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  • 101
    Electronic Resource
    Electronic Resource
    Pseudo-phase ion-exchange model for micellar catalysis in the acid hydrolysis of vinyl ethers (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 269-276 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of the perchloric acid hydrolysis of aqueous ethyl and butyl vinyl ethers at 25.0°C, in the presence of micellar aggregates [anionic, sodium dodecyl sulfate (SDS); cationic, cetyl trymethyl ammonium bromide (CTAB); and nonionic, polyoxyethylen—23—dodecanol, (Brij 35)], has been studied. Negligible effects were observed in the cases of cationic and nonionic micelles. Anionic micelles produce an enhancement in the reaction velocity, and the rate constants go through maxima with increasing SDS concentration. These maxima disappear in the presence of excess sodium perchlorate. All these facts are interpreted quantitatively by means of the pseudo-phase ion-exchange model.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160309
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  • 102
    Electronic Resource
    Electronic Resource
    Kinetic characteristics of chloride-assisted oxidative dealkylation of alkylcobalamins (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 277-287 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The recent experiments on the chloride-assisted dealkylation of alkylcobalamins by a variety of oxidants (IrCl62-, AuCl4-, Fe(H2O)5Cl2+, and PtCl62-), which are scattered in several previous publications, and their general kinetic characteristics are summarized. The kinetic studies are also extended to include the dealkylations of (methylaquo)-3,5,6-trimethylbenzimidazolylcobamide and protonated base-off ethylcobalamin by IrCl62- (1.0M Cl-) and by Fe(III) ions at 0.1M Cl-, and the demethylation of (methylaquo)-3,5,6-trimethylbenzimidazolylcobamide by AuCl4- (1.0M Cl-). This extension is in an effort to substantiate the general mechanism which has been previously proposed for these oxidative dealkylations. The general kinetic characteristics are described in terms of a preassociation of the reactants, followed by a rate-determining electron-transfer process to yield the R-B12+ radical, which then undergoes further reactions to produce the products observed. The overall reactions are discussed within the framework of chlorine-bridging inner sphere electron-transfer reactions.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160310
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  • 103
    Electronic Resource
    Electronic Resource
    Reaction of CF3 radicals with H2S (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 335-344 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydrogen abstration from H2S by CF3 radicals, generated by the photolysis of both CF3COCF3 and CF3I, has been studied in the temperature range 314-434 K. The rate constant, based on the value of 1013.36 cm3/mol · s for the recombination of CF3 radicals, is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log }\,k_2 \, = \,\left( {12.20\, \pm \,0.05} \right)\, - \,{{\left( {19,220\, \pm \,360} \right)} \mathord{\left/ {\vphantom {{\left( {19,220\, \pm \,360} \right)} {19.145T}}} \right. \kern-\nulldelimiterspace} {19.145T}} $$\end{document} with CF3COCF3 as the radical source, and \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log }\,k_2 \, = \,\left( {12.00\, \pm \,0.07} \right)\, - \,{{\left( {18,270\, \pm \,470} \right)} \mathord{\left/ {\vphantom {{\left( {18,270\, \pm \,470} \right)} {19.145T}}} \right. \kern-\nulldelimiterspace} {19.145T}} $$\end{document} with CF3I as the radical source, where k2 is in cm3/mol · s and E is in J/mol. These results resolve a previously existing controversy concerning the values of the rate constants for this reaction. They show that CF3 radicals are less reactive than CH3 radicals in attacking H2S, and this behavior indicates that polar effects play a significant role in the hydrogen transfer reactions of CF3 radicals.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160404
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  • 104
    Electronic Resource
    Electronic Resource
    Photodecomposition reaction of ethyl bromide at 147 nm (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 397-405 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A vacuum ultraviolet photolysis of C2H5Br at 147 nm was studied over a pressure range of 0.5-50 torr at 298 K. The effects of additives He and NO were also investigated.The principal reaction products were found to be C2H4 and C2H6, with lesser yields of CH4 and C2H2. With increasing pressure the product quantum yields Φi of C2H4, CH4, and CH2H6 remained constant, while that of C2H2 decreased from 0.03 to almost 0. The effect of He as an additive was found to be extremely small on the quantum yields of the major products. Addition of NO completely suppresses the formation of CH4, C2H2, and C2H6, and reduces partially the production of C2H4. The primary processes appear to involve two electronically excited states. One state mainly yields C2H4 by molecular elimination of HBr and is thought to be due to a Rydberg transition. The other state decomposes to C2H5 and Br radicals by C—Br bond fission. These two competitive reaction modes contribute to the photodecomposition in proportions of 50% and 50%. The extinction coefficient for C2H5Br at 147 nm and at 298 K has been determined as ∊ = (1/PL) In(Io/It) = 712 ± 7 atm-1 · cm-1.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160409
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  • 105
    Electronic Resource
    Electronic Resource
    Masthead (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160501
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  • 106
    Electronic Resource
    Electronic Resource
    Reaction of hot H atoms with CD3Br (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 213-220 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Energetic H atoms produced by photolysis of gaseous HI react with CD3Br by D abstraction (1) and Br abstraction (2) and possibly also by the substitution reactions (4) and (5). Yields of HD and CD3H have been determined for several defined initial translational energies of H*. The phenomenological threshold energy of reaction (1) is 53 ± 5 kJ/mol. Over the range of initial energies of 76-109 kJ mol the integral probability of reaction (1) increases substantially, but the sum of the integral probabilities of reactions (2) and (5) shows little change. The ratio of the sum of the integral yields of reactions (2) and (5) to the integral yield of reaction (1), when normalized to equal numbers of Br and D atoms, is 69 ± 33 at an initial energy of 76 kJ/mol and 31 ± 6 at 109 kJ/mol.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160304
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  • 107
    Electronic Resource
    Electronic Resource
    Shock tube study of cyanogen oxidation kinetics (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 231-250 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mixtures of cyanogen and nitrous oxide diluted in argon were shock-heated to measure the rate constants of A broad-band mercury lamp was used to measure CN in absorption at 388 nm [B2Σ+(v = 0) ← X2Σ+(v = 0)], and the spectral coincidence of a CO infrared absorption line [v(2 ← 1), J(37 ← 38)] with a CO laser line [v(6 → 5), J(15 → 16)] was exploited to monitor CO in absorption. The CO measurement established that reaction (3) produces CO in excited vibrational states. A computer fit of the experiments near 2000 K led to \documentclass{article}\pagestyle{empty}\begin{document}$$ k_2 \, = \,10^{11.70\left( { + 0.25, - 0.19} \right)} \,{{{\rm cm}^3 } \mathord{\left/ {\vphantom {{{\rm cm}^3 } {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}}\, \cdot \,{\rm s} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_3 \, = \,10^{13.26 \pm 0.26} \,{{{\rm cm}^3 } \mathord{\left/ {\vphantom {{{\rm cm}^3 } {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}}\, \cdot \,{\rm s} $$\end{document} An additional measurement of NO via infrared absorption led to an estimate of the ratio k5/k6: with k5/k6 ≃ 103.36±0.27 at 2150 K. Mixtures of cyanogen and oxygen diluted in argon were shock heated to measure the rate constant of and the ratio k5/k6 by monitoring CN in absorption. We found near 2400 K: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_4 \, = \,10^{12.68\left( { + 0.27, - 0.19} \right)} \,{{{\rm cm}^3 } \mathord{\left/ {\vphantom {{{\rm cm}^3 } {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}}\, \cdot \,{\rm s} $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$ {{k_5 } \mathord{\left/ {\vphantom {{k_5 } {k_6 }}} \right. \kern-\nulldelimiterspace} {k_6 }}\, = \,10^{2.68 \pm 0.28} $$\end{document} The combined measurements of k5/k6 lead to k5/k6 ≃ 10-3.07 exp(+31,800/T) (±60%) for 2150 ≤ T ≤ 2400 K.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160306
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  • 108
    Electronic Resource
    Electronic Resource
    Rate constants for the reactions of O3 and OH radicals with a series of alkynes (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 259-268 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the reactions of O3 and OH radicals with acetylene, propyne, and 1-butyne have been determined at room temperature. The rate constants obtained at 294 ± 2 K for the reactions of O3 with acetylene, propyne, and 1-butyne were (7.8 ± 1.2) × 10-21 cm3/molecule · s, (1.43 ± 0.15) × 10-20 cm3/molecule · s, and (1.97 ± 0.26) × 10-20 cm3/molecule · s, respectively. The rate constants at 298 ± 2 K and atmospheric pressure for the reactions with the OH radical, relative to a rate constant for the reaction of OH radicals with cyclohexane of 7.57 × 10-12 cm3/molecule · s, were determined to be (8.8 ± 1.4) × 10-13 cm3/molecule · s, (6.21 ± 0.31) × 10-12 cm3/molecule · s, and (8.25 ± 0.23) × 10-12 cm3/molecule · s for acetylene, propyne, and 1-butyne, respectively. These data are discussed and compared with the available literature rate constants.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160308
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  • 109
    Electronic Resource
    Electronic Resource
    Mechanism and kinetics of the shock-tube decomposition of vinylsilane (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 289-305 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The shock-induced thermal decompositions of vinylsilane and vinylsilane-d3 (0.2% on argon) have been studied in the temperature range of 1085-1275 K, and at total pressures of about 3100 torr. In systems without silylene traps, some induced decomposition occurs which is attributed to the silylene chain sequence VSiH → C2H2 + SiH2, S̈iH2 + VSiH3 ⇄ VSiH2SiH3 → VSiH2S̈iH + H2, VSiH2S̈iH → VSiH + S̈iH2. In the presence of silylene traps (butadiene and acetylene), the overall decomposition kinetics are log k(VSiH3, s-1) = 14.95 - 63,268 cal/2.303RT and log k(VSiD3, s-1) = 15.14 - 64,815 cal/2.303RT. Three primary processes contribute to the decomposition: 1,1-H2 elimination, 1,2-H2 elimination, and ethylene elimination. Two mechanisms are proposed, one for exclusive primary process formation of C2H4, and the other for both primary and secondary formation routes. Modeling studies are reported which show that both mechanisms can be made compatible with the rate and product yield data within experimental errors.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160402
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  • 110
    Electronic Resource
    Electronic Resource
    Rate constants for the reactions of OH radicals with alkyl substituted olefins (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 879-886 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate constants for the reactions of hydroxyl radicals with a series of alkyl substituted olefins were measured by competitive reactions between pairs of olefins at 298 ± 2 K and 1 atmospheric pressure. Hydroxyl radicals were produced by the photolysis of H2O2 with 254-nm irradiation. The obtained rate constants were (× 10-11 cm3 molecule-1 s-1): 2.53 ± 0.06, propylene; 5.49 ± 0.17, cis-2-butene; 5.47 ± 0.1, isobutene; 6.46 ± 0.13, 2-methyl-1-butene; 6.37 ± 0.16, cis-2-pentene; 6.23 ± 0.1, 2-methyl-1-pentene; 8.76 ± 0.14, 2-methyl-2-pentene; 6.24 ± 0.08, trans-4-methyl-2-pentene; 10.3 ± 0.1, 2,3-dimethyl-2-butene; 9.94 ± 0.1, 2,3-dimethyl-2-pentene; 5.59 ± 0.07, trans-4,4-dimethyl-2-pentene. A trend in alkyl substituent effect on the rate constant was found, which is useful to predict kOH on the basis of the number of alkyl substituents on the double bond.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160708
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  • 111
    Electronic Resource
    Electronic Resource
