摘要:

AbstractThe reactionswhere Y = CH3(M), C2H5(E),iC3H7(I), andtC4H9(T) have been studied between 488 and 606 K. The pressures of CHD ranged from 16 to 124 torr and those of YE from 57 to 625 torr. These reactions are homogeneous and first order with respect to each reagent. The rate constants (in L/mol·s) are given by\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} k_{{\rm NMBO}} = - {{\left( {26530 \pm 80} \right)} \mathord{\left/ {\vphantom {{\left( {26530 \pm 80} \right)} {4.576T + \left( {6.05 \pm 0.03} \right)}}} \right. \kern-\nulldelimiterspace} {4.576T + \left( {6.05 \pm 0.03} \right)}} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} k_{{\rm XMBO}} = - {{\left( {28910 \pm 130} \right)} \mathord{\left/ {\vphantom {{\left( {28910 \pm 130} \right)} {4.576T + \left( {6.32 \pm 0.05} \right)}}} \right. \kern-\nulldelimiterspace} {4.576T + \left( {6.32 \pm 0.05} \right)}} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} k_{{\rm NEBO}} = - {{\left( {26150 \pm 120} \right)} \mathord{\left/ {\vphantom {{\left( {26150 \pm 120} \right)} {4.576T + \left( {5.85 \pm 0.05} \right)}}} \right. \kern-\nulldelimiterspace} {4.576T + \left( {5.85 \pm 0.05} \right)}} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} k_{{\rm XEBO}} = - {{\left( {28560 \pm 120} \right)} \mathord{\left/ {\vphantom {{\left( {28560 \pm 120} \right)} {4.576T + \left( {6.07 \pm 0.05} \right)}}} \right. \kern-\nulldelimiterspace} {4.576T + \left( {6.07 \pm 0.05} \right)}} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} k_{{\rm NIBO}} = - {{\left( {26560 \pm 80} \right)} \mathord{\left/ {\vphantom {{\left( {26560 \pm 80} \right)} {4.576T + \left( {5.57 \pm 0.03} \right)}}} \right. \kern-\nulldelimiterspace} {4.576T + \left( {5.57 \pm 0.03} \right)}} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} k_{{\rm XIBO}} = - {{\left( {28350 \pm 100} \right)} \mathord{\left/ {\vphantom {{\left( {28350 \pm 100} \right)} {4.576T + \left( {5.47 \pm 0.04} \right)}}} \right. \kern-\nulldelimiterspace} {4.576T + \left( {5.47 \pm 0.04} \right)}} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} k_{{\rm NTBO}} = - {{\left( {28920 \pm 50} \right)} \mathord{\left/ {\vphantom {{\left( {28920 \pm 50} \right)} {4.576T + \left( {5.86 \pm 0.02} \right)}}} \right. \kern-\nulldelimiterspace} {4.576T + \left( {5.86 \pm 0.02} \right)}} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} k_{{\rm XTBO}} = - {{\left( {32890 \pm 120} \right)} \mathord{\left/ {\vphantom {{\left( {32890 \pm 120} \right)} {4.576T + \left( {6.19 \pm 0.05} \right)}}} \right. \kern-\nulldelimiterspace} {4.576T + \left( {6.19 \pm 0.05} \right)}} $$\end{document}The Arrhenius parameters are used as a test for a biradical mechanism and to discuss theendoselectivity of the react

ISSN:0538-8066    

DOI:10.1002/kin.550160202

出版商:John Wiley&Sons, Inc.    

年代:1984

数据来源: WILEY

摘要:

AbstractThe kinetics of the thermal reaction between CF3OF and C3F6have been investigated between 20 and 75°C. It is a homogeneous chain reaction of moderate length where the main product is a mixture of the two isomers 1‐C3F7OCF3(68%) and 2‐C3F7OCF3(32%). Equimolecular amounts of CF3OOF3and C6F14are formed in much smaller quantities. Inert gases and the reaction products have no influence on the reaction, whereas only small amounts of oxygen change the course of reaction and larger amounts produce explosions.The rate of reaction can be represented by eq. (I):The following mechanism explains the experimental results:Reaction (5) can be replaced by reactions (5a) and (5b), without changing the result:Reaction (4) is possibly a two‐step reaction:\documentclass{article}\pagestyle{empty}\begin{document}$$ E_1 = 15.90 \pm 0.45{\rm kcal}\,{\rm mol}^{ - 1} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = \left( {7.60 \pm 0.68} \right)10^8 {\rm exp}\left( { - 15,900\,\, \pm \,\,450\,\,{{{\rm cal}} \mathord{\left/ {\vphantom {{{\rm cal}} {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \right)M^{ - 1} \cdot s^{ - 1} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ E^ * \, = \,12.30\, \pm \,0.25\,{\rm kcal}\,{\rm mol}^{ - 1} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ k^ * \, = \,\left( {6.11\, \pm \,0342} \right)10^7 \,{\rm exp}\left( { - 12,300\, \pm \,250\,{{{\rm cal}} \mathord{\left/ {\vphantom {{{\rm cal}} {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \right)M^{ - 1} \, \cdot \,{\rm s}^{ - 1} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {E^ * \, - \frac{1}{2}E_1 \, = \,4.35\,{\rm kcal}\, = \,E_3 \, - \,\frac{1}{2}E_4 ;} & {E_3 \,} \\ \end{array} > \,4.35\,{\rm kcal} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ \nu \,\left( {{\rm chain}\,{\rm length}} \right)\, = \,1 + \,\frac{{k_3 }}{{k_1 ^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} \left( {2k_4 } \right)^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} }}\left( {\frac{{\left| {{\rm CR}_{\rm 3} {\rm OF}} \right|}}{{\left| {{\rm C}_{\rm 3} {\rm F}_{\rm 6} } \right|}}} \right)^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} $$\end{document}For ∣CF3= ∣C3F6∣, ν20°C= 36.8, ν50°C= 24.0,

ISSN:0538-8066    

DOI:10.1002/kin.550160203

出版商:John Wiley&Sons, Inc.    

