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  • 1980-1984  (249)
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  • 101
    Electronic Resource
    Electronic Resource
    The reaction of atomic oxygen O(3P) with isobutane (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 585-591 
    Details
    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 isobutane has been studied by using the discharge-flow system described previously [1]. The rate constant was measured from determinations of the isobutane concentration in the presence of an excess of O atoms and is given by k1 = (7.9 ± 1.4) × 107 dm3/mol·s at 307 K. In order to explain the observed reaction products, the mechanism requires that the principal process be the successive abstraction of H atoms from isobutane and from the t-butyl radical to give isobutene. A minor part of the reaction between O(3P) and the t-butyl radical gives the t-butoxy radical, which decomposes to acetone. The branching ratios are .
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140513
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  • 102
    Electronic Resource
    Electronic Resource
    Temperature dependence of the rate constant for the reaction OH + H2S (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 593-598 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate constants for the reaction of OH with H2S have been measured over the temperature range of 239-425 K using the flash photolysis-resonance fluorescence technique. The results showed that the rate constants deviate slightly from Arrhenius behavior but can still be represented adequately by the following Arrhenius equation: \documentclass{article}\pagestyle{empty}\begin{document}$$k_{II} {\rm =}(7.8{\rm} \pm {\rm 2}{\rm .6}){\rm} \times {\rm 10}^{{\rm - 12}} {\rm exp[- (146} \pm {\rm 105)/}T]{\rm cm}^{\rm 3} /{\rm molec} \cdot {\rm s}s$$\end{document} Comparisons with recent literature values are presented.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140514
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  • 103
    Electronic Resource
    Electronic Resource
    Small effect on the rate of complexation of some dialkyl-2,2′-bipyridyl-5,5′-dicarboxylates with the ion of Ni(II) in methanol (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 599-603 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of formation of the 1:1 complexes of some dialkyl-2,2′-bipyridyl-5,5′-dicarboxylates with the ion of Ni(II) have been determined by the stopped-flow spectrophotometric method. Second-order formation rate constants have been correlated with the Taft modification of the Hammett equation. A linear regression has been found (P = 0.95 confidence) with the following characteristics: slope = -0.6 ± 0.1; intercept = 1.32 ± 0.02 (log k0). An inductive effect of the alkyl groups upon the reaction of the complexation is proposed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140515
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  • 104
    Electronic Resource
    Electronic Resource
    Gas-phase thermolysis of sulfur compounds. Part IV. n-propyl allyl sulfide (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 605-612 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of n-propyl allyl sulfide has been studied in static and stirred-flow systems at temperatures between 270 and 400°C. Propene and 2,4,6-triethyl-1,3,5-trithiane were the only reaction products. The order of the reaction was 0.99 ± 0.05 at 377°C. The first-order rate coefficients followed the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$k{\rm (s}^{- 1} {\rm) = 10}^{{\rm 11}{\rm .52} \pm {\rm 0}{\rm .16}} {\rm exp[(- 157} \pm {\rm 2) kJ/mol/R}T]$$\end{document} The rate coefficients and the product distribution remained unchanged when cyclohexene was used as carrier gas. A molecular mechanism involving a six-centered cyclic transition state is proposed to explain the present results. This mechanism is further supported by the pyrolysis of 4-thia-5-dideutero-1-heptene at 377°C, where only 3-deuteropropene is formed. The kinetic deuterium isotope effect had a value of 2.6 ± 0.3 at this temperature. The results are compared with those obtained in the pyrolysis of n-butyl allyl sulfide previously reported.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140602
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  • 105
    Electronic Resource
    Electronic Resource
