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  • 1980-1984  (123)
  • 1981  (123)
  • Physical Chemistry  (123)
  • Nuclear reactions
  • 1
    Electronic Resource
    Electronic Resource
    Kinetics of the bimolecular initiation process in the thermal reactions of ethylene (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 897-911 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The initial rates of formation of the major products in the thermal reactions of ethylene at temperatures in the neighborhood of 750 K have been measured in the presence and absence of the additive butene-1. It has been shown that this ratio of rates is related to the ratio of rate constants for the two initiation processes: The ratio k′1/k1 has been measured over the temperature range of 700-773 K and may be expressed as (R = 1.987 cal/mol deg) log k′1k1(mol/L) = 2.8 - 4400/2.3RT. Assuming a value for k′1 of log k′1 (s-1) = 16 - 71,500/2.3RT, the value of k1 may be expressed as log k1(L/mol) = 13.2 - 67,000/2.3RT. The values for the frequency factor and activation energy for reaction (1) are discussed in relation to the heat of formation of the vinyl radical, and it is concluded that reaction (1) is the main initiation process in the thermal decomposition of ethylene under the present conditions.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130913
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  • 2
    Electronic Resource
    Electronic Resource
    Kinetics of acid catalyzed and Ag(I) catalyzed decomposition of peroxodisulfate in aqueous medium (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 555-564 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of acid catalyzed decomposition of peroxodisulfate, (S2O82-) in aqueous perchlorate medium involves the hydrolysis of the species H2S2O8 and HS2O8- and the homolysis of the species H2S2O8, HS2O8- and S2O82- at the O—O bond. The overall rate law when 1.4M 〉 [HClO4] 〉 0.1M is \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{ - d[{\rm S}_{\rm 2}{\rm O}_8^{2 - }]}}{{dt}}\, = \,k_0 [{\rm S}_{\rm 2}{\rm O}_8^{2 - }]\, + \,k' [{\rm S}_{\rm 2}{\rm O}_8^{2 - }][{\rm H}+]\, + \,k{''}[{\rm S}_{\rm 2}{\rm O}_8^{2 - }][{\rm H}+]^2 $$\end{document}The constants k′ and k″ contain the hydrolysis and homolysis rate constants of HS2O8- and H2S2O8, respectively. With added Ag(I), the acid catalyzed and Ag(I) catalyzed reactions take place independently. Ag(I) catalyzed decomposition appears to involve the species AgS2O8- (aq).
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130605
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  • 3
    Electronic Resource
    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.550130701
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  • 4
    Electronic Resource
    Electronic Resource
    Study of ionic catalytic systems by the electrodialysis method (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 603-613 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A special method of electrodialysis has been developed for investigation of the kinetics and mechanism of polymerization reactions involving ions. The ionic composition of homogeneous systems such as Cp2TiRClAlRCl2, RTiCl3 + AlRCl2, Ti(OR)4 + AlR3, and (RLi)n has been studied. The composition of catalytically active ions has been determined. Using the regularities of “open” systems, the methods of determining the carbocation reactivity under electrodialysis conditions havebeen worked out. The impulse electrodialysis method has been suggested for studying ionic polymerization kinetics and evaluating the rate constants ofion reactions with the monomer and gegenion.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130702
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  • 5
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 9 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130309
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  • 6
    Electronic Resource
    Electronic Resource
    The hydrolysis of phosphoranes in aqueous dioxanePresented at the International Conference on Reactions in Solution, Canterbury, England, July 8-13, 1979 (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 411-416 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The entropy of activation for the hydrolysis of pentaphenoxyphosphorane in 25% aqueous dioxane is -188 J/mol deg. The enthalpy of activation is 22.5 kJ/mol, which is small for the relatively slow reaction. This suggests that the reaction is a multistep process having a preliminary equilibrium with a negative heat of reaction. This conclusion is supported by the results obtained for the hydrolysis of C6H5[OCH(CF3)2]2. A kinetic isotope effect kH2O/kD2O of 3.46 was found for the latter reaction. Orders in water were obtained, and a mechanism of hydrolysis is proposed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130407
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  • 7
    Electronic Resource
    Electronic Resource