    Kinetic study for addition of the phenylthio radicals to vinylpyridines (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 909-918 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absolute rate constants for reversible addition of the substituted phenylthio radicals to vinylpyridines in solution at 23°C have been determined by flash photolysis method. For each phenylthio radical, the reactivities of vinylpyridines is 3-5 times lower than that of styrene. The relative equilibrium constants estimated with flash photolysis indicate that the stabilities of the adduct carbon-centered radicals generated from vinylpyridines are similar to that from styrene. The Hammett plots suggest that the difference in the reactivities originates in the polar transition state; the nitrogen atom in 4-vinylpyridine withdraws the electrons of vinylic double bond.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160711
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  • 112
    Electronic Resource
    Electronic Resource
    An investigation of the dark formation of nitrous acid in environmental chambers (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 919-939 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The formation of nitrous acid (HONO) in the dark from initial concentrations of NO2 of 0.1-20 ppm in air, and the concurrent disappearance of NO2, were monitored quantitatively by UV differential optical absorption spectroscopy in two different environmental chambers of ca.4300- and 5800-L volume (both with surface/volume ratios of 3.4 m-1). In these environmental chambers the initial HONO formation rate was first order in the NO2 concentration and increased with the water vapor concentration. However, the HONO formation rate was independent of the NO concentration and relatively insensitive to temperature. The initial pseudo-first-order consumption rate of NO2 was (2.8 ± 1.2) × 10-4 min-1 in the 5800-L Teflon-coated evacuable chamber and (1.6 ± 0.5) × 10-4 min-1 in a 4300-L all-Teflon reaction chamber at ca.300 K and ca.50% RH. The initial HONO yields were ca.40-50% of the NO2 reacted in the evacuable chamber and ca.10-30% in the all-Teflon chamber. Nitric oxide formation was observed during the later stages of the reaction in the evacuable chamber, but ca.50% of the nitrogen could not be accounted for, and gas phase HNO3 was not detected. The implications of these data concerning radical sources in environmental chamber irradiations of NOx- organic-air mixtures, and of HONO formation in polluted atmospheres, are discussed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160712
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  • 113
    Electronic Resource
    Electronic Resource
    Kinetics of the reactions of O3 and OH radicals with a series of dialkenes and trialkenes at 294 ± 2 K (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 967-976 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the gas phase reactions of O3 and OH radicals with 1,3-cycloheptadiene, 1,3,5-cycloheptatriene, and cis- and trans-1,3,5-hexatriene and also of O3 with cis-2,trans-4-hexadiene and trans -2,trans -4-hexadiene have been determined at 294 ± 2 K. The rate constants determined for reaction with O3 were (in cm3 molecule-1s-1 units): 1,3-cycloheptadiene, (1.56 ± 0.21) × 10-16; 1,3,5-cycloheptatriene, (5.39 ± 0.78) × 10-17; 1,3,5-hexatriene, (2.62 ± 0.34) × 10-17; cis-2,trans-4-hexadiene, (3.14 ± 0.34) × 10-16; and trans -2, trans -4-hexadiene, (3.74 ± 0.61) × 10-16; with the cis- and trans-1,3,5-hexatriene isomers reacting with essentially identical rate constants. The rate constants determined for reaction with OH radicals were (in cm3 molecule-1 s-1 units): 1,3-cycloheptadiene, (1.31 ± 0.04) × 10-10; 1,3,5-cycloheptatriene, (9.12 × 0.23) × 10-11; cis-1,3,5-hexatriene, (1.04 ± 0.07) × 10-10; and trans 1,3,5-hexatriene, (1.04 ± 0.17) × 10-10. These data, which are the first reported values for these di- and tri-alkenes, are discussed in the context of previously determined O3 and OH radical rate constants for alkenes and cycloalkenes.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160804
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  • 114
    Electronic Resource
    Electronic Resource
    Masthead (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160901
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  • 115
    Electronic Resource
    Electronic Resource
    Basic hydrolysis of glyceryl nitrate esters. II. 1,2-glyceryl and 1, 3-glyceryl dinitrate esters (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1009-1026 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of the basic hydrolysis of 1,2-glyceryl dinitrate (1,2-DNG) and 1,3-glyceryl dinitrate (1,3-DNG) esters were investigated in CO2-free aqueous calcium hydroxide solutions. The hydrolysis reactions were carried out in a temperature controlled reactor vessel with provision for continuous N2 sparging of the reaction mixture. Both glyceryl dinitrate esters hydrolyzed via second-order reaction at 25°C. 1,2-DNG in basic solutions isomerized to 1,3-DNG which subsequently hydrolyzed to yield products. The main hydrolysis product of 1,3-DNG was identified as glycidyl nitrate. Other products formed during the basic hydrolysis of DNGs were nitrites and nitrates.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160807
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  • 116
    Electronic Resource
    Electronic Resource
    The high temperature oxidation of the methyl side chain of toluene (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1053-1074 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: From the results of order of magnitude analyses, it is concluded that during the oxidation of toluene, radical-atom and radical-radical reactions (1) and (3) play an unusually important and approximately equal role in the formation of benzaldehyde, an intermediate that leads eventually to the complete removal of the side chain. An additional radical-radical system, reaction (2), is shown to be the most likely source of benzyl alcohol observed during toluene oxidation.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160902
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  • 117
    Electronic Resource
    Electronic Resource
    Reaction of methyl radicals with haloalkanes (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 579-590 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of reactions involving halogen atom abstraction from haloalkanes by methyl radicals have been studied in the gas phase. Arrhenius parameters for halogen atom transfer were determined relative to those for methyl radical combination: TextRXlog10A2(L/mol · s)E2(kcal/mol)CFCl38.3 ± 0.210.7 ± 0.4CF3CCl37.9 ± 0.39.7 ± 0.6CF2Cl29.1 ± 0.411.3 ± 0.7CF3Cl8.8 ± 0.511.8 ± 1.0CF3CF2Cl8.3 ± 0.310.9 ± 0.7CF3Br8.6 ± 0.29.3 ± 0.5CF3I8.1 ± 0.14.3 ± 0.2CH3CH2I8.9 ± 0.37.4 ± 0.6The rate data obtained are used to provide information on the importance of polar effects for halogen abstraction processes.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550160507
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  • 118
    Electronic Resource
    Electronic Resource
    Sensitivity analysis in chemical kinetics: Recent developments and computational comparisons (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 559-578 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The advantages and disadvantages of various methods of parametric sensitivity analysis in chemical kinetic modeling are discussed. Particular attention is given to estimates of computational labor for realistic problems, and quantitative comparisons are made utilizing a 52-reaction, 11-species CO oxidation mechanism. The authors′ CHEMSEN/AIM program compares favorably to other techniques in many circumstances, and provides the additional convenience of accepting input information in familiar chemical notation. This paper also reviews recent developments in theory of sensitivity analysis, relevant to chemical kinetic modeling.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550160506
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  • 119
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    Electronic Resource
    The kinetics and mechanism of aqueous cleavage of imide bond in 5, 5-diethyl barbituric acid (5, 5-diethyl-2,4,6-(1H, 3H) pyrimidinetrione) in a highly alkaline medium (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1301-1310 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetic study of alkaline hydrolysis of 5, 5-diethyl barbituric acid has been carried out at various [OH] and different temperatures ranging from 85-95°C. The reaction follows an irreversible first-order consecutive reaction path of the type \documentclass{article}\pagestyle{empty}\begin{document}${\rm A}\buildrel{{k1{\rm obs}}}\over\longrightarrow{\rm B}\buildrel{{k2{\rm obs}}}\over\longrightarrow$\end{document} X under pseudo-first-order kinetic conditions. A, B, and X represent for 5, 5-diethyl barbituric acid, diethyl malonuric acid, and ammonia, respectively. The pH-rate profiles obtained at three different temperatures reveal distinct phases which are attributed to a change in rate-determining step with change in [OH]. On the basis of the observed data, a possible mechanism has been discussed.
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    URL: http://dx.doi.org/10.1002/kin.550161102
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    Kinetics of thermal decomposition of CuSO4 · 5H2O to CuO (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 655-668 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of particle size, type of crucible, and heating rate on the thermal curves obtained simultaneously for CuSO4 · 5H2O were discussed. The dissociation steps were confirmed. Thermogravimetric techniques for determining the rate-controlling processes and kinetic parameters were applied for the dehydration steps and the calcination of CuSO4 and CuSO4 · CuO. For the dehydration of the monohydrate one mechanism operates but the activation energy and preexponential factor vary over wide ranges. Differentiating between various mechanisms using the same technique was sometimes difficult giving completely different values for the kinetic parameters. In view of such difficulties the various methods were assessed, the best techniques to treat similar results were recommended and the operating mechanisms and kinetic parameters for the various steps were thus established.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550160604
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    Gas phase reaction of NO2 with alkenes and dialkenes (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 697-706 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas phase reactions of NO2 with a series of organics have been studied at 295 ± 2 K. It was observed that only 2,3-dimethyl-2-butene and the conjugated dialkenes studied reacted at observable rates, with rate constants which ranged from 1.5 × 10-20 cm3 molecule-1 s-1 for 2,3-dimethyl-2-butene to 1.3 × 10-17 cm3 molecule-1 s-1 for α-phellandrene. These rate constants are compared with the available literature data and the mechanisms of these reactions are discussed.
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    URL: http://dx.doi.org/10.1002/kin.550160607
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  • 122
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    Gas phase reactions of CF3, C2F5, and n-C3F7 with carbon tetrachloride (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1351-1356 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of some perfluoroalkyl radicals with carbon tetrachloride have been studied using the photolysis of the corresponding perfluoroalkyl iodide as the free radical source. The Arrhenius parameters, based on the value of 2.3 × 1013 cm3 mol-1 s-1 for the self-combination rate constant of all radicals are: TextReactionlog(A/cm3 mol-1 s-1)E/kcal mol-1CF3 + CCl412.811.3C2F5 + CCl412.811.6n-C3F7 + CCl412.912.0
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    URL: http://dx.doi.org/10.1002/kin.550161107
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  • 123
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    The kinetics and mechanism of the shock induced gas phase decomposition of ethylsilane (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1371-1383 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition kinetics of ethylsilane under shock tube conditions (PT ca. 3100 torr, T ≃ 1080-1245 K), both in the absence and presence of silylene trapping agents (butadiene and acetylene) are reported. Arrhenius parameters under maximum butadiene inhibition are: log k(C2H5SiH3) = 15.14-64,769 ± 1433 cal/2.303 RT; log k(C2H5SiD3) = 15.29-66,206 ± 1414/2.303 RT. The uninhibited reaction is subject to silylene induced decomposition (63% lowest T -- 24% highest T). Major reaction products are ethylene and hydrogen, consistent with two dominant primary dissociation reactions: C2H5SiD3 → C2H5SiD + D2, φ ≃ 0.66; C2H5SiD3 → CH3CH = SiD2 + HD, φ ≃ 0.30. Minor products suggest several other less important primary processes: alkane elimination, φ ≃0.02, and free-radical production via simple bond fission, φ ≃0.02. An upper limit for the activation energy of the decomposition, C2H5SiH → C2H4 + SiH2, of E 〈 30 ± 4 kcal is established, and speculations on the mechanism of this decomposition (concerted or stepwise) with conclusions in favor of the stepwise path are made. Computer modeling studies for the reaction both in the absence and presence of butadiene are shown to be in good agreement with the experimental observations.