    High-temperature kinetics of the reactions of SO2 and SO3 with atomic oxygen (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 679-697 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A nozzle-beam-skimmer sampling system is used to measure species concentration profiles for a lean one-dimensional premixed CO—O2—Ar flame, into which small amounts of sulfur dioxide are introduced. The net formation rate for sulfur trioxide is obtained from the flux fraction profile for this species. The kinetic scheme is then utilized, along with the measured temperature profiles, to evaluate the rate coefficients k1 and k2 over the temperature range of 1435-1850 K. The most satisfactory agreement between the measured net formation rate for SO3 and that calculated on the basis of reactions (1) and (2) is obtained with the rate coefficients \documentclass{article}\pagestyle{empty}\begin{document}$$k_1 = 4.4 \times 10^{14} \exp [3163/T]{\rm cm}^{\rm 6} {\rm /mol}^{\rm 2} \cdot {\rm s}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$k_2 = 1.32 \times 10^{12} \exp [- 3070/T]{\rm cm}^{\rm 3} {\rm /mol} \cdot {\rm s}$$\end{document} Reactions (1) and (2) are found to be nearly balanced in a substantial region of the flame. Here the data are more sensitive to the difference in activation energies, as opposed to a particular value for either. Implications of this observation on the uncertainty of the deduced temperature dependence for each reaction are discussed, as are some of the procedures used in the data analysis.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140610
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  • 106
    Electronic Resource
    Electronic Resource
    Erratum (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 733-733 
    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.550140613
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  • 107
    Electronic Resource
    Electronic Resource
    Kinetics of the reactions of CH3 with O(3P) and O2 at 295 K (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 861-874 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of CH3 radicals with O(3P) and O2 have been studied at 295 K in a gas flow reactor sampled by a mass spectrometer. For the reaction between CH3 and O, conditions were such that [O] » [CH3] and the methyl radicals decayed under pseudo-first-order conditions giving a rate coefficient of (1.14 ± 0.29) × 10-10 cm3/s. The reaction between CH3 and O2 was studied in separate experiments in which CH3 decayed under pseudo-first-order conditions. In this case, the rate coefficient obtained increased with increasing concentration of the helium carrier gas. This was varied over the range of 2.5-25 × 1016 cm-3, resulting in values for the apparent two-body rate coefficient ranging from 1 × 10-14 to 5.2 × 10-14 cm3/s. No evidence was found for the production of HCHO by a direct two-body process involving CH3 + O2, and an upper limit of 3 × 10-16 cm3/s was placed on the rate coefficient for this reaction. The experimental results for the apparent two-body rate coefficient exhibit the curvature one would expect for an association reaction in the fall-off region. Calculations used to extrapolate these measurements to the low-pressure limit yield a value for k0 of (3.4 ± 1.1) × 10-31 cm6/s, which is more than a factor of 2 higher than previous estimates.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140806
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  • 108
    Electronic Resource
    Electronic Resource
    Photolysis of carbon tetrachloride in the presence of alkanes (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1033-1045 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of carbon tetrachloride in the presence of a number of alkanes has been investigated in the gas phase. The products obtained from the photolysis experiments were those expected from a chain reaction in which trichloromethyl radicals abstract hydrogen atoms from the alkane. The data have been used to determine Arrhenius parameters for hydrogen abstraction from the series of alkanes CH4, C2H6, C3H8, and i-C4H10 by trichloromethyl radicals, The rate data obtained are used to explain why termination reactions involving alkyl radicals become less significant as the alkane becomes more complex.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140908
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  • 109
    Electronic Resource
    Electronic Resource
    A double-barreled chemical oscillator (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1047-1051 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A chemical system, based on the Briggs-Rauscher reaction, which unperturbed undergoes rhythmic activity followed by a long period of iodine production-consumption prior to return of the rhythmic activity, is described. The effect of the various variables on the system is reported.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140909
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  • 110
    Electronic Resource
    Electronic Resource
    Arrhenius parameters for the decomposition of the t-butoxy radical (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1053-1055 
    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.550140910
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  • 111
    Electronic Resource
    Electronic Resource
    Masthead (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982) 
    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.550141001
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  • 112
    Electronic Resource
    Electronic Resource