    Enhancement of the bimolecular reaction of hydrogen iodide by vibrational excitation (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1085-1099 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bimolecular reaction of HI in CO2, which was excited vibrationally by irradiation of a continuous-wave CO2 laser light, was investigated in the temperature range of 721-980 K. An enhancement of the reaction rate by a factor of about 2.5 was observed in the 1:1 HI—CO2 mixture in comparison with the rate in pure HI when both sample gases were irradiated by a CO2 laser (50 W) at 1 torr. However, in the HI-SF6 mixtures the decomposition rate of HI was not accelerated by irradiation of the CO2 laser. Thus the enhancement is attributed to vibrational excitation of HI through collisional energy transfers from laser-excited CO2 (00°1). At lower total pressures or at lower partial pressures of HI in HI-CO2 mixtures the enhancement was more significant because of inefficient vibrational deactivation of excited HI. A model calculation gave the result in agreement with the experimental one if the effective activation energy is assumed as Ea† = Ea - αEvib, where Ea is the activation energy for the thermal reaction, Evib is the vibrational energy of two colliding HI molecules, and α is estimated to be about 0.7. This means that a part of the vibrational energy of reacting HI is employed to reduce the activation energy for the translational or rotational degree of freedom.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550131008
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  • 8
    Electronic Resource
    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.550131101
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  • 9
    Electronic Resource
    Electronic Resource
    On the photodissociation of nitromethane at 266 nm (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1125-1131 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In a crossed laser-molecular beam study of nitromethane it was found that the excitation of nitromethane at 266 nm did not yield dissociation products under collision-free conditions. When a small cluster of nitromethane was excited at the same frequency, the product was seen only at energies and masses consistent with the rupture of the van der Waals bond by vibrational predissociation of the excited state.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550131103
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  • 10
    Electronic Resource
    Electronic Resource
    High-energy kinetic study of chemically activated 1,1-dichlorocyclopropane (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1107-1123 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,1-Dichlorocyclopropane has been produced by addition of CH2(1A1) to 1,1-dichloroethylene. CH2(1A1) was generated by the photolysis of ketene at 277-334 nm. The 1,1-dichlorocyclopropane was formed in a chemically activated state, had an energy content between 386 and 400 kJ/mol, and reacted in two parallel channels to 2,3-dichloropropene and 1,1-dichloropropene. 1,1-Dichloropropene was also formed directly by insertion of CH2(1A1) into the CH bond of 1,1-dichloroethylene. As secondary reactions elimination of HCl from chemically activated 2,3-dichloropropene occurred with 3-chloropropyne and chloroallene as products. In some of the experiments perfluoropropane was added as an inert gas. The apparent rate constants for the isomerization and elimination reactions are reported. The results of RRKM calculations including distribution functions for the activated 1,1-dichlorocyclopropane and a step-ladder model for the deactivation verify the proposed reaction scheme.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550131102
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  • 11
    Electronic Resource
    Electronic Resource
    Rate constants for the gas-phase reactions of O3 with a series of carbonyls at 296 K (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1133-1142 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the gas-phase reactions of O3 with the carbonyls acrolein, crotonaldehyde, methacrolein, methylvinylketone, 3-penten-2-one, 2-cyclohexen-1-one, acetaldehyde, and methylglyoxal have been determined at 296 ± 2 K. The rate constants ranged from 〈6 × 10-21 cm3 molecule-1 s-1 for acetaldehyde to 2.13 × 10-17 cm3 molecule-1 s-1 for 3-penten-2-one. The substituent effects of —CHO and CH3CO— groups on the rate constants are assessed and discussed, as are implications for the atmospheric chemistry of the natural hydrocarbon isoprene.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550131104
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  • 12
    Electronic Resource
    Electronic Resource
    Kinetics of free-radical decay reactions in polymeric solids (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1143-1150 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetic equations for the decay of the free radicals in polymeric solids are given for the following assumptions on which they are based: (1) two simultaneous first-order but physically separated decay reactions; (2) two simultaneous noninteracting second-order decay reactions; (3) combined simultaneous but intermingled first- and second-order decay reactions; (4) the same but for independent, i.e., not intermingled, first- and second-order decay reactions; (5) a second-order decay reaction in the presence of some free radicals that do not decay; and (6) a first-order decay reaction in the presence of some free radicals that do not decay. In all of the above physical systems the total concentration only can be measured. Hence the above kinetic equations refer to the change of the total concentration with time. It is found that the data for the decay of the free radicals in irradiated isotactic polypropylene and 61% styrene-39% butadiene block copolymer agree best with the equations for the second-order decay in the presence of a fraction of nondecaying free radicals.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550131105