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    URL: http://dx.doi.org/10.1002/kin.550161109
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  • 124
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    Kinetics and mechanism of the shock induced thermal decomposition of n-propylsilane (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 801-816 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and mechanism of the thermal decomposition of n-propylsilane have been studied by the single pulse shock tube-comparative rate technique at pressures around 4700 torr between 1095-1240 K. The primary dissociation processes are 1,1 and 1,2 H2 elimination with ø1,1 ⋍ 0.75 and ø1,2 ⋍ 0.25, respectively. Subsequent decompositions of the primary process product, n-propylsilylene, to propylene and ethylene is complete even in the presence of excess butadiene. Possible mechanistic paths for these decompositions are discussed and an activation energy range of 30 ± 4 kcal is established for both processes. Induced decomposition via silylene chains accounts for 36-46% of the overall reaction in the uninhibited decomposition of n-propylsilane. The silylene chains are quenched in excess butadiene, and studies under maximum inhibition give overall decomposition kinetics of, log k(nPrSiD3, s-1) = 15.26-65,300 ± 1950 cal/2.303. Computer modeling results of the overall reaction both in the absence and presence of butadiene are also presented and shown to be in acceptable agreement with the experimental observations.
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    URL: http://dx.doi.org/10.1002/kin.550160703
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  • 125
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    Efficient production of electronically excited BiF(AO+) via collisions with NF(a1Δ) (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 849-866 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An efficient process for converting the energy stored in electronically excited NF(a1Δ) into blue-green BiF (A—X) band emissions has been discovered. Bismuth atoms are converted to BiF and then repeatedly pumped to the (AO+) state in two steps via collisions with NF(a1Δ). A model has been formulated that predicts BiF emission intensities that are in excellent agreement with the observed values. Some of the rate coefficients required for this model are estimated by means of charge-transfer theories. The cyclic nature of this system, along with its other basic properties, suggests that it has a strong potential to be an efficient blue-green laser system.
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    URL: http://dx.doi.org/10.1002/kin.550160706
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  • 126
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    Kinetics of the gas-phase reactions of NO3 radicals with a series of aromatics at 296 ± 2 K (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 887-898 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants have been determined at 296 ± 2 K for the gas phase reaction of NO3 radicals with a series of aromatics using a relative rate technique. The rate constants obtained (in cm3 molecule-1 s-1 units) were: benzene, 〈2.3 × 10-17; toluene, (1.8 ± 1.0) × 10-17; o—xylene, (1.1 ± 0.5) × 10-16; m—xylene, (7.1 ± 3.4) × 10-17; p—xylene, (1.4 ± 0.6) × 10-16; 1,2,3-trimethylbenzene, (5,6 ± 2.6) × 10-16; 1,2,4-trimethylbenzene (5.4 - 2.5) × 10-16; 1,3,5-trimethylbenzene, (2.4 ± 1.1) × 10-16; phenol, (2.1 ± 0.5) × 10-12; methoxybenzene, (5.0 ± 2.8) × 10-17; o-cresol, (1.20 ± 0.34) × 10-11; m-cresol, (9.2 ± 2.4) × 10-12; p-cresol, (1.27 ± 0.36) × 10-11; and benzaldehyde, (1.13 ± 0.25) × 10-15. These kinetic data, together with, in the case of phenol, product data, suggest that these reactions proceed via H-atom abstraction from the substituent groups. The magnitude of the rate constants for the hydroxy-substituted aromatics indicates that the nighttime reaction of NO3 radicals with these aromatics can be an important loss process for both NO3 radicals and these organics, as well as being a possible source of nitric acid, a key component of acid deposition.
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    URL: http://dx.doi.org/10.1002/kin.550160709
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    Masthead (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160801
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  • 128
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    Kinetics and equilibria of the reaction between bromine and ethyl ether. The C—H bond dissociation energy in ethyl ether (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 949-960 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and equilibria of the reaction: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Br} + {\rm CH}_{\rm 3} {\rm CH}_{\rm 2} {\rm OCH}_{\rm 2} {\rm CH}_{\rm 3} {\rm}\mathop {{\rm \rightleftharpoons}}\limits^{\rm 1} {\rm HBr} + {\rm CH}_{\rm 3} {\rm CHOCH}_{\rm 2} {\rm CH}_{\rm 3} $$\end{document} have been studied in the temperature range 298-333 K by using the very low pressure reactor (VLPR) technique. Combining the estimated entropy change of reaction (1), ΔS°1 = 8.1 ± 1.0 eu, with the measured ΔG°1, we find ΔH°1 = 4.2 ± 0.4 kcal/mol; ΔH°f(CH3CHOC2H5) = -20.2 kcal/mol, and DH° [Et OCH(Me)-H] = 91.7 ± 0.4 kcal/mol. We find: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_1 (1/{\rm mol s)} = 10.8(\pm 0.7) - (3.9 \pm 4.0)/\theta $$\end{document} where θ = 2.3 RT in kcal/mol. It has been shown that the reaction proceeds via a loose transition state and the “contact TS” model calculation gives a very good agreement with the observed value.
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    URL: http://dx.doi.org/10.1002/kin.550160802
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  • 129
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    Yields of singlet nitrenes from halogen atom - azide molecule reactions (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 977-993 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chemiluminescence from the a1Δ and b1Σ+ excited electronic states of nitrogen halide diatomics is observed when HN3 is allowed to react with mixtures of halogen atoms in a discharge-flow apparatus. Excited NF (a1Δ) is produced by the F + HN3 reaction, and NCl (a1Δ, b1Σ+) and NBr (a1Δ, b1Σ+) are produced by the F, Cl, + HN3 and F, Br + HN3 reactions, respectively. In the low-density limit, the yield of NF(a1Δ) was found to be near unity. The yields of the b1Σ+ states of NCl and NBr were determined to have a lower limit of ca. 10%. A number of results from these experiments, including direct observation of N3 radicals in the flow, support a hypothetical mechanism in which N3 acts as an intermediate. A second possible mechanism proceeding via an HNF intermediate cannot be ruled out.
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    URL: http://dx.doi.org/10.1002/kin.550160805
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  • 130
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    Mechanism of the chain process forming H2 in the photooxidation of formaldehyde (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1599-1608 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A mechanism for the formation in a chain of H2, CO, and HCOOH in the photooxidation of formaldehyde is proposed. This mechanism is initiated by the addition of HO2 to formaldehyde. Hydrogen atoms are produced by the thermal dissociation of the HOCH2O radical: HOCH2O → H + HCOOH; ΔH = + 3.2 kcal/mol [5]. Photolysis of CH2O—O2—NO mixtures and product analysis were carried out in conjunction with kinetic simulation yielding an estimate for the activation energy of the dissociation reaction : E5 = 14.9 ± 1.0 kcal/mol. Previous observations of this chain process are considered in view of this mechanism.
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    URL: http://dx.doi.org/10.1002/kin.550161213
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  • 131
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    Formation of alkyl nitrates from the reaction of branched and cyclic alkyl peroxy radicals with NO (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1085-1101 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The yields of C5 and C6 alkyl nitrates from neopentane, 2-methylbutane, 2-methylpentane, 3-methylpentane, and cyclohexane have been measured in irradiated CH3ONONO-alkane-air mixtures at 298 ± 2 K and 735-torr total pressure. Additionally, OH radical rate constants for neopentyl nitrate, 3-nitro-2-methylbutane, 2-nitro-2-methylpentane, 2-nitro-3-methylpentane, and cyclohexyl nitrate, relative to that for n-butane, have been determined at 298 ± 2 K. Using a rate constant for the reaction of OH radicals with n-butane of 2.58 × 10-12 cm3 molecule-1 s-1, these OH radical rate constants are (in units of 10-12 cm3 molecule-1 s-1): neopentyl nitrate, 0.87 ± 0.21; cyclohexyl nitrate, 3.35 ± 0.36; 3-nitro-2-methylbutane, 1.75 ± 0.06; 2-nitro-2-methylpentane, 1.75 ± 0.22; and 2-nitro-3-methylpentane, 3.07 ± 0.08. After accounting for consumption of the alkyl nitrates by OH radical reaction and for the yields of the individual alkyl peroxy radicals formed in the reaction of OH radicals with the alkanes studied, the alkyl nitrate yields (which reflect the fraction of the individual RO2 radicals reacting with NO to form RONO2) determined were: neopentyl nitrate, 0.0513 ± 0.0053; cyclohexyl nitrate, 0.160 ± 0.015; 3-nitro-2-methylbutane, 0.109 ± 0.003; 2-nitro-2methylbutane, 0.0533 ± 0.0022; 2-nitro-2-methylpentane, 0.0350 ± 0.0096; 3- + 4-nitro-2-methylpentane, 0.165 ± 0.016; and 2-nitro-3-methylpentane, 0.140 ± 0.014. These results are discussed and compared with previous literature values for the alkyl nitrates formed from primary and secondary alkyl peroxy radicals generated from a series of n-alkanes.
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    URL: http://dx.doi.org/10.1002/kin.550160904
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    The kinetics of the addition of alkyl radicals to carbonyl groups. II. The addition of methyl radicals to trifluoroacetone in the gas phase. The formation reaction of the trifluoro-t-butoxy radical (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1327-1335 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By photolyzing azomethane over the temperature range 331-491 K in the presence of trifluoroacetone the kinetics of the addition reaction (1), ĊH3 + CF3COCH3 → CF3C(Ȯ)(CH3)2 have been studied. Detailed analyses have shown that the principal product of the adduct radical, CF3C(Ȯ)(CH3)2, is CH3COCH3 from reaction (-2), CF3C(Ȯ)(CH3)2 → CH3COCH3 + ĊF3. The rate constant of the addition reaction has been determined to be k1(dm3/mol s) = (4.5 ± 1.4) × 107 exp(-(3370 ± 120)/T) over the temperature range 331-491 K, based on the value k3 = 2.2 × 1010 dm3/mol s for the reaction (3), 2ĊH3 → C2H6. The results are discussed in relation to existing data for radical additions to groups.