年代:1984

数据来源: WILEY

摘要:

AbstractThe static vessel pyrolysis of bicyclo[2.2.2]octa‐2,5,7‐triene (barrelene) has been studied between 483 and 523 K. The products were acetylene and benzene (in equal quantities) with no other detectable C8H8isomer (down to less than 1% of total). The time dependence fitted first‐order kinetics, and the data are consistent with a homogeneous unimolecular reaction close to, if not at, its high‐pressure limit at 0.25 torr. The rate constant was fitted to the Arrhenius equation\documentclass{article}\pagestyle{empty}\begin{document}$$ \log \left( {{k \mathord{\left/ {\vphantom {k {s^{ - 1} }}} \right. \kern-\nulldelimiterspace} {s^{ - 1} }}} \right)\, = \,\left( {14.27\, \pm \,0.18} \right)\, - \,{{\left( {41.71\, \pm \,0.41\,{{{\rm kcal}} \mathord{\left/ {\vphantom {{{\rm kcal}} {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}}} \right)} \mathord{\left/ {\vphantom {{\left( {41.71\, \pm \,0.41\,{{{\rm kcal}} \mathord{\left/ {\vphantom {{{\rm kcal}} {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}}} \right)} {RT}}} \right. \kern-\nulldelimiterspace} {RT}}\,\ln \,10 $$\end{document}These Arrhenius parameters are shown to imply a concerted single‐step process. Alternative mechanisms are discussed and a comparison is made with the retro‐Diels—Alder reactions of other bicyclo[2.2.2]octa

ISSN:0538-8066    

DOI:10.1002/kin.550160204

出版商:John Wiley&Sons, Inc.    

年代:1984

数据来源: WILEY

摘要:

AbstractVinylacetylene was pyrolyzed at 300–450°C in a packed and an unpacked static reactor with a pinhole bleed to a quadrupole mass spectrometer. The reactant and C8H8products were monitored continuously during a reaction by mass spectrometry. In some runs, the products were also analyzed by gas chromatography after the run. In these runs CH4, C2H6, C3H6, and C2H4were also detected.The reaction for vinylacetylene removal and C8H8formation is homogeneous, second order in reactant, and independent of the presence of a large excess of N2or He. However, C8H8formation is about half‐suppressed by the addition of the free‐radical scavengers NO or O2. The rate coefficient for total vinylacetylene removal is 1.7 × 106exp(−79 ± 13 kJ/molRT) L/mol · s. The major reaction for C4H4removal is polymerization. In addition four C8H8isomers, carbon, and small hydrocarbons are formed. The three major C8H8isomers are styrene, cyclooctatetraene (COT), and 1,5dihydropentalene (DHP).The C8H8compounds are formed by both molecular and free‐radical processes in a second‐order process with an overallk≃ 3 × 108exp(−122 kJ/molRT) L/mol · s (average of packed and unpacked cell results). The molecular process occurs with an overallk= 8.5 × 107exp (−118 kJ/molRT) L/mol · s. The COT, DHP, and an unidentified isomer (d), are formed exclusively in molecular processes with respective rate coefficients of 4.4 × 104exp(−77 kJ/molRT), 1.7 × 105exp(−89 kJ/molRT), and 3.1 × 109exp(− 148 kJ/molRT) L/mol · s. The styrene is formed both by a direct free‐radi

ISSN:0538-8066    

DOI:10.1002/kin.550160205

出版商:John Wiley&Sons, Inc.    

年代:1984

数据来源: WILEY

摘要:

AbstractThe reaction between ozone and carbon monoxide was reinvestigated in the range of 80–160°C. The previously reported rate law −d[O3]/dt=ka[O3][CO]+kb[O3]2was confirmed and simulated using a mechanism based on an impurity‐initiated chain reaction. When the CO was sufficiently purified,kbtended to zero andkareduced to the value expected for the thermal decomposition of O3. Subsequent reactions of O atoms with CO produced chemiluminescence which was used to measurek3for\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm O}\,\, + \,\,{\rm CO}\,\,\mathop {\longrightarrow}\limits^{\rm 3} \,\,{\rm CO}_{\rm 2} \left( {^3 B_2 } \right) $$\end{document}as 10−14.0±0.3exp[−(1630 ± 325)/T] cm3molecule−1s−1. The implications of th

ISSN:0538-8066    

DOI:10.1002/kin.550160206

出版商:John Wiley&Sons, Inc.    

年代:1984

数据来源: WILEY

摘要:

AbstractA new reaction mechanism describing the atmospheric photochemical oxidation of toluene is formulated and tested against environmental chamber data from the University of California, Riverside, Statewide Air Pollution Research Center (SAPRC). On simulations of toluene—NOxand toluene—benzaldehyde—NOxirradiations, the average predicted O3and PAN maxima are within 3% of the experimental values. Simulations performed with the new mechanism are used to investigate various mechanistic paths, and to gain insight into areas where our understanding is not complete. Specific areas that are investigated include benzaldehyde photolysis, organic nitrate formation, alternate ring fragmentation pathways, and conjugated γ‐dicarbonyl condensation to the aeros

ISSN:0538-8066    

DOI:10.1002/kin.550160207

出版商:John Wiley&Sons, Inc.    

年代:1984

数据来源: WILEY

ISSN:0538-8066    

DOI:10.1002/kin.550160201

出版商:John Wiley&Sons, Inc.    

年代:1984

数据来源: WILEY