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  • 13
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130107
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  • 14
    Electronic Resource
    Electronic Resource
    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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  • 15
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130205
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  • 16
    Electronic Resource
    Electronic Resource
    Kinetic studies of free radical reactions by mass spectrometry. II. The reactions of SO + ClO, SO + OClO and SO + BrO (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 187-197 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates of several novel elementary reactions involving ClO, BrO and SO free radicals in their ground states were studied in a discharge-flow system at 295 K, using mass spectrometry. The rate constant k2 was determined from the decay of SO radicals in the presence of excess ClO radicals: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm SO} + {\rm ClO} \to {\rm SO}_{\rm 2} + {\rm Cl;}} & {k_{\rm 2} = (2.3{\rm } \pm {\rm 0}{\rm .6}) \times 10^{ - 11} {\rm cm}^3 \sec ^{ - 1} } \\ \end{array}$$ \end{document}The SO + OClO overall reaction has a complex mechanism, with the primary step having a rate constant k5 equal to (1.9 ± 0.7) × 10-12 cm3 sec-1: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm SO} + {\rm OClO } \to {\rm SO}_{\rm 2} + {\rm ClO} $$\end{document}A lower limit for the rate constant of the rapid reaction of SO radicals with BrO radicals was determined: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm SO} + {\rm BrO} \to {\rm SO}_{\rm 2} + {\rm Br;}} & {k_{17} } \\ \end{array} \ge 4 \times 10^{ - 11} {\rm cm}^3 \sec ^{ - 1} $$\end{document}
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550130208
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  • 17
    Electronic Resource
    Electronic Resource
    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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  • 18
    Electronic Resource
    Electronic Resource
    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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  • 19
    Electronic Resource
    Electronic Resource
    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.
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    URL: http://dx.doi.org/10.1002/kin.550130306
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  • 20
    Electronic Resource
    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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  • 21
    Electronic Resource
    Electronic Resource
    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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    Electronic Resource
    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.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550130406
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    Electronic Resource
    Electronic Resource
    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.
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    URL: http://dx.doi.org/10.1002/kin.550130409
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  • 24
    Electronic Resource
    Electronic Resource
    Very-low-pressure pyrolysis of ethylbenzene, isopropylbenzene, and tert-butylbenzene (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 445-462 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal unimolecular decomposition of ethylbenzene, isopropylbenzene, and tert-butylbenzene was studied using the very-low-pressure pyrolysis (VLPP) technique. Each reactant decomposed by way of β C—C bond homolysis, producing methyl radicals and benzyl or benzylic-type radicals. RRKM calculations show that the observed rate constants, when combined with thermochemical estimates, are consistent with the following high-pressure rate expressions: \documentclass{article}\pagestyle{empty}\begin{document}$ \log k(\sec ^{ - 1}) = 15.3 - (72.7/{\rm \theta)} $\end{document} for ethylbenzene between 1053 and 1234 K, \documentclass{article}\pagestyle{empty}\begin{document}$ \log k(\sec ^{ - 1}) = 15.8 - (71.3/{\rm \theta)} $\end{document} for isopropylbenzene between 971 and 1151 K, and \documentclass{article}\pagestyle{empty}\begin{document}$ \log k(\sec ^{ - 1}) = 15.9 - (69.1/{\rm \theta)} $\end{document} for tert-butylbenzene between 929 and 1157 K, where θ (kcal/mol) = 2.303RT. Resulting activation energies combined with heat capacity and heat of formation data led to the following dissociation enthalpies and enthalpies of formation at 298 K: DH° (øCH(CH3)—CH3) = 73.8 kcal/mol, ΔHf° (øÇCH(CH3)) = 39.6 kcal/mol, DH° (øC(CH3)2—CH3) = 72.9 kcal/mol, and ΔHf° (øÇ(CH3)2) = 32.4 kcal/mol. Derived high-pressure rate constants are in good accord with results of lower temperature toluene- and aniline-carrier experiments.