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    URL: http://dx.doi.org/10.1002/kin.550161105
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  • 133
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    The photolysis of 3,4-dimethylcyclopentanone (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1337-1350 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of trans-3,4-dimethylcyclopentanone has been studied in the gas phase, principally at 313 nm. However, a few experiments have also been performed using laser sources at 308 and 325 nm. Additionally, experiments were also carried out using the cis isomer. The major products produced by all three wavelengths and in the temperature range 100 to 150°C were propene, 1,2-dimethylcyclobutane, carbon monoxide, and 3,4-dimethylpent-4-en-al. The formation of the cyclobutane was stereospecific and the effects of temperature, pressure, and wavelength on the relative product yields could be rationalized in terms of a mechanism involving the formation of a vibrationally excited triplet state which could yield both hydrocarbons and the aldehyde and a nonexcited triplet yielding only the aldehyde. Some high intensity experiments with an exciplex laser at 308 nm gave results which could be due to the occurrence of some two photon absorption by the cyclopentanone or absorption by an excited intermediate. The results are compared with those previously reported for other substituted cyclopentanones.
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    Optimizing the use of the Kezdy-Mangelsdorf-Swinbourne method for analysis of data following a exp(-kt) + Z (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1427-1454 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The use of the KMS method for the evaluation of the exponent by the experimentalist requires that a lag or retardation be chosen. The best choice of lag is discussed quantitatively. Its dependence upon the decade range of the data, the relative magnitude of the background, the level and character of the noise, the number and distribution of the data, and the weighted least-squares method of analysis are all detailed. A table of lags and error factors is given, for various ranges, backgrounds, and kinds of noise. Bias in the extracted rate (k), due to noise and treatment of the data, is also discussed.
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    URL: http://dx.doi.org/10.1002/kin.550161112
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  • 135
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    High temperature collisional energy transfer in highly vibrationally excited molecules: Isotope effects in tert-butyl chloride systems (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1455-1470 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The average downward collisional energy transfer (〈ΔEdown〉) is obtained for highly vibrationally excited tert-butyl chloride, both undeuterated and per-deuterated, with Kr, N2, CO2, and C2H4 bath gases, at ca. 760 K. Data are obtained using the technique of pressure-dependent very low-pressure pyrolysis. Reactant internal energies to which the data are sensitive are in the range 200-250 kJ mol-1. For C4H9Cl, the 〈ΔEdown〉 values (cm-1) are 255 (Kr), 265 (N2), 440 (CO2), and 585 (C2H4), and for C4D9Cl, 245 (N2), 370 (CO2), and 540 (C2H4). The uncertainties in these values are ca. 20% (40% for Kr); the uncertainties in the deuteration ratios are 10-15%. The value for Kr is in agreement with theoretical predictions of a biased random walk model for internal energy change in monatomic/substrate collisions. The effect of deuteration of 〈ΔEdown〉 is also in accord with that predicted by a modification of the theory. Extrapolated highpressure rate coefficients for the thermal decomposition of reactant are 1013.6 exp(-187 kJ mol-1/RT) s-1 (C4H9Cl) and 1014.2 exp(-196 kJ mol-1/RT) s-1 (C4D9Cl), in accord with other studies and the expected isotope effect.
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    Cerium (IV) oxidation rate of p-chloromandelic acid in perchlorate and sulfate media (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 135-148 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of the cerium (IV) oxidation of p-chloromandelic acid has been studied in perchlorate media at an ionic strength of 1.50 mol/dm3 by the stopped-flow technique and in H2SO4—MHSO4 (M+ = Li+, Na+, K+) and H2SO4—MClO4 (M+ = H+, Li+, Na+) mixtures at constant total electrolyte concentrations of 1.00 and 2.00 mol/dm3 using the conventional spectrophotometric method. In perchlorate media the kinetic data indicate the formation of two intermediate complexes between cerium (IV) and the organic substrate, but only one is significantly involved in the intramolecular electron-transfer process. The oxidation rate is markedly lower in sulfate media, where two reaction paths have been found to contribute to the overall redox reaction. The univalent cations examined exhibit negative specific effects upon the overall oxidation rate increasing in the order H+ 〈 Li+ 〈 Na+ 〈 K+. Activation parameters have been also estimated.
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    URL: http://dx.doi.org/10.1002/kin.550130205
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    Masthead (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130301
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    Studies of the photochemical reactions of sulfur dioxide with pentane in the presence of nitrogen oxide (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 231-243 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The spectrum of the intermediate product ascribed to nitrosopentane has been detected in the photolysis of the SO2-pentane (RH)-NO mixture. This result has been interpreted in terms of the radical mechanism by assuming the H-atom abstraction from RH by the excited SO2 molecules to be the primary act. The contribution of the singlet and triplet SO2 states to the product formation rate and the ratio of the singlet-to-triplet rate constants have been evaluated. At NO pressures above 5 torr, the product formation rate significantly deviates from the Stern-Volmer dependence.
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  • 139
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    The infrared chemiluminescent reaction of Cl atoms with H2CO (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 325-332 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction Cl + H2CO → HCl + HCO has been studied at 295 K. Chlorine atoms were produced via the infrared laser induced dissociation of CCl3F, using a pulsed CO2 TEA laser. Using HCl infrared chemiluminescence as the diagnostic, we find the rate constant to be 7.4 ± 0.7 × 10-11 cm3/molecule sec, in good agreement with several recent studies. An evaluation of TEA laser photolysis as a technique for the generation of chlorine atoms is made, and the relationship of this experiment to recent theories of infrared laser induced chemistry is discussed.
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    URL: http://dx.doi.org/10.1002/kin.550130402
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  • 140
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    Kinetics of the oxidation of U (IV) by hydrogen peroxide in sulfuric acid medium (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 385-401 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction have been investigated in H2SO4 medium under different conditions. The observed bimolecular rate constant kobs, has been found to depend on [H+]-0.55 and to increase with the initial concentration ratio of the reactants R0 = [H2O2]0/[U (IV)]0 above 0.49. The activation energy of the overall reaction has been determined as 13.79 and 14.3 kcal/mol at R0 = 1 and 0.35, respectively. Consistent with experimental data, a detailed reaction mechanism has been proposed where the hydrolytic reaction (4) followed by the rate-controlling reaction (10) and subsequent fast reactions of U (V) and OH radicals are involved: A kinetic expression has been derived from which a graphical evaluation of (kK4)-1 and k-1 has been made at R0 = 1 as (12.30 ± 0.09) × 10-3 M min, (6.23 ± 2.19) × 10-4 M min; and at R0 = 0.35 as (12.63 ± 2.13) × 10-3 M min, (8.32 ± 6.62) × 10-4 M min, respectively. Indications of some participation of a chain reactionat R0 = 1 have been obtained without affecting thesecond-order kinetics as observed.
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  • 141
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    Masthead (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130501
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  • 142
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    An indirect measurement of the absolute rate constant of the self-reaction of tert-butoxy radicalsPublication No. 251 from the Photochemistry Unit. (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 433-444 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No reliable rate constant is available for the self-reaction of tert-;butoxy radicals. We have set up a competition between hydrogen abstraction and self-reaction of tert-butoxy radicals in a flash photolysis electron spin resonance study to extract this information. Experimental values of hydrogen abstraction product radical concentrations under various hydrogen donor concentrations were then compared with theoretically calculated values with different values of 2k4 to obtain the best fit. Hydrogen donors such as cyclopentane, anisole, methyl tert-butyl ether, and methanol were chosen for the study. A value of (1.3 ± 0.5) × 109M-1 sec-1 for the rate constant of the self-reaction of tert-butoxy radicals has been determined at 293°K.
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  • 143
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    Consistency of theory and experiment in the ethane-methyl radical system (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 481-495 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of ethane has been reinvestigated using the single pulse, reflected shock technique. Reflected shock temperatures were corrected for boundary layer-induced nonidealities using the thermal decomposition of cyclohexene as a kinetic standard. The rate constant for the reaction was calculated from the rate of formation of methane under conditions of very low extent of reaction, over a temperature range of 1000-1241 K. Ethane compositions of 1% and 3% in argon at total reaction pressures of 3 and 9 atm were used, and a small pressure dependence of k1 was observed.An RRKM model is described which gives excellent agreement with this and other recent dissociation and recombination rate constant data in light of a recent revision to the thermochemistry of the methyl radical. In the range of 1000-1300 K an RRKM extrapolated k1∞ is given by the expression, log k1∞ = 17.2 - 91,000/2.3RT, while at 298 K the calculation gives log k-1∞ (l/mol sec) = 10.44, where k-1∞ is calculated from k1∞ and the equilibrium constant.
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  • 144
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    Kinetics of the gas-phase reaction between iodine and monosilane and the bond dissociation energy D(H3Si—H)A preliminary account of this work has appeared in Ref. [1]. (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 503-514 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reaction has been investigated in the temperature range of 494-545 K. During the early stages of reaction the only observed products were silyl iodide and hydrogen iodide. Initial rates were found to obey the rate law over a wide range of initial iodine and monosilane pressures. Secondary reactions, most probably of SiH3I with I2, became more important as the reaction progressed. However, provided [SiH4]0/[I2]0 〉 20, these secondary processes had a negligible effect on the kinetics, and an integrated rate expression could be used. These kinetics are consistent with an iodine atom abstraction chain mechanism, and for the step has been deduced. From this the bond dissociation energy D(SiH3—H) = 378 ± 5 kJ/mol (90 kcal/mol) is obtained. The kinetic and thermochemical implications of this value, especially to the pyrolysis of monosilane, are discussed.
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  • 145
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    The estimation of a factors for atom fissions in polyatomics (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 591-601 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that A factors for atom fissions in polyatomics can be reliably estimated by an improved version of the restricted free rotor model (RFRM). No adjustable parameters are used in the evaluation of A factors for the dissociation of the RO—F bond (R: NO2, SF5, CF3, FSO2), and the authors' predictions are compared with high-pressure kinetic data for these reactions. In the case of O2NOF, for which full spectroscopic information is available, RFRM reproduces the observed value Am well within a factor of 2. Similar agreement is reached for F5SOF and FO2SOF, assigning reasonable limits to their —OF torsional frequencies. For F3COF, Am and the calculated back reaction rate constant, which is independent of the model, are both much too small to be plausible, suggesting falloff effects rather than a failure of RFRM.
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  • 146
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    Infrared photochemistry of bis(trifluoromethyl) peroxide (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 627-638 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis(trifluoromethyl) peroxide is readily dissociated by multiple infrared photon excitation at CO2 laser wavelengths. The primary dissociation product is CF3O; approximately 85% of the nascent radicals are further dissociated in the laser field to form CF2O and F. The F atoms then react with the remaining CF3O to produce CF3OF. The formation of CF3OF is strongly inhibited by addition of HI, which reacts preferentially with the F atoms.
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  • 147
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    Micellar catalyzed enolization of acetone (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 695-705 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The acid-catalyzed enolization of acetone in the presence of bromine is found to be catalyzed by the anionic micelles of sodium dodecyl sulfate. The rate acceleration expected on the basis of lowering of activation energy is largely nullified by the decrease in the entropy of activation, leading to a very small rate enhancement, i.e., kψ/k0 = 1.2 at 30°C. The binding constant for the micelle-substrate complex is determined. The micellar rate enhancement is the same, irrespective of the halogen used, chlorine, bromine, or iodine.