    Self- and cross-disproportionation-to-combination rations for cyclopentyl and cyclohexyl radicals and their deuterated analogues (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1059-1070 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydrogen, cycloalkene, and bicycloalkyl were found to be the principal products which account for ≍97% of all products formed in the gas-phase radiolysis of water vapor containing low concentrations of cycloalkanes. From the ratios of cycloalkene-to-bicycloalkyl yields extrapolated to the zero dose, the self- and cross-disproportionation-to-recombination rate constant ratios Δ = kd/kc were determined for the following 12 reactions: Δ(c-C5H9, c-C5H9) = 0.73; Δ(c-C5D9, c-C5D9) = 0.58; Δ(c-C6H11, cC6H11) = 0.59; Δ(c-C6D11, c-C6D11) = 0.46; Δ(c-C5H9, c-C6H11) = 0.28; Δ(c-C5D9, c-C6H11) = 0.28; Δ(c-C5H9, c-C6D11) = 0.24; Δ(c-C5D9, c-C6D11) = 0.24; Δ(c-C6H11, c-C5H9) = 0.33; Δ(c-C6H11, c-C5D9) = 0.25; Δ(c-C6D11, c-C5H9) = 0.35; and Δ(c-C6D11, c-C5D9) = 0.28, where in the case of the cross-disproportionation the symbol Δ(R1,R2) is used to represent kd/kc for the disproportionation in which radical R1 captures a hydrogen (deuterium) atom from radial R2. The geometrical mean rule holds in the cross-combination reactions of cyclopentyl and cyclohexyl radicals. The kinetic isotope effect in the disproportionation reaction was determined as 1.24 ± 0.06.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550141002
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  • 113
    Electronic Resource
    Electronic Resource
    Mechanism of oxidation of diphenyl sulfide by peroxyanions (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1139-1147 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of diphenyl sulfide with the two oxidants peroxydisulfate and peroxydiphosphate are described. With each oxidant, the reaction is first order in the oxidant and zero order in the substrate. The rate of the reaction is also independent of the effect of the substituent. Hydrogen ion catalyzes the reactions. The lack of inhibition of the reaction rate by added acrylamide rules out the possibility of a radical reaction initiated by the homolysis of the peroxyanions. From the effect of [H+] on the oxidation rates, the active species involved in the reactions have been determined. The redox reaction is essentially proceeding via hydrolysis of the protonated peroxy anions in a rate-determining step, followed by a fast step involving the oxidation of diphenyl sulfide to diphenyl sulfoxide. This has been confirmed by estimating the hydrolyzed products in each case and also by the product analyses.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550141007
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  • 114
    Electronic Resource
    Electronic Resource
    A flash photolysis resonance fluorescence investigation of the reaction OH + H2O2 → HO2 + H2O (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1149-1161 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The flash photolysis resonance fluorescence technique has been used to measure the rate constant for the reaction over the temperature range of 250-370 K. The present results are in excellent agreement with three very recent studies, and the combined data set can been used to derive the expression similar to that currently used in atmospheric modeling applications.A summary of our computer simulation of this reaction system is presented. The results of the computations indicate the absence of secondary reaction complications in the present work while revealing significant problems in the earlier (pre-1980) studies of the title reaction.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550141008
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  • 115
    Electronic Resource
    Electronic Resource
    Experimental determination of the equilibrium constant of the reaction CH3 + O2 ⇄ CH3O2 during the gas-phase oxidation of methane (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1231-1241 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For the experimental determination of the equilibrium constant of the reaction CH3 + O2 ⇄ CH3O2 (1), the process of methane oxidation has been studied over the temperature range of 706-786 K. The concentration of CH3O2 has been measured by the radical freezing method, and that of CH3 from the rate of accumulation of ethane, assuming that C2H6 is produced by the reaction CH3 + CH3 → C2H6 (2). The equilibrium constant of reaction (1) has been obtained at four temperatures. For the heat of the reaction the value Δ˚H298 = -32.2 ± 1.5 kcal/mol is recommended.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550141107
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  • 116
    Electronic Resource
    Electronic Resource
    Reactions of isopropylperoxy radicals with NO and NO2 (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1243-1251 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constants for the reactions have been measured directly by flash photolysis and kinetic spectroscopy. At room temperature, k3 = (3.4 ± 0.1) × 109 L/mol·s, independent of pressure in the range of 55-400 torr, and k6 = (2.1 ± 0.2) × 109 L/mol·s.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550141108