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    URL: http://dx.doi.org/10.1002/kin.550130503
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  • 25
    Electronic Resource
    Electronic Resource
    Consistency of theory and experiment in the ethane-methyl radical system (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 481-495 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of ethane has been reinvestigated using the single pulse, reflected shock technique. Reflected shock temperatures were corrected for boundary layer-induced nonidealities using the thermal decomposition of cyclohexene as a kinetic standard. The rate constant for the reaction was calculated from the rate of formation of methane under conditions of very low extent of reaction, over a temperature range of 1000-1241 K. Ethane compositions of 1% and 3% in argon at total reaction pressures of 3 and 9 atm were used, and a small pressure dependence of k1 was observed.An RRKM model is described which gives excellent agreement with this and other recent dissociation and recombination rate constant data in light of a recent revision to the thermochemistry of the methyl radical. In the range of 1000-1300 K an RRKM extrapolated k1∞ is given by the expression, log k1∞ = 17.2 - 91,000/2.3RT, while at 298 K the calculation gives log k-1∞ (l/mol sec) = 10.44, where k-1∞ is calculated from k1∞ and the equilibrium constant.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550130506
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  • 26
    Electronic Resource
    Electronic Resource
    Chain reactions in stirred-flow reactors-a tool for exploring initiation and termination steps independently (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1297-1301 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that chain reactions may be studied in stirred-flow reactors under conditions in which the escape of radicals from the reactor competes significantly with the chemical termination reaction. The appropriate rate law permits the independent evaluation of the rate constants of the initiation and termination steps. Such information is of special interest in the study of surface effects on chain reactions.
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    URL: http://dx.doi.org/10.1002/kin.550131209
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    Kinetic investigation of the bromate-ascorbic acid-malonic acid system (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1277-1288 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: According to our experiments the bromide ion concentration exhibits in the bromate-ascorbic acid-malonic acid-perchloric acid system three extrema as a function of time. To describe this peculiar phenomenon, the kinetics of four component reactions have been studied separately. The following rate equations were obtained:Bromate-ascorbic acid reaction: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} { - d[{\rm BrO}_3^ -]/dt = k_1 [{\rm BrO}_3][{\rm H}_2 {\rm A],}} & {k_1 = 8.3 \times 10^{ - 3} M^{ - 1} \cdot {\rm s}^{ - {\rm 1}} } \\ \end{array} $$\end{document}Bromate-bromide ion reaction: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} { - d[{\rm BrO}_3^ -]/dt = k_2 [{\rm BrO}_3][{\rm Br}^ -][{\rm H}^ +]^2,} & {k_2 = 3.6M^{ - 3} \cdot {\rm s}^{ - 1} } \\ \end{array} $$\end{document}Bromide-ascorbic acid reaction: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} { - d[{\rm Br}_{\rm 2}]/dt = k_3 [{\rm Br}_2][{\rm H}_2 {\rm A],}} & {k_3 \ge 1.7 \times 10^{ - 3} \cdot {\rm s}^{ - 1} } \\ \end{array} $$\end{document}Bromine-malonic acid reaction: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} { - d[{\rm Br}_{\rm 2}]/dt = k_4 k_4 [{\rm Br}_2][{\rm H}_2 {\rm M}]/(k_4 + k_5 [{\rm Br}_2]),} & {k_4 = 6 \times 10^{ - 3} {\rm s}^{ - 1} } \\ \end{array}, \quad {\rm }k_{ - 4} \ge 1.7 \times 10^{ - 3} \cdot {\rm s}^{ - 1} \quad {\rm }k_5 \ge 1 \times 10^7 M^{ - 1} \cdot {\rm s}^{ - 1} $$\end{document} k4 = 6 × 10-3 s-1, k-4 ≥ 1.7 × 103 s-1, k5 ≥ 1 × 107M-1 · s-1Taking into account the stoichiometry of the component reactions and using these rate equations, the concentration versus time curves of the composite system were calculated. Although the agreement is not as good as in the case of the component reactions, it is remarkable that this kinetic structure exhibits the three extrema found.
    Additional Material: 5 Ill.