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  • 148
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    Minor products and initiation rate in the chain pyrolysis of propaneThis paper summarizes a part of the dissertation submitted by C. Juste for the degree of Docteur-Ingénieur, Nancy, France, 1980. (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 855-864 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: With a continuous jet-stirred tank reactor operating at small space time (0.05-1.2 s) the kinetics of the formation of six minor products (ethane, isobutane, butene-1, 2,3-dimethyl-butane, 4-methylpentene-1, and 1,5-hexadiene) are studied during the pyrolysis of propane, at small extents of reaction and over the temperature range of 600-780°C. The experimental results are in agreement with the free radical mechanism proposed by Jezequel, Baronnet, and Niclause for this reaction. They show that the two most important termination processes are The measured rates of formation of the minor products are consistent with the quasi-identical values estimated by Jezequel and co-workers (between 475 and 505°C) and by Allara and Edelson (between 510 and 560°C) for kinetic parameters (A1 ≃ 1016.65 s-1 and E1 ≃ 84.7 kcal/mole) of the chain initiation process
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  • 149
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    A study of the reactions of fluorine with hydrogen and methane in the initiation phase using a miniature tubular reactor (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 39-58 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A small tubular reactor having an inner diameter of 1-2 mm andused as the source in a molecular beam apparatus is described in detail. This arrangement allows the study of fast reactions with reaction times smaller than 1 msec. The preexplosive reaction phase between F2 and H2 and CH4, respectively, is investigated to find out the initiation reactions. In the F2/H2 reaction, initiation is brought about by heterogeneous generation of F atoms or some other surface reaction. Evidence is also obtained for chain branching reactions. In the F2/CH4 case the dominant initiation reaction is the homogeneous reaction CH4 + F2 → CH3 + HF + F. The rate constant for the reaction between 300 and 400 K is 1012.3±0.3 exp[-47 ± 8 kJ/mol/RT] cm3/mol sec. The analysis of the experimental data also yields the rate constant for the propagation reaction CH3 + F2 → CH3 F + F, which is 1012.3±0.3 exp[-4.6 ±2.1 kJ/mol/RT] cm3/mol sec.
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  • 150
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    A novel type of chemical oscillator (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 321-322 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130311
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  • 151
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    The thermal decomposition of fluorinated esters (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 463-471 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of thermal decomposition of ethyl, isopropyl, and t-butyl trifluoroacetates have been studied in the gas phase. In each case initial decomposition follows the normal ester route to give an olefin and trifluoroacetic acid, and elimination of hydrogen fluoride does not occur. However, trifluoroacetic acid is thermally unstable at ethyl and isopropyl ester decomposition temperatures, and further products result, including those from the difluorocarbene produced by decomposing trifluoroacetic acid. Placing a CF3 group at an ester's γ carbon increases the polarity of its transition state and decreases its thermal stability. The activation energies of the ethyl and isopropyl esters are lowered by 3.8 and 4.7 kcal/mol compared to the corresponding acetates, and the primary decomposition kinetics, which are homogeneous and of the first order, are expressed by α-Methylation enhances the reactivity of the trifluoroacetates, and the t-butyl ester, the transition state for which is sufficiently polar for heterogeneous decomposition to occur, shows signs of thermal instability at room temperature. The equilibrium was also investigated and gave ΔH° = +13,580 cal/mol and ΔS° = +31.07 gibbs/mol in the forward direction. The results obtained extend and support the known structure-rate correlations in the gas-phase elimination of esters.
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  • 152
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    Very-low-pressure pyrolysis of ethylbenzene, isopropylbenzene, and tert-butylbenzene (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 445-462 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal unimolecular decomposition of ethylbenzene, isopropylbenzene, and tert-butylbenzene was studied using the very-low-pressure pyrolysis (VLPP) technique. Each reactant decomposed by way of β C—C bond homolysis, producing methyl radicals and benzyl or benzylic-type radicals. RRKM calculations show that the observed rate constants, when combined with thermochemical estimates, are consistent with the following high-pressure rate expressions: \documentclass{article}\pagestyle{empty}\begin{document}$ \log k(\sec ^{ - 1}) = 15.3 - (72.7/{\rm \theta)} $\end{document} for ethylbenzene between 1053 and 1234 K, \documentclass{article}\pagestyle{empty}\begin{document}$ \log k(\sec ^{ - 1}) = 15.8 - (71.3/{\rm \theta)} $\end{document} for isopropylbenzene between 971 and 1151 K, and \documentclass{article}\pagestyle{empty}\begin{document}$ \log k(\sec ^{ - 1}) = 15.9 - (69.1/{\rm \theta)} $\end{document} for tert-butylbenzene between 929 and 1157 K, where θ (kcal/mol) = 2.303RT. Resulting activation energies combined with heat capacity and heat of formation data led to the following dissociation enthalpies and enthalpies of formation at 298 K: DH° (øCH(CH3)—CH3) = 73.8 kcal/mol, ΔHf° (øÇCH(CH3)) = 39.6 kcal/mol, DH° (øC(CH3)2—CH3) = 72.9 kcal/mol, and ΔHf° (øÇ(CH3)2) = 32.4 kcal/mol. Derived high-pressure rate constants are in good accord with results of lower temperature toluene- and aniline-carrier experiments.
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    Masthead (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130601
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  • 154
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    An overall and detailed kinetic study of the pyrolysis of propane (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 149-172 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Overall and detailed kinetic descriptions of the pyrolysis of C3H8 have been proposed as a result of a turbulent flow reactor investigation in the temperature range of 1110-1235 K and at atmospheric pressure. The overall reaction was described by a first-order rate expression with an activation energy of 58.65 kcal/mol and a preexponential factor of 3.2 × 1012 sec-1. This expression agrees with previously reported rate data. In addition, a kinetic mechanism involving 13 chemical species and 32 elementary reactions has been postulated to describe the kinetics. Experimental data from the present flow reactor experiments and from static vessel and shock tube experiments reported in the literature were used to verify the mechanism. Agreement over the temperature range of 800-1400 K and over the pressure range of 0.1-8.5 atm was obtained by adjusting three rate constants. Previously reported values for these rate constants appear to require reexamination. The reactions in question are the following: The sum of the rate constants for reactions (2a) and (2b) and the rate constant for reaction (23) are best represented by \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{2a} + k_{2b} = 10^{- 0.1} T^4 \exp (-8300/{\rm RT}){\rm cm}^3 /{\rm mol}\;{\rm sec} $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{23} = 10^{14.55} \exp (-14,340/{\rm RT}){\rm cm}^3 /{\rm mol}\;{\rm sec} $$\end{document} which differ with the expressions in the literature.
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  • 155
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    Rate constants for ozone-alkene reactions under atmospheric conditions (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 209-217 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By measuring the rates of decay of ozone in a large excess of reactant, second-order rate constants have been obtained for the reactions of ozone with ethene, propene, but-1-ene, trans-but-2-ene, isobutene, hex-1-ene, cyclopentene, cyclohexene, isoprene, vinyl fluoride, 1,1-difluoroethene, cis-1,2-difluoroethene, trans-1,2-difluoroethene, trifluoroethene, tetrafluoroethene, and 2,5—dihydrofuran. The reactions have been studied in synthetic air at atmospheric pressure and at temperatures of 294 and 260 K. The rate constants and Arrhenius parameters are discussed in relation to existing kinetic data on ozone-alkene reactions.
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  • 156
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    Very low-pressure pyrolysis (VLPP) of pentynes. II. 4-methylpent-2-yne and 4,4-dimethylpent-2-yne. Heats of formation and resonance stabilization energies of methyl-substituted propargyl radicals (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 255-272 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies of the unimolecular decomposition of 4-methylpent-2-yne (M2P) and 4,4-dimethylpent-2-yne (DM2P) have been carried out over the temperature range of 903-1246 K using the technique of very-low pressure pyrolysis (VLPP). The primary reaction for both compounds is fission of the C—C bond adjacent to the acetylenic group producing the resonance-stabilized methyl-substituted propargyl radicals, CH3C≡ĊH(CH3) from M2P and CH3C≡CĊ(CH3)2 from DM2P. RRKM calculations were performed in conjunction with both vibrational and hindered rotational models for the transition state. Employing the usual assumption of unit efficiency for gas-wall collisions, the results show that only the rotational model with a temperature-dependent hindrance parameter gives a proper fit to the VLPP data over the entire experimental temperature range. The high-pressure Arrhenius parameters at 1100 K are given by the rate expressions log k2 (sec-1) = (16.2 ± 0.3) - (74.4 ± 1.5)/θ for M2P and log k3 (sec-1) = (16.4 ± 0.3) - (71.4 ± 1.5)/θ for DM2P where θ = 2.303RT kcal/mol. The A factors were assigned from the results of recent shock-tube studies of related alkynes. Inclusion of a decrease in gas-wall collision efficiency with temperature would lower both activation energies by ∼1 kcal/mol. The critical energies together with the assumption of zero activation energy for recombination of the product radicals at 0 K lead to DH0[CH3CCCH(CH3)—CH3] = 76.7 ± 1.5, ΔHf0[CH3CCCH(CH3)] = 65.2 ± 2.3, DH0[CH3CCCH(CH3)—H] = 87.3 ± 2.7, DH0[CH3CCC(CH3)2—CH3] = 72.5 ± 1.5, ΔHf0[CH3CCĊ(CH3)2] = 53.0 ± 2.3, and DH0[CH3CCC(CH3)2—H] = 82.3 ± 2.7, where all quantities are in kcal/mol at 300 K. The resonance stabilization energies of the 1,3-dimethylpropargyl and 1,1,3-trimethylpropargyl radicals are 7.7 ± 2.9 and 9.7 ± 2.9 kcal/mol at 300 K. Comparison with results obtained previously for other propargylic radicals indicates that methyl substituents on both the radical center and the terminal carbon atom have little effect on the propargyl resonance energy.
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  • 157
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    Temperature-dependent a factor in thermal unimolecular reactions II. Exponential dependence (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 283-293 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is assumed that A∞ in the limiting high-pressure unimolecular rate constant expression k∞ = A∞ exp(-Ea∞/kT) is given by A∞ = A″∞eBkT. The test case is the decomposition butane → 2 ethyl, where a negative B reproduces the temperature dependence of A∞ about as well as the previously considered power law A∞ = A′∞(kT)n. It is shown that the term eBkT modifies significantly the high-temperature falloff of the general-pressure rate constant kuni and its various derivatives, and admits of a fairly simple interpretation in terms of Benson's restricted rotor theory. On physical grounds, the exponential law appears more reasonable than the power law.