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  • 117
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of chlorination of toluene and some substituted toluenes by chloramine-T (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1267-1279 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of chlorination of toluene, o-methyl toluene, p-methyl toluene, m-methyl toluene, and m-chlorotoluene by chloramine-T(CAT) in aqueous acetic acid in the presence of HClO4 have been studied. The reaction is first order with respect to [CAT] as well as [H+]. The order with respect to the substrate is unity in the case of toluene and m-chlorotoluene, fractional in the case of o-methyl toluene and p-methyl toluene, and zero order in the case of m-methyl toluene. Nuclear halogenation has been observed with m-methyl toluene, while nuclear and side-chain halogenation for p-methyl toluene and o-methyl toluene, and sidechain halogenation for toluene and m-chlorotoluene are the pathways. An increase in the proportion of acetic acid accelerates the rate. Added acetate ions inhibit the reaction, and added p-toluene sulfonamide causes a pronounced retardation. A mechanism involving AcO+HCl as the important electrophile is discussed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550141110
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  • 118
    Electronic Resource
    Electronic Resource
    Integrated rate laws for reversible reactions (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1285-1286 
    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.550141112
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  • 119
    Electronic Resource
    Electronic Resource
    Comments on the linear free-energy correlation between O3 and OH addition reactions reported in “rate constants for the gas-phase reactions of O3 with a series of carbonyls at 296 K” (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1281-1283 
    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.550141111
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  • 120
    Electronic Resource
    Electronic Resource
    Studies in nickel(IV) chemistry. Part 6. Kinetics of electron transfer from phenylhydrazine to tris-(dimethylglyoximato) nickelate(IV) in aqueous mediumFor Parts 1-5 see [1-5]. (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1253-1266 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of electron transfer from phenylhydrazine(S) to tris-(dimethylglyoximato) nickelate(IV), Ni(dmg)32- (dmg2- = dimethylglyoximate dianion), have been studied in aqueous medium in the range of 6.21 ≤ pH ≤ 12.2. The kinetics exhibit a pseudo-first-order disappearance of Ni(dmg)32- when excess S is present. The pseudo-first-order rate constants kobs are almost linearly dependent on [S]0 for varying concentrations of the reductant. At constant [S]0, the kobs-pH profile is U shaped. The kobs values register a decrease as the [H+] is increased in the pH range of ∽12.2-9.5, remain almost constant (minimum) in the range of ∽9-8, and then again linearly increase as [H+] is increased in the pH range of ∽7-6.21. Results are interpreted in terms of a probable mechanism involving outer-sphere electron transfer from the phenylhydrazine and phenylhydrazinium cation species to the unprotonated and one-protonated species of the Ni(IV) complex. The reduction rate appears to be dependent on the nature of the species (unprotonated and one-protonated) of the oxidant Ni(IV) complex. The phenylhydrazinium cation reduces the Ni(IV) complex at least one order of magnitude faster than does the neutral reductant species. The major product of the oxidation of phenylhydrazine by the Ni(IV) complex is 4-hydroxyazobenzene with a small amount of phenol.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550141109
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  • 121
    Electronic Resource
    Electronic Resource
    Masthead (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982) 
    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.550141201
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  • 122
    Electronic Resource
    Electronic Resource
    Mechanism of the pyrolysis of C2HCl5, molecular and radical steps (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1287-1304 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An analysis of the thermochemistry of the kinetic parameters of the elementary reactions involved in the pyrolysis of pentachloroethane has resolved several disputed, unclarified, or inconsistent aspects of the reaction mechanism. The resulting mechanisms for the inhibited and uninhibited pyrolysis account for all reported experimental findings. On the basis of this interpretation, first experimentally based values have been derived for the following: DH0(CCl3-CHCl2) = 79.0 ± 1.0 kcal/mol, ΔHf0(CHCl2) = 25.7 ± 1.0 kcal/mol, and E1 = 59.7 ± 1.0 kcal/mol C2HCl5 .