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    Erratum (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1303-1303 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550131210
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    Electronic Resource
    Infrared photochemistry of bis(trifluoromethyl) peroxide (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 627-638 
    Details
    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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  • 30
    Electronic Resource
    Electronic Resource
    The rate of reaction of methyl radicals with ozone (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 667-675 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absolute rate constant for the reaction of methyl radicals with ozone has been measured as a function of temperature. Small concentrations of CH3 were generated by flash photolyzing CH3NO2 at 193 nm with an ArF laser. A photoionization mass spectrometer was used to follow the rate of decay of CH3 at various ozone concentrations. The resulting rate constants could be fit by the expressions \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = (5.4 \pm 1.5) \times 10^{ - 12} \exp [(- 216 \pm 80)/T]{\rm cm}^3 /{\rm molec}\,{\rm s} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = (2.6 \pm 0.7) \times 10^{ - 12} {\rm (T/300)}^{{\rm 0}{\rm .71} \pm {\rm 0}{\rm .34}} {\rm cm}^3 /{\rm molec}\,{\rm s} $$\end{document} over the temperature range of 243-384 K. These rate constants can be modeled by simple transition state theory using reasonable parameters for the activated complex. Use of this rate constant shows that less than 1% of the methyl radicals formed in the stratosphere react with ozone.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550130707
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    Electronic Resource
    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.550130801
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  • 32
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    Electronic Resource
    The √t law in solid-phase reactions. Analysis of the hypothesis on rate constant distribution (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 707-728 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction C2H5 + O2 → C2H5O2 in glassy methanol-d4 and the H-atom abstraction by CH3, C2H5, and n-C4H9 radicals in C2H5OH + C2D5OH and CD3CH2OH + C2D5OH glassy mixtures have been studied by electron spin resonance. The analysis of the dependence of the reaction rates on the concentration of O2 (oxidation) and C2H5OH, CD3CH2OH (H-atom abstraction) has shown that the √t law is not conditioned by the existence of regions characterized by different rate constants.
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    URL: http://dx.doi.org/10.1002/kin.550130803
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    Electronic Resource
    Reaction of hydrogen atoms with diethyldisulfide and ethylmethyldisulfide (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 799-815 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: H atoms react with C2H5SSC2H5 to give C2H5SH as the sole retrievable product with φ = 2.32 at 25°C and 2.84 at 145°C. The primary reaction is postulated to be H + C2H5SSC2H5 ← C2H5SH + C2H5S with k1 = (4.73 ± 0.64) × 1013 exp [-(1710 ± 69)/RT] cm3/mol·s relative to the rate constant of the H + C2H4 ← C2H5 reaction. The high value of the entropy of activation suggests the presence of partial hydrogen bonding in diethyldisulfide which is broken in the transition state.Ethylmethyldisulfide reacts similarly: H + C2H5SSCH3 ← C2H5SH + CH3S or CH3SH + C2H5S. The thiyl radicals propagate a chain of radical exchange reactions forming the symmetrical disulfides with exposure-time-dependent quantum yields. The overall kinetics conform to a 16-step mechanism from which the rate constants of the elementary reactions could be established by computer modeling. Thiyl radicals react considerably more slowly with disulfides than H atoms.
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    URL: http://dx.doi.org/10.1002/kin.550130905
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    Electronic Resource
    Reactions of the fluorobromocarbene radical studied by laser-induced fluorescence (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 873-881 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: CFBr radicals produced by the reaction of atomic oxygen with F2CCFBr were monitored in a discharge flow system by fluorescence excited at 424 nm. The rate coefficients for reactions of the CFBr radicals were measured between 298 and 358 K, and the following values were obtained in units of cm3/molec·s: O2 〈 2 × 10-16 at 353 K; NO 〈 10-14 at 298 K; F2CCFBr 〈 10-15 at 298 K; Cl2 (1.9 ± 0.6) × 10-12 exp(-762 ± 92/T) Br2 (1.4 ± 0.3) × 10-12 exp(-533 ± 62/T).
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    URL: http://dx.doi.org/10.1002/kin.550130911
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  • 35
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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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    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 
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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 and mechanism of the free-radical chain dechlorination of C2Cl6, C2Cl5H, and sym-C2Cl4H2 in Et3SiH wereinvestigated over a wide temperature range. The propagation step of the dechlorination of chloroethanes (C2Clx H6-x) proceeds by the following reactions: Analysis of the temperature dependence of product formation gave the Arrhenius expressions for k4/k3 which in turn were utilized for the estimation of the absolute Arrhenius parameters for hydrogen abstraction from Et3SiH. Our results show that the values of Eabs are lower in Et3SiH than in c-C6H12 by about 2-3 kcal/mol, while the A factors are almost equal. In competitive studies k2 was determined versus Br abstraction from n-C5H11Br. The relative Arrhenius parameters determined by this method show that variations in both A factors and activationenergies are responsible for the reactivity trends observed in the Cl transfer reactions of Et3Si radicals.