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  • 158
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    Preliminary announcement (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 323-323 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130312
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  • 159
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    From energy profiles to structure-reactivity correlations (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 333-365 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Models for the energy profile along the reaction coordinate are utilized to determine the barrier's height and location as a function of ΔG. These form the basis for structure-reactivity correlations and afford a unified formulation for various postulates in the field of physical organic chemistry. Current experimental evidence is examined for the resulting correlations, and some of their applications as an aid to the chemical kineticist are presented.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550130403
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  • 160
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    The hydrolysis of phosphoranes in aqueous dioxanePresented at the International Conference on Reactions in Solution, Canterbury, England, July 8-13, 1979 (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 411-416 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The entropy of activation for the hydrolysis of pentaphenoxyphosphorane in 25% aqueous dioxane is -188 J/mol deg. The enthalpy of activation is 22.5 kJ/mol, which is small for the relatively slow reaction. This suggests that the reaction is a multistep process having a preliminary equilibrium with a negative heat of reaction. This conclusion is supported by the results obtained for the hydrolysis of C6H5[OCH(CF3)2]2. A kinetic isotope effect kH2O/kD2O of 3.46 was found for the latter reaction. Orders in water were obtained, and a mechanism of hydrolysis is proposed.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550130407
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  • 161
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    Persulfate and perphosphate oxidation of 2-propanol: A relative rate study (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 497-501 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A competitive reaction study for two isoelectronic peroxides (peroxodisulfate S2O82- and peroxodiphosphate P2O84-) interacting with the free radical ·Clpar;CH3)2OH is described. The radical formation is initiated by photolysis, the amounts of peroxide remaining analyzed volumetrically. It is found that persulfate reacts with the organic radical over 100 times more rapidly than does perphosphate. Mechanistic consequences in relation to previous work are briefly discussed.
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  • 162
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    Rate constants for the reaction of tert-butyl radicals with chloroform in solution (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 527-541 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decay of photochemically generated tert-butyl radicals in methylcyclopentane solutions containing chloroform is studied by time-resolved ESR spectroscopy. In the pure solvent it perfectly follows the second-order rate law for radical self-termination. Increasing chloroform concentrations cause increasing admixture of a pseudo-first-order decay from which the rate constant of the title reaction is obtained. For 273 K ≦ T ≦ 323 K, \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}\,{\rm k(}M^{{\rm - 1}}\sec ^{ - 1}) = (8.41 \pm 0.14) - \frac{{8.12 \pm 0.18}}{\theta } $$\end{document} where θ = 2.303RT kcal/mol. CIDNP studies of the reaction mechanism and NMR product yields show H and Cl abstractions to occur with the temperature-independent ratio kH/kCl = 1.4 ± 0.1. The results point to polar effects in the transfer reactions of tert-butyl. The potential of time-resolved ESR spectroscopy in studies of first- and pseudo-first-order reaction rates is discussed.
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  • 163
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    Masthead (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130701
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  • 164
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    Infrared photochemistry of cyclobutyl chloride (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 615-625 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of cyclobutyl chloride following multiple infraredphoton excitation has been investigated. The primary photolysis products are butadiene, from elimination of HCl, and ethylene and vinyl chloride, fromring scission. The vinyl chloride undergoes secondary decomposition to acetylene and HCl. In addition to these products, known from thermal VLPP experiments, we also find 1-butene, which may arise from a higher energy C—Cl homolysis channel. Collisions with either reactant molecules oradded buffer gas lead to cooling of the laser-produced vibrational energy distributions. The average amount of energy removed per collision is 15-20 kcal/mol for self-collisions and 2-4 kcal/mol with argon.
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    URL: http://dx.doi.org/10.1002/kin.550130703
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  • 165
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    The rate of reaction of methyl radicals with ozone (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 667-675 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absolute rate constant for the reaction of methyl radicals with ozone has been measured as a function of temperature. Small concentrations of CH3 were generated by flash photolyzing CH3NO2 at 193 nm with an ArF laser. A photoionization mass spectrometer was used to follow the rate of decay of CH3 at various ozone concentrations. The resulting rate constants could be fit by the expressions \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = (5.4 \pm 1.5) \times 10^{ - 12} \exp [(- 216 \pm 80)/T]{\rm cm}^3 /{\rm molec}\,{\rm s} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = (2.6 \pm 0.7) \times 10^{ - 12} {\rm (T/300)}^{{\rm 0}{\rm .71} \pm {\rm 0}{\rm .34}} {\rm cm}^3 /{\rm molec}\,{\rm s} $$\end{document} over the temperature range of 243-384 K. These rate constants can be modeled by simple transition state theory using reasonable parameters for the activated complex. Use of this rate constant shows that less than 1% of the methyl radicals formed in the stratosphere react with ozone.
    Additional Material: 3 Ill.
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  • 166
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    Erratum (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 693-693 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550130709
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  • 167
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    The √t law in solid-phase reactions. Analysis of the hypothesis on rate constant distribution (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 707-728 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction C2H5 + O2 → C2H5O2 in glassy methanol-d4 and the H-atom abstraction by CH3, C2H5, and n-C4H9 radicals in C2H5OH + C2D5OH and CD3CH2OH + C2D5OH glassy mixtures have been studied by electron spin resonance. The analysis of the dependence of the reaction rates on the concentration of O2 (oxidation) and C2H5OH, CD3CH2OH (H-atom abstraction) has shown that the √t law is not conditioned by the existence of regions characterized by different rate constants.
    Additional Material: 18 Ill.
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  • 168
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    Masthead (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130901
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  • 169
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    Reaction of hydrogen atoms with diethyldisulfide and ethylmethyldisulfide (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 799-815 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: H atoms react with C2H5SSC2H5 to give C2H5SH as the sole retrievable product with φ = 2.32 at 25°C and 2.84 at 145°C. The primary reaction is postulated to be H + C2H5SSC2H5 ← C2H5SH + C2H5S with k1 = (4.73 ± 0.64) × 1013 exp [-(1710 ± 69)/RT] cm3/mol·s relative to the rate constant of the H + C2H4 ← C2H5 reaction. The high value of the entropy of activation suggests the presence of partial hydrogen bonding in diethyldisulfide which is broken in the transition state.Ethylmethyldisulfide reacts similarly: H + C2H5SSCH3 ← C2H5SH + CH3S or CH3SH + C2H5S. The thiyl radicals propagate a chain of radical exchange reactions forming the symmetrical disulfides with exposure-time-dependent quantum yields. The overall kinetics conform to a 16-step mechanism from which the rate constants of the elementary reactions could be established by computer modeling. Thiyl radicals react considerably more slowly with disulfides than H atoms.
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    URL: http://dx.doi.org/10.1002/kin.550130905
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  • 170
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    Reactions of the fluorobromocarbene radical studied by laser-induced fluorescence (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 873-881 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: CFBr radicals produced by the reaction of atomic oxygen with F2CCFBr were monitored in a discharge flow system by fluorescence excited at 424 nm. The rate coefficients for reactions of the CFBr radicals were measured between 298 and 358 K, and the following values were obtained in units of cm3/molec·s: O2 〈 2 × 10-16 at 353 K; NO 〈 10-14 at 298 K; F2CCFBr 〈 10-15 at 298 K; Cl2 (1.9 ± 0.6) × 10-12 exp(-762 ± 92/T) Br2 (1.4 ± 0.3) × 10-12 exp(-533 ± 62/T).
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    URL: http://dx.doi.org/10.1002/kin.550130911
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  • 171
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    On the frequency factor in electron transfer reactions and its role in the highly exothermic regime (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 865-872 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Consideration of current information on the dependence of the electron transfer rate on the radial separation distance and on the reactants′ radial distribution function suggests for adiabatic transfers a frequency factor closer to 1012M-1 s-1 than to 1011M-1 s-1. One effect is to raise the λ values estimated from self-exchange rate constants, and to extend thereby the range of ΔG°'s in which the “inverted region′” is masked by a diffusion-controlled reaction rate.
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  • 172
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    Masthead (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130201
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  • 173
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    Effect of brownian diffusion on chemical kinetics (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 125-133 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new method of theoretical prediction of the kinetic rate constants of fast chemical reactions in solutions is presented. It takes into account the effect of finite diffusive displacements of the reacting molecules. The approach is based on the solution of the steady-state Fokker-Planck equation by the moments method of Grad developed in the theory of coagulation of aerosol particles. A comparison of the predicted rate constants with the experimental data provided by Schuh and Fischer for the self-reaction of tert-butyl radicals in n-alkanes shows a good correspondence.
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    URL: http://dx.doi.org/10.1002/kin.550130204
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  • 174
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    On the prediction of reaction rates by simple correlations (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 317-320 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130310
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  • 175
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    The rate constant for t-C4H9 → H + i-C4H8 and the thermodynamic parameters of t-C4H9 (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 303-316 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of the reverse reaction of the system has been measured in the range of 584-604 K from a study of the azomethane sensitized pyrolysis of isobutane. Assuming the published value for the rate constant of recombination of t-butyl we obtain \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_{{\rm - 1}} (\sec ^{- 1}) = 14.67 - 39.4\,{\rm kcal}/{\rm mol}/(2.3{\rm RT}) $$\end{document} Combination with our published data for k1 permits the evaluation \documentclass{article}\pagestyle{empty}\begin{document}$$ \log K_1 ({\rm atm}^{ - 1}) = 7.94\,\,{\rm at}\,\,600{\rm K} $$\end{document}We have modified a previously published structural model of t-butyl by the inclusion of a barrier to free rotation of the methyl groups in order to calculate values of the entropy and enthalpy of t-butyl as a function of temperature. Using standard data for H and for i-C4H8 we obtain \documentclass{article}\pagestyle{empty}\begin{document}$$ \Delta H_ f^\circ(t - {\rm butyl},\,300\,{\rm K})({\rm kcal}/{\rm mol}) = 10.6 \pm 0.5 $$\end{document}We have obtained other, independent values of this quantity by a reworking of published data using our new calculations of the entropy and enthalpy of t-butyl. There is substantial agreement between the different values with one exception, namely, that derived from published data on the equilibrium \documentclass{article}\pagestyle{empty}\begin{document}$$ i - {\rm C}_{\rm 4} {\rm H}_{{\rm 10}} + {\rm I}\rightleftharpoons t{-} {\rm C}_4 {\rm H}_9 + {\rm HI} $$\end{document} which is significantly lower than the other values.We conclude that the value \documentclass{article}\pagestyle{empty}\begin{document}$$ \Delta H_ f^\circ(t - {\rm butyl},\,300\,{\rm K})({\rm kcal}/{\rm mol}) = 10.5 \pm 1.0 $$\end{document}obtained from the present work and a reworking of published data which involves the use of experimental data on t-butyl recombination is incompatible with the result based on iodination data.
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  • 176
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    The pyrolysis kinetics of 4-chloro-2-butanone in the gas phase (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 403-410 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates of pyrolysis of 4-chloro-2-butanone in the gas phase have been determined in a static system seasoned with the products of decomposition of allyl bromide. The reaction is catalyzed by hydrogen chloride. Under maximum catalysis of HCl, the kinetics were found to be of order 1.5 in the substrate suggesting that a complex elimination is involved. The reaction, when maximally inhibited with propene, appears to undergo a unimolecular elimination and follows a first-order law kinetics. The products are methylvinyl ketone and hydrogen chloride. The kinetics have been measured over the temperature range of 402.0-424.4°C.The rate coefficients are given by the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$ \log k_1 (\sec ^{ - 1}) = (13.67 \pm 0.69) - (225.2 \pm 8.6)\,{\rm kj}/{\rm mol}/2.303RT\angle $\end{document}. Thepyrolysis of 4-chloro-2-butanone is 31 times greater in rate than that of ethyl chloride at 440°C. This large difference in rate may be attributed to the -M effect of the acetyl substituent in the pyrolysis of the former halo compound.
