1 \left[{{\rm H}^ +} \right]\left[{{\rm hydroxylamine}} \right]}}{{\left({1 + {\rm K}_{\rm 1} \left[{{\rm H}^ +} \right]} \right){\rm K}_{\rm 2}}} $$\end{document}where [hydroxylamine] is total initial hydroxylamine concentration, K1= 0.5 M−1, K2= 106M−1, andk= 2.57 × 103M−1s−1at 298.15 K andI= 2.0 M.The rate constant for the bromine oxidation of hydroxylamine in sulfuric aqueous solution has been determined. © 1994 John

ISSN:0538-8066    

DOI:10.1002/kin.550260305

出版商:John Wiley&Sons, Inc.    

年代:1994

数据来源: WILEY

摘要:

AbstractThe kinetics of the title reactions were investigated in a discharge flow tube by using laser magnetic resonance detection of HO2. The upper limits for the bimolecular rate constants for the reactions of HO2with H2S (k1), CH3SH (k2), and CH3SCH3(k3) are<3 × 10−15,<4 × 10−15, and<5 × 10−15cm3molecule−1s−1, respectively, at 298 K. Our upper limit fork1is three orders of magnitude lower than the previously reported value.Measurements at higher temperatures also yield similar upper limits. Our results suggest that HO2is not an important oxidant for these reduced compounds in the atmosphere. © 1994 John Wi

ISSN:0538-8066    

DOI:10.1002/kin.550260306

出版商:John Wiley&Sons, Inc.    

年代:1994

数据来源: WILEY

摘要:

AbstractRate coefficients for the reaction of NO3with dimethyl ether, diethyl ether, di‐n‐propyl ether, and methylt‐butyl ether (MTBE) have been determined. Absolute rates were measured at temperatures between 258 and 373 K using the fast flow‐discharge technique. Relative rate experiments were also made at 295 K in a reactor equipped with White optics and using FTIR spectroscopy to follow the reactions. The measured rate coefficients (in units of 10−15cm3molecule−1s−1) at 295 K are: 0.26 ± 0.11, 2.80 ± 0.23, 6.49 ± 0.65, and 0.64 ± 0.06 for dimethyl ether, diethyl ether, di‐n‐propyl ether, and methylt‐butyl ether, respectively. The corresponding activation energies are 21.0 ± 5.0, 17.2 ± 4.0, 15.5 ± 2.1, and 20.1 ± 1.7 kJ mole−1. The error limits correspond to the 95%‐confidence interv

ISSN:0538-8066    

DOI:10.1002/kin.550260307

出版商:John Wiley&Sons, Inc.    

年代:1994

数据来源: WILEY

摘要:

AbstractThe gas‐phase thermal decomposition rate of peroxy‐n‐butyryl nitrate (n‐C3H7C(O)OONO2, PnBN) has been measured at ambient temperature (296 K) and 1 atm of air relative to that of peroxyacetyl nitrate (CH3C(O)OONO2, PAN) using mixtures of PAN (14–19 ppb), PnBN (22–46 ppb), and nitric oxide (1.35–1.90 ppm). The PnBN/PAN decomposition rate ratio was 0.773 ± 0.030. This ratio, together with a literature value of 3.0 × 10−4s−1for the thermal decomposition rate of PAN at 296 K, yields a PnBN thermal decomposition rate of (2.32 ± 0.09) × 10−4s−1. The results are briefly discussed by comparison with data for other peroxyacyl nitrates and with respect to the atmospheric persistence of PnBN. ©

ISSN:0538-8066    

DOI:10.1002/kin.550260308

出版商:John Wiley&Sons, Inc.    

年代:1994

数据来源: WILEY

ISSN:0538-8066    

DOI:10.1002/kin.550260301

出版商:John Wiley&Sons, Inc.    

年代:1994

数据来源: WILEY