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550141202
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  • 123
    Electronic Resource
    Electronic Resource
    Mechanism of oxidation of triphenylphosphine, triphenylarsine, and triphenylstibine by potassium peroxodisulfate (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1315-1324 
    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 triphenyl derivatives of group V elements Ph3M (M = P, As, Sb) by potassium peroxodisulfate have been investigated spectrophotometrically in 60% acetonitrile-40% water (v/v) mixture. The reaction follows second-order kinetics, first order in each reactant. Changes in the [H+] and ionic strength have negligible effect on the reaction rate. Addition of acrylonitrile fails to inhibit the rate. The results indicate a rate-determining nucleophilic displacement of the Ph3M molecule on the peroxide linkage. The relative rate order has been found to be Ph3P 〉 Ph3Sb 〉 Ph3As. This can be attributed to two conflicting trends.
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    URL: http://dx.doi.org/10.1002/kin.550141204
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    Free-energy correlation for catalysis of outer sphere electron-transfer reactions by noncoordinated pyridine derivatives (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1305-1313 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Recent experimental data concerning the rate constants and their free energy of the outer sphere electron-transfer reactions, as catalyzed by noncoordinated pyridine derivatives in aqueous solution, are examined for possible correlation. For the electron transfer reactions between Vaq2+ or Euaq2+ and the bipyridyl derivatives, such as N,N'-dimethyl-4,4′-bipyridyl (paraquat) or diquat, the data are correlated quite well by the Marcus equation. The electron exchange rate constant, 5 × 107M-1·s-1, for an organic radical ion and its parent molecule obtained from semiquinones or their related compounds can be applied to these pyridine derivatives. However, in some cases such as electron transfer from paraquat or diquat cation radical to Co(en)33+, positive departures from the Marcus model are observed. These positive departures are interpreted in terms of interaction between the molecular orbitals of electron donors and electron acceptors in the transition state.
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    URL: http://dx.doi.org/10.1002/kin.550141203
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  • 125
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    Determination of the gas-phase decomposition rate constants of heptyl-1 and heptyl-2 hydroperoxides C7H15OOH (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1325-1337 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase decomposition of n-heptyl-1 and n-heptyl-2 hydroperoxides C7H15OOH, which split into two radicals C7H15O and OH, has been investigated in the temperature range of 250-360°C. The decomposition has been carried out in a hydrogen-oxygen mixture (the hydroperoxide represents about 50 ppm) so as to avoid secondary reactions between the formed radicals and the reactants. Although the H2-O2 mixture is not spontaneously reactive in our conditions, it operates the transformation, through a fast and well-known process, of the OH radicals into HO2 radicals and then into H2O2. However, C7H15O radicals are also transformed into HO2 radicals and then into H2O2, but through an unknown process. To avoid heterogeneous reactions, vessel and probe are coated by B2O3 and then treated by the slow combustion of hydrogen at 510°C and 250 torr before the experiments are performed. As the reaction scheme is very simple, due to the use of the H2-O2 mixture, the determination of the evolutions of the HO2 concentration (followed by electronic paramagnetic resonance) lead to the determination of the gas-phase decomposition rate constant of hydroperoxides. For the n-heptyl-1 hydroperoxide the rate constant is \documentclass{article}\pagestyle{empty}\begin{document}$$(1.1 \pm 0.25) \times 10^{16} \exp - \left({\frac{{43,500 \pm 1000}}{{RT}}} \right){\rm s}^{{\rm - 1}}$$\end{document} and for the n-heptyl-2 hydroperoxide it is \documentclass{article}\pagestyle{empty}\begin{document}$$(7 \pm 2) \times 10^{15} \exp - \left({\frac{{41,500 \pm 1000}}{{RT}}} \right){\rm s}^{{\rm - 1}}$$\end{document}.