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  • 177
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    Gas-phase pyrolysis of neopentyl bromide (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 7-21 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of gaseous neopentyl bromide to 2-methyl-2-butene, 2-methyl-1-butene, and hydrogen bromide was studied under conditions of maximal inhibition by cyclohexene over the temperature range of 389-444°C. This reaction was shown to beconsistent with a first-order homogeneous molecular process, with Arrhenius parameters of E = 247 ± 5 kJ/mol and log A (sec-1) = 14.2 ± 0.3. Examination of the uninhibited reaction showed it to be a radical process, simpler than that with neopentyl chloride, there being only one propagation step, thedissociation of the γ-radical to 1,1-dimethylcyclopropane and a bromine atom.
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  • 178
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    The reaction of atomic oxygen O(3P) with propane (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 69-84 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of O(3P) atoms with propanehas been studied at temperatures near 300 K by using a discharge flow system. Oxygen atoms were generated in the absence of molecular oxygen by the reaction N + NO → N2 + O, nitrogen atoms having been generated in a microwave discharge. Rate constants for the reaction were measured in two ways, either by measurement of O-atom decay in the presence of excess propane or by measuring the change in propane concentration after an appropriate time in the presence of an excess of oxygen atoms. The two methods were in good agreement, and the mean rate constant at 306 K is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = (4.7 \pm 0.8) \times 10^6 {\rm dm}^3 /{\rm mol}\;\sec $$\end{document} A study of the products of the reaction under conditions corresponding to complete removal of oxygen atoms has shown that an important product of the reaction in the early stages is propene. This is difficult to explain interms of a mechanism involving alkoxy radicals similar to that which has been proposed for some other O(3P)-hydrocarbon reactions. An alternative mechanism is proposed in terms of successive hydrogen abstraction reactions.
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  • 179
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    Reactivity of amines toward tert-butoxy radicals: Effect of solvent and amine structure (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 119-123 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactivity of amines towards tert-butoxy radicals depends upon the amine ionization potential and the solvent, indicating that polar structures contribute to the reactivity of these compounds. Nevertheless, the dependence with the amine potential is smaller than the one obtained for the quenching of carbonyl excited states by amines and other factors as the strength of the broken hydrogen bond and steric hindrance are also significant in determining the rate of the process.
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  • 180
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    Thermal reactions of ethane-d6-acetylene and D2-acetylene mixtures behind shock waves (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 741-753 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of the thermal decomposition of an acetylene-ethane-d6 mixture indicates that the rate constant for hydrogen abstraction from acetylene by methyl is more than 20 times less than for abstraction from ethane. Isotopic exchange is initiated by a rapid reaction between product D atoms and C2H2. A series of experiments involving the reactions of a D2-acetylene mixture indicated that a molecular exchange process was also occurring, and it was shown that d[C2HD]/dt = k[D2]0.7[C2H2]0.3, effective activation energy = 15.8 kcal/mol. This mechanism made an insignificant contribution to isotope exchange in C2H2-C2D6 mixtures.
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  • 181
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    Nonisothermal decomposition of methyl nitrate: Anomalous reaction order and activation energies and their correction (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 817-831 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methyl nitrate decomposition is accompanied by self-heating. Using very fine thermocouples, direct measurements of excess temperatures have been made to establish the intensity and extent of self-heating in nonisothermal reaction. The measurements are displayed as contourlines of equal degrees of temperature excess on the pressure-temperature ignition diagram.A twofold kinetic investigation has been made of the overall reaction. One part concentrates on achieving isothermal conditions and full characterization of intermediate products. It uses mass-spectrometric analyses both to establish stoichiometry throughout decomposition and to validate velocity constant measurements derived from continuous pressure-time records. The best value for E = 151 ± 3 kJ/mol is about 10 kJ/mol less than previously.The other part deliberately invades the nonisothermal region to test the qualitative and quantitative predictions of theory (1) that uncorrected reaction orders and activation energies will exceed their isothermal values, (2) that their relative excess (δn/n, δE/E) will be about the same, and (3) that they will be dependent in a simple and predictable way on the reduced excess central temperature.
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  • 182
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    Editor's note (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 785-786 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130902
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  • 183
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    Professor Keith J. Laidler (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 787-788 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130903
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  • 184
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    Arrhenius parameters for the alkoxy radical decomposition reactions (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 833-844 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Arrhenius parameters for the decomposition reactions of various alkoxy radicals are evaluated. The recommended values for tert-butoxy radical decomposition reaction are log A (s-1) = 14.1, Ea = 15.3 kcal/mol. The parameters give reasonably self-consistent results with related rate constants, product distributions of hydrocarbon oxidation reactions, and the values reported in different laboratories in different environments.A reworking of data by Batt et al. on RO + NO and RO + NO2 leads to a lowering of his A factors for these reactions by a factor of 5. It also leads to a similar lowering of the A factors for RO decompositions. The intrinsic activation energies E for the addition of alkyl radicals R to the carbonyl group are not only found to be a function of the exothermicity of reaction, but they are also dependent on the nucleophilicity of the alkyl radicals. For each radical R (Me, Et, i-Pr) the data can be fit to an Evans-Polanyi plot E = a + b (δH), where a uniform slope b = 0.58 can be found for all R. The intercepts a are then found to decrease nearly linearly with the decreasing ionization potential of R, namely, a = 2.1 [IP] - 6.2 (kcal/mol), with the ionization potential given in electron volts.
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    URL: http://dx.doi.org/10.1002/kin.550130907
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  • 185
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    Anchimeric assistance in the gas phase dehydrohalogenation of 5-chloro-2-methylpent-2-ene (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1-6 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 5-Chloro-2-methylpent-2-ene decomposes at temperatures of 370-420°C with initial pressures from 61to 158 torr to yield hydrogen chloride and a mixture of methylpentadiene isomers. In a static system, with seasoned vessel and propene inhibitor, the reaction is homogeneous, unimolecular, and of the first order. The rate coefficient is expressed by the following Arrhenius equation: log k (sec-1) = (13.43 ± 0.30) - (215.0 ± 3.7) kJ/mol/2.303RT. The result ofthe present work additionally supports the participation of the neighboringaliphatic olefinic double bond in the rate of HCl elimination of alkenyl chlorides in the gas phase. Moreover, it also confirms the three-membered conformation as the most favored structure for anchimeric assistance.
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    URL: http://dx.doi.org/10.1002/kin.550130102
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  • 186
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    The kinetics of the reactions of C2F5 radicals with Br2 and HBr (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 59-67 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A mixture of Br2 + HBr + C2F5I was photolyzed in the vapor phase. The reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Br + C}_{\rm 2} {\rm F}_{\rm 5} {\rm I} \to {\rm IBr + C}_{\rm 2} {\rm F}_{\rm 5} $$\end{document} forms C2F5 radicals which are removed by Competitive studies over the range of 74-146°C gave ratios of k10/k9, and these were combined with values obtained previously by different methods at higher temperatures upto 515°C to give \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log(}k_{10} /k_9) = (- 0.47 \pm 0.03) - (12,500 \pm 300)/\theta $$\end{document} where θ = 2.303RT J/mol. A value is assigned to the activation energy E10, and this, with other data, leads to \documentclass{article}\pagestyle{empty}\begin{document}$$ D{\rm (C}_{\rm 2} {\rm F}_{\rm 5} - {\rm H}) = 429.8 \pm 2.1{\rm KJ}/{\rm mol} $$\end{document} at 25°C. This result is in excellent agreement with two previous independent determinations.
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    URL: http://dx.doi.org/10.1002/kin.550130106
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  • 187
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    Coupling rates and kinetics of arenediazonium cations with couplers utilized in the diazo reprographic process (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 97-107 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stoichiometric and, in most cases, absolute rates of coupling of a series of m- and p-substituted benzenediazonium ions with 2,3-dihydroxynaphthalene-6-sulfonate ion (1) have been determined (i) at pH 5.6 (when one OH group is partly monoionized) and (ii) at pH 9.9 (when one OH group is completely ionized and the second slightly so). The rates at both pH values correlate with the σ+ parameter (except for the most reactive ArN2+ at pH 9.9) and the contributions of the two reactive forms of the coupler evaluated. Detailed pH dependences of the coupling rate of the p-chlorobenzenediazonium ion with (1) reveal a strong interaction between (1) and the borate ion, which strongly influences the coupling rate. Coupling rates have also been measured for both diazonium ions and couplers of importance in the diazo reprographic process.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550130109
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  • 188
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    Kinetic studies of free radical reactions by mass spectrometry. II. The reactions of SO + ClO, SO + OClO and SO + BrO (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 187-197 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates of several novel elementary reactions involving ClO, BrO and SO free radicals in their ground states were studied in a discharge-flow system at 295 K, using mass spectrometry. The rate constant k2 was determined from the decay of SO radicals in the presence of excess ClO radicals: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm SO} + {\rm ClO} \to {\rm SO}_{\rm 2} + {\rm Cl;}} & {k_{\rm 2} = (2.3{\rm } \pm {\rm 0}{\rm .6}) \times 10^{ - 11} {\rm cm}^3 \sec ^{ - 1} } \\ \end{array}$$ \end{document}The SO + OClO overall reaction has a complex mechanism, with the primary step having a rate constant k5 equal to (1.9 ± 0.7) × 10-12 cm3 sec-1: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm SO} + {\rm OClO } \to {\rm SO}_{\rm 2} + {\rm ClO} $$\end{document}A lower limit for the rate constant of the rapid reaction of SO radicals with BrO radicals was determined: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm SO} + {\rm BrO} \to {\rm SO}_{\rm 2} + {\rm Br;}} & {k_{17} } \\ \end{array} \ge 4 \times 10^{ - 11} {\rm cm}^3 \sec ^{ - 1} $$\end{document}
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550130208
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  • 189
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    Effect of cyano group substitution on metathetical reactions. IV. Substituent effects on the rates of cyanomethyl radical reaction with haloalkanesReference [5] of this article is part III of this series (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 219-230 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Gamma radiation-induced free radical chain reactions in liquid mixtures of BrCH2CN, eyelohexane (RH), and haloalkanes (XCCl3) were studied. The kinetics of hydrogen and chlorine atom abstraction from CHCl3, CH3CCl3, CH2ClCCl3, CHCl2CCl3, CF3CCl3, C2Cl6, CCl3CN, and CCl4 by CH2CN radicals were investigated by a competitive method. The reactions investigated were Rate constant ratios k3/k2, k5/k6, k7/k2, and k3/k7 were determined at 180°C. In the CCl4—RH—BrCH2CN system k3/k2 was determined in the temperature range of 100-180°C, yielding log k2 k3 = -0.11 ± 0.2 -(3.34 ± 0.39/θ): where θ = 2.3RT in kcal/mol. The value E2—E3 was combined with existing data on E3 to yield E2(CCl4) = 17.57 kcal/mol. The reactivity trend of CH2CN is compared with that of R radicals. It is shown that in spite of a difference of about four orders of magnitude in kCl values, the reactive cyclohexyl radical is somewhat more selective than CH2CN. It is proposed that the relative reactivities log[k2(XCCl3)/k2(CH3CCl3)] can be correlated in terms of a dual-parameter Taft equation which takes into account both resonance and inductive substituent effects.
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    URL: http://dx.doi.org/10.1002/kin.550130302
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  • 190
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    The rate constant for H + i-C4H8 → t-C4H9 in the range of 298-563 K (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 295-301 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The overall rate constant for hydrogen-atom addition to isobutene has been measured in the temperature range of 298-563 K in a flow discharge system coupled to a quadrupole mass spectrometer. Previously published results allow the determination of \documentclass{article}\pagestyle{empty}\begin{document}$$ \log {\rm }k_1 ({\rm cm}^3 /{\rm mol\,\, sec}) = 13.59 \pm 0.11 - 1.79 \pm 0.19\,\,{\rm kcal/mol/(2}{\rm .3}RT{\rm)} $$\end{document} where the error limits are 95% confidence limits.
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    URL: http://dx.doi.org/10.1002/kin.550130308
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  • 191
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    Kinetics of acid catalyzed and Ag(I) catalyzed decomposition of peroxodisulfate in aqueous medium (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 555-564 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of acid catalyzed decomposition of peroxodisulfate, (S2O82-) in aqueous perchlorate medium involves the hydrolysis of the species H2S2O8 and HS2O8- and the homolysis of the species H2S2O8, HS2O8- and S2O82- at the O—O bond. The overall rate law when 1.4M 〉 [HClO4] 〉 0.1M is \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{ - d[{\rm S}_{\rm 2}{\rm O}_8^{2 - }]}}{{dt}}\, = \,k_0 [{\rm S}_{\rm 2}{\rm O}_8^{2 - }]\, + \,k' [{\rm S}_{\rm 2}{\rm O}_8^{2 - }][{\rm H}+]\, + \,k{''}[{\rm S}_{\rm 2}{\rm O}_8^{2 - }][{\rm H}+]^2 $$\end{document}The constants k′ and k″ contain the hydrolysis and homolysis rate constants of HS2O8- and H2S2O8, respectively. With added Ag(I), the acid catalyzed and Ag(I) catalyzed reactions take place independently. Ag(I) catalyzed decomposition appears to involve the species AgS2O8- (aq).
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    URL: http://dx.doi.org/10.1002/kin.550130605
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  • 192
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    Photolysis of ethyl-iodide in lithium chloride glassy aqueous solutions with light, λ = 254 nm at 77 K (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 543-554 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of C2H5I in a glassy salt matrix (5M, 7.5M, 10M) of aqueous LiCl at 77 K with light of λ = 254 nm has been conducted, product analysis being by ESR and UV spectroscopy. The electrolytic medium causes the ionization of product HI, and I- concentrations can be continuously determined. During photolysis [I-] is less than the amount of C2H5I decomposed. But after photolysis thaw-freeze cycling is accompanied by progressive growth in [I-] until the yield matches the C2H5I loss, the quantum yields being 0.26, 0.20, and 0.17 for the three LiCl solutions, respectively. The quantum yield of unionized HI is unchanged, however, at around 0.36, the overall change being due to a fall in the extent to which the HI is ionized in the direct photolysis (ø = 0.22, 0.16, and 0.11). It is proposed that this is a consequence of the density increase of matrix packing as the LiCl concentration is increased so that fewer HI are in contact with the aqueous medium and cage recombination is favored.The results establish that the primary reaction is essentially exclusive: and that substantial aggregates of C2H5I exist within which HI are caged and cannot be ionized. The direct reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 2}{\rm H}_{\rm 5}{\rm I}+ h\nu \to {\rm C}_{\rm 2}{\rm H}_5^. + {\rm I}^. $$\end{document} occurs only to a trivial extent, ø; = 10-4, C2H5 arising virtually totally via \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 2}{\rm H}_{\rm 4}+ {\rm H}^. \to {\rm C}_{\rm 2}{\rm H}_5^. $$\end{document}
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    URL: http://dx.doi.org/10.1002/kin.550130604
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  • 193
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    Steric factors in the kinetically controlled direction of elimination of secondary and tertiary esters in the gas phase. The pyrolysis of 4,4-dimethylpent-2-yl acetate (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 577-589 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis kinetics of 4,4-dimethylpent-2-yl acetate, in a static system and in a vessel seasoned with allyl bromide, have been studied in the temperature range of 300-350°C and the pressure range of 48-211 torr. The olefin products were 4,4-dimethylpent-1-ene, cis-4,4-dimethylpent-2-ene, and trans-4,4-dimethylpent-2-ene. The rate coefficient for the homogeneous unimolecular elimination of this ester is given by the following Arrhenius equation: log k(sec-1) = (12.87 ± 0.31) - (181.2 ± 3.4)kJ/mol/2.303RT. The direction of elimination of this acetate has been found to proceed to the formation of the corresponding olefin by kinetic control. The present data, together with other pyrolysis work subject to kinetic control, imply that the direction of elimination of bulky alkyl esters is determined by steric hindrance in the eclipsed cis conformation. However, further analyses reveal that if a series of esters are compared, in the case of a gradual increase of alkyl branching when adjacent to a hydrogen atom (alkyl-H interactions), the rate was determined by steric acceleration, owing to the crowding effect at the highly substituted carbon atom. Otherwise if this gradual alkyl increase in size happened to be adjacent to another alkyl substituent (alkyl-alkyl interactions), the rate was affected by steric hindrance of the eclipsed cis conformation.
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    URL: http://dx.doi.org/10.1002/kin.550130607
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  • 194
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    The correlation of rate coefficients for H-atom abstraction by HO radicals with C—H bond dissociation enthalpies (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 651-665 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For H-atom abstraction reactions by HO radicals it has been shown that If Di is taken as the C—H bond dissociation enthalpy at 298 K, then a = 0.323 and D0is obtained from the empirical formula \documentclass{article}\pagestyle{empty}\begin{document}$$ D_0 ^{ - 1} = 1.062 \times 10^{ - 2} + 3.52 \times 10^{ - 6} T $$\end{document} where D0 is in kcal/mol and T is in K. Thisrelationship is valid for T between 200 and 400 K. Finally empiricalrelationships are given to help estimate Di.
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    URL: http://dx.doi.org/10.1002/kin.550130706
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  • 195
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    The temperature coefficient of the rates in the system Cl + CH4 ⇆ CH3 + HCl, thermochemistry of the methyl radical (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 677-691 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bimolecular rate constant for the title reaction has been measured by very-low-pressure reactor techniques at 233 〈 T K 〈 338. The equilibrium constant has also been measured between 253 and 338 K. Our rate constants are in excellent agreement with recent measurements using very different techniques and reaction conditions, and the general agreement probably makes this one of the most accurately measured rateconstants. Transition state models of the reaction rule out a bent TS in favor of a TS with colinear Cl···H···C bonds. The curvature at higher temperatures (〉350 K) is quantitatively accounted for by transition state theory analysis. Tunneling is shown not to play a role. The measured values of K1 allow an experimental value of S° (CH3) to be fixed to only ±2.4 e.u. However, using known values of S° for all species gives ΔH°f298(CH3.) = 35.1 plusmn; 0.1 kcal/mol in excellent agreement with other measured values.
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    URL: http://dx.doi.org/10.1002/kin.550130708
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  • 196
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    Evidence for chamber-dependent radical sources: Impact on kinetic computer models for air pollution (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 735-740 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of NOx-air irradiations, with trace amounts of propane and propene present to monitor OH radical concentrations, have been carried out in a 5800-L evacuable environmental chamber to investigate radical levels and sources during such irradiations. The data obtained show conclusively that unknown radical sources are present, and that photolysis of initial nitrous acid can be, at best, only a minor source of radicals after ∼30-60 min of irradiation.
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    URL: http://dx.doi.org/10.1002/kin.550130805
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  • 197
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    Kinetics and mechanism of the thermal decomposition of cyclopentyl cyanide (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 755-770 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of cyclopentyl cyanide has been investigated in the temperature range of 905-1143 K using both conventional stirred-flow reactor and very low-pressure pyrolysis (VLPP) techniques. The results from both techniques are consistent. The main primary processes are HCN elimination to form cyclopentene: and ring fragmentation to form vinyl cyanide plus propylene and ethylene plus cyanopropenes: Under the experimental conditions cyclopentene undergoes further decomposition to cyclopentadiene plus hydrogen. There is evidence for conversion of some of the reactant to a solid residue, presumably polymer. From the stirred-flow reactor results the following Arrhenius expressions were obtained: log k1(s-1) = (12.8 ± 0.3) - (65.6 ± 1.3)/θ and log k2(s-1) = (16.0 ± 0.3) - (80.0 ± 1.1)/θ, where θ = 2.303RT kcal/mol. Application of RRKM theory shows that the VLPP experimental rate constants are consistent with high-pressure Arrhenius parameters given by log k1(s-1) = (12.8 ± 0.3) - (67.8 ± 2.5)/θ for HCN elimination, and log k4(s-1) = (16.3 ± 0.3) - (80.1 ± 2.0)/θ for the sum of the ring fragmentation pathways. The rate parameters for HCN elimination are in good agreement with previous VLPP studies of alkyl cyanides and with theoretical predictions. The difference in activation energies for the ring opening of cyclopentane and cyclopentyl cyanide is reasonably close to the established value for the cyano stabilization energy. This supports the assumption of a biradical mechanism.
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    URL: http://dx.doi.org/10.1002/kin.550130807
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    Masthead (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130101
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  • 199
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    Free-radical chain dechlorination of chloroethanes in liquid triethylsilane (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 23-38 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and mechanism of the free-radical chain dechlorination of C2Cl6, C2Cl5H, and sym-C2Cl4H2 in Et3SiH wereinvestigated over a wide temperature range. The propagation step of the dechlorination of chloroethanes (C2Clx H6-x) proceeds by the following reactions: Analysis of the temperature dependence of product formation gave the Arrhenius expressions for k4/k3 which in turn were utilized for the estimation of the absolute Arrhenius parameters for hydrogen abstraction from Et3SiH. Our results show that the values of Eabs are lower in Et3SiH than in c-C6H12 by about 2-3 kcal/mol, while the A factors are almost equal. In competitive studies k2 was determined versus Br abstraction from n-C5H11Br. The relative Arrhenius parameters determined by this method show that variations in both A factors and activationenergies are responsible for the reactivity trends observed in the Cl transfer reactions of Et3Si radicals.
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    URL: http://dx.doi.org/10.1002/kin.550130104
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  • 200
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    On the Michaelis-Menten behavior of pyridinium chloro chromate oxidations: Oxidation of dimethyl, dipropyl, and diphenyl sulfide in chlorobenzene-nitrobenzene mixtures (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 85-96 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of oxidation of dimethyl, dipropyl, and diphenyl sulfides by pyridinium chloro chromate in chlorobenzene-nitrobenzene mixtures are reported. The rate data show Michaelis-Menten behavior. The oxidation process is catalyzed by the organic acids like dichloro and trichloro acetic acids. The rate-determining step appears to be a unimolecular decomposition of a complex of the reactants.
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    URL: http://dx.doi.org/10.1002/kin.550130108
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