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  • 126
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    The use of transition-state theory to extrapolate rate coefficients for reactions of oh with alkanes (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1339-1362 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is described for extrapolating existing experimental data on the reactions of OH radicals with alkanes to higher temperatures using conventional transition-state theory. Expressions are developed for the estimation of the structural properties of the activated complex necessary for calculating ΔS± and ΔH±. The vibrational frequencies and internal rotations of the activated complex are given by those of the reacting alkane or the analogous alcohol and a set of additional internal modes that is the same for all OH + alkane reactions considered. Differences between primary, secondary, and tertiary hydrogen attack are discussed, and the validity of representing the activated complexes of all OH + alkane reactions by a fixed set of vibrational frequencies and other internal modes is evaluated. Calculations are presented for the reaction of OH with CH4, C2H6, C3H8, n-C4H10, i-C4H10, c-C4H8, c-C5H10, c-C6H12, (CH3)2CHCH(CH3)2, (CH3)3CCH(CH3)2, (CH3)4C, and (CH3)3CC(CH3)3, and the results are compared with experiments.
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  • 127
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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 
    Details
    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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  • 128
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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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  • 129
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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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  • 130
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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 
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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 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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  • 131
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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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    URL: http://dx.doi.org/10.1002/kin.550130405
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  • 132
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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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  • 133
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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 
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    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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  • 134
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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 
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    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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  • 135
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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 
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    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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  • 136
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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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    URL: http://dx.doi.org/10.1002/kin.550130608
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  • 137
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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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    URL: http://dx.doi.org/10.1002/kin.550130704
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  • 138
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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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  • 139
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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 
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    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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    URL: http://dx.doi.org/10.1002/kin.550130909
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  • 140
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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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  • 141
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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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  • 142
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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 
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    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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  • 143
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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 
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    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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  • 145
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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 
    Details
    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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    URL: http://dx.doi.org/10.1002/kin.550130206
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  • 146
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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 
    Details
    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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    URL: http://dx.doi.org/10.1002/kin.550130210
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  • 147
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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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  • 148
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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 
    Details
    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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    URL: http://dx.doi.org/10.1002/kin.550130307
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  • 149
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    Preliminary announcement (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 323-323 
    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.550130312
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  • 150
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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.
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    URL: http://dx.doi.org/10.1002/kin.550130403
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  • 151
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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.
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    URL: http://dx.doi.org/10.1002/kin.550130407
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  • 152
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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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    URL: http://dx.doi.org/10.1002/kin.550130507
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  • 153
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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 
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    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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    URL: http://dx.doi.org/10.1002/kin.550130603
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  • 154
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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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  • 155
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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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  • 156
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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.
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    URL: http://dx.doi.org/10.1002/kin.550130707
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  • 157
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    Erratum (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 693-693 
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    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.550130709
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  • 158
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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 
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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 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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    URL: http://dx.doi.org/10.1002/kin.550130803
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  • 159
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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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  • 160
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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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  • 161
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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 
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    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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  • 162
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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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  • 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.550130201
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  • 164
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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 
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    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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  • 165
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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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  • 166
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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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  • 167
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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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    URL: http://dx.doi.org/10.1002/kin.550130406
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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 
    Details
    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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    URL: http://dx.doi.org/10.1002/kin.550130103
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  • 169
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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 
    Details
    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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    URL: http://dx.doi.org/10.1002/kin.550130107
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  • 170
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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 
    Details
    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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  • 171
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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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  • 172
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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 
    Details
    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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  • 173
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    Editor's note (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 785-786 
    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.550130902
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  • 174
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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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  • 175
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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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  • 176
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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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  • 177
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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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  • 178
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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.
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    URL: http://dx.doi.org/10.1002/kin.550130109
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  • 179
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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}
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    URL: http://dx.doi.org/10.1002/kin.550130208
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  • 180
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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 
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    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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  • 181
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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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  • 182
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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 
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    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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  • 183
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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 
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    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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  • 184
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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 
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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 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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  • 185
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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 
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    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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  • 186
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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 
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    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.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550130708
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  • 187
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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.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130805
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  • 188
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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.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130807
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  • 189
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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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  • 190
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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.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550130104
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  • 191
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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.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130108
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  • 192
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    Peroxy radical reactivities in the cooxidation of ethylbenzene and substituted 3-phenylindans (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 111-118 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constants of peroxy radical recombination in the oxidation of 1-methyl-3-phenylindan, 1,3-dimethyl-3-phenylindan, and 1,1-dimethyl-3-phenylindan were measured using the nonstationary-state technique. A cooxidation method was applied to obtain the reactivities of these compounds with respect to α-phenylethyl peroxy radicals.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130202
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  • 193
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    Use of two-parameter correlations for studying the radical reactivity of aromatic compounds (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 173-186 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two-parameter equation correlations are reported for radical reactions of aromatic compounds. In these correlations polar and resonance substituent constants identical with the substituent constants of aliphatic compounds were used. The equations correlate the rate constants for H abstraction reactions and for the addition of a variety of free radicals to the ortho-, meta-, and para-substituted aromatic compounds. Besides, they correlate parameters of the spectra for substituted aromatic radicals. The correlations show that the effects of para substituents on the reactions studied are nearly entirely resonance effects, whereas for the meta- and ortho-substituted compounds polar (inductive) effects become essential. Application of the two-parameter correlations permits also to determine the structure of transition states (σ or π-complex) in free-radical reactions.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130207
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  • 194
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    Mechanism of the azide-bromine reaction in aqueous medium (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 199-207 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Results on the oxidation of N3- by Br2 in neutral and acid media are presented. The rate of the reaction is found to be proportional to [N3-] and [Br2]. The gaseous product of oxidation is found to be pure nitrogen. The stoichiometry of the reaction is \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Br}_2 + 2{\rm N}_{\rm 3}^ - \to 2{\rm Br}^ - + 3{\rm N}_{\rm 2} {\rm ([N}_{\rm 3}^ -]) 〉 [{\rm Br}_2] $$\end{document} The reaction shows a positive salt effect. It is found that the addition of Br- stabilizes the complex BrN3, which decomposes into Br- and N2: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm Br}_2 + {\rm N}_{\rm 3}^ - \rightleftharpoons {\rm BrN}_{\rm 3} + {\rm Br}^ - } \\ {{\rm BrN}_3 + {\rm N}_{\rm 3}^ - \to {\rm Br}^ - + 3{\rm N}_{\rm 2} } \\ \end{array} $$\end{document} The spectroscopic measurements also support the kinetic observation. The equilibrium constant K, the rate constants and the thermodynamic parameters were calculated. It is observed that H+ ion inhibits the reaction. The mechanism is discussed in terms of the kinetic results.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550130209
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  • 195
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    Very low-pressure pyrolysis (VLPP) of pentynes. I. Kinetics of the retro-ene decomposition of pent-1-yne (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 245-254 
    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 pent-1-yne has been investigated over the temperature range of 923-1154 K using the technique of very low-pressure pyrolysis (VLPP). Under the experimental conditions the reaction proceeds predominantly via a molecular retro-ene pathway to yield allene and ethylene. There was some evidence for the occurrence of the higher energy C3—C4 bond fission pathway at the high end of the temperature range. Interpretation of the data with the aid of RRKM theory and taking into account a decrease in gas-wall collision efficiency with temperature yields the following high-pressure rate constant expression for the retro-ene pathway: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k(\sec ^{ - 1}) = (12.8 \pm 0.4) - (57.0 \pm 2.0)/\theta $$\end{document} at 1100 K where θ = 2.303 RT kcal/mol and the A factor was assigned from the results of shock-tube studies of similar molecules. These rate parameters are independent of the inclusion of the bond fission pathway in the RRKM calculations. The results are compared with previous data on the retro-ene decomposition of alkynes.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550130304
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  • 196
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    Kinetics of competitive pathways in the thermal unimolecular decomposition of hex-1-yne (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 273-282 
    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 hex-1-yne has been investigated over the temperature range of 903-1153 K using the technique of very low-pressure pyrolysis (VLPP). The reaction proceeds via the competitive pathways of C3—C4 fission and molecular retro-ene decomposition, with the latter being the major pathway under the experimental conditions. RRKM calculations, generalized to take into account two competing pathways, show that the experimental unimolecular rate constants are consistent with the high-pressure Arrhenius parameters at 1100 K given by \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k(\sec ^{ - 1}) = (12.7 \pm 0.4) - (56.4 \pm 1.0)/\theta \;\;\;\hbox{for retro-ene} $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k(\sec ^{ - 1}) = (15.9 \pm 0.3) - (70.7 \pm 2.0)/\theta \;\;{\rm for}\;{\rm C} {-} {\rm C}\,{\rm fission} $$\end{document} where θ = 2.303 RT kcal/mol and the A factors were assigned from the results of recent shock-tube studies of hex-1-yne and related alkynes. The results for C—C fission are consistent with previous VLPP and shock-tube determinations of the propargyl resonance energy, and the parameters for the molecular pathway are consistent with systematic trends for the retro-ene decomposition of unsaturated hydrocarbons.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550130306
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  • 197
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    Electronic Resource
    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.550130401
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  • 198
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    A quantitative study of alkyl radical reactions by kinetic spectroscopy. IV. The flash photolysis of azopropanes (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 367-384 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The flash photolysis of azo-n-propane and of azoisopropane has been studied by kinetic spectroscopy. Transient absorption spectra in theregion of 220-260 nm have been assigned to the n-propyl and isopropyl radicals. For the n-propyl radical, ∊max = 744 ± 39 l/mol cm at 245 nm and the rate constants for the mutual reactions were measured to be kc = (1.0 ± 0.1) × 1010 l/mol sec (combination) and kd = (1.9 ± 0.2) × 109 l/mol sec (disproportionation). For the isopropyl radical, ∊max = 1280 ± 110 l/mol cm at 238 nm, with kc = (7.7 ± 1.6) × 109 l/mol sec and kd = (5.0 ± 1.2) × 109 l/mol secThe rate constant for the dissociation of the vibrationally excited triplet state of the azopropanes into radicals was measured from the variation in the quantum yield of radicals with pressure. For azo-n-propane kdT = (6.6 ± 1.3) × 107 sec-1, and for azoisopropane kdT = (1.6 ± 0.4) × 108 sec-1. Collisional deactivation of the vibrationally excited singlet and triplet states was found to occur on every collision for n-pentane; but nitrogen and argon were inefficient with a rate constant of 1.1 × 1010 l/mol sec.Spectra observed in the region of 220-260 and 370-400 nm areattributed to the cis isomers of the parent trans-azopropanes. These are formed, as permanent products, in increasing amounts as the pressure is increased.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550130404
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  • 199
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    The determination of the arrhenius parameters for the reaction Cl + C2F5I → ICl + C2F5 using a competitive method (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 427-432 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions have been studied competitively over the range of 28-182°C by photolysis of mixtures of Cl2 + C2F5I+ CH4. We obtain \documentclass{article}\pagestyle{empty}\begin{document}$$ \log {\rm }k_1 /k_2 = (0.96 \pm 0.06) + (1210 + 440)/\theta $$\end{document} where θ = 2.303RT J/mol. The use of published data on reaction (2) leads to log (k1cm3/mol sec) = (13.96 ± 0.2) - (11,500 ± 2000)/θ.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130409
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  • 200
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    Studies on the effect of the cation nature on the kinetics of the isotopic exchange reaction between chloride ion and O,O-diphenylphosphorochloridothionate in acetonitrile (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 417-425 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants and activation parameters for the isotopic exchange reactions between (PhO)2PSCl and M36Cl (M = Me4N+, Et4N+, n-Bu4N+, Et3HN+, EtH3N+, Li+) in acetonitrile were measured in order to find the effect of the cation nature onthe kinetics of the reaction. The rate constants measured for a range of concentrations of Et3HN36Cl, EtH3N36Cl, and Li36Cl were analyzed using the Acree equation. The equivalent conductance of LiCl in acetonitrile was determined. The nature of the cation has no effect on the mechanism of the reaction. The cation changes only the experimental rate constant proportionally to the dissociation degree of the salt. Smaller values of the rate constant and smaller activation parameters ΔH
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130408
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