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    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 
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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 oxidation of dimethyl, dipropyl, and diphenyl sulfides by pyridinium chloro chromate in chlorobenzene-nitrobenzene mixtures are reported. The rate data show Michaelis-Menten behavior. The oxidation process is catalyzed by the organic acids like dichloro and trichloro acetic acids. The rate-determining step appears to be a unimolecular decomposition of a complex of the reactants.
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    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.550130201
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    Electronic Resource
    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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    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 
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    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.
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    URL: http://dx.doi.org/10.1002/kin.550130207
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  • 41
    Electronic Resource
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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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  • 42
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    Temperature-dependent a factor in thermal unimolecular reactions II. Exponential dependence (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 283-293 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is assumed that A∞ in the limiting high-pressure unimolecular rate constant expression k∞ = A∞ exp(-Ea∞/kT) is given by A∞ = A″∞eBkT. The test case is the decomposition butane → 2 ethyl, where a negative B reproduces the temperature dependence of A∞ about as well as the previously considered power law A∞ = A′∞(kT)n. It is shown that the term eBkT modifies significantly the high-temperature falloff of the general-pressure rate constant kuni and its various derivatives, and admits of a fairly simple interpretation in terms of Benson's restricted rotor theory. On physical grounds, the exponential law appears more reasonable than the power law.
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    URL: http://dx.doi.org/10.1002/kin.550130307
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    Electronic Resource
    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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    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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  • 45
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    Electronic Resource
    The correlation of rate coefficients for H-atom abstraction by HO radicals with C—H bond dissociation enthalpies (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 651-665 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For H-atom abstraction reactions by HO radicals it has been shown that If Di is taken as the C—H bond dissociation enthalpy at 298 K, then a = 0.323 and D0is obtained from the empirical formula \documentclass{article}\pagestyle{empty}\begin{document}$$ D_0 ^{ - 1} = 1.062 \times 10^{ - 2} + 3.52 \times 10^{ - 6} T $$\end{document} where D0 is in kcal/mol and T is in K. Thisrelationship is valid for T between 200 and 400 K. Finally empiricalrelationships are given to help estimate Di.
    Additional Material: 7 Ill.
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  • 46
    Electronic Resource
    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.550131001
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  • 47
    Electronic Resource
    Electronic Resource
    Micellar catalyzed enolization of acetone (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 695-705 
    Details
    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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  • 48
    Electronic Resource
    Electronic Resource
    Evidence for chamber-dependent radical sources: Impact on kinetic computer models for air pollution (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 735-740 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of NOx-air irradiations, with trace amounts of propane and propene present to monitor OH radical concentrations, have been carried out in a 5800-L evacuable environmental chamber to investigate radical levels and sources during such irradiations. The data obtained show conclusively that unknown radical sources are present, and that photolysis of initial nitrous acid can be, at best, only a minor source of radicals after ∼30-60 min of irradiation.
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  • 49
    Electronic Resource
    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.550130901
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  • 50
    Electronic Resource
    Electronic Resource
    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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  • 51
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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
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  • 52
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    Electronic Resource
    The thermal decomposition of fluorinated esters (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 463-471 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of thermal decomposition of ethyl, isopropyl, and t-butyl trifluoroacetates have been studied in the gas phase. In each case initial decomposition follows the normal ester route to give an olefin and trifluoroacetic acid, and elimination of hydrogen fluoride does not occur. However, trifluoroacetic acid is thermally unstable at ethyl and isopropyl ester decomposition temperatures, and further products result, including those from the difluorocarbene produced by decomposing trifluoroacetic acid. Placing a CF3 group at an ester's γ carbon increases the polarity of its transition state and decreases its thermal stability. The activation energies of the ethyl and isopropyl esters are lowered by 3.8 and 4.7 kcal/mol compared to the corresponding acetates, and the primary decomposition kinetics, which are homogeneous and of the first order, are expressed by α-Methylation enhances the reactivity of the trifluoroacetates, and the t-butyl ester, the transition state for which is sufficiently polar for heterogeneous decomposition to occur, shows signs of thermal instability at room temperature. The equilibrium was also investigated and gave ΔH° = +13,580 cal/mol and ΔS° = +31.07 gibbs/mol in the forward direction. The results obtained extend and support the known structure-rate correlations in the gas-phase elimination of esters.
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  • 53
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    Electronic Resource
    Cl-atom transfer from CFCl3 to the c-C6H11 radical. An indirect estimation of the CFCl2—Cl bond dissociation energy (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 473-480 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Cl-transfer reaction between CFCl3 and c-C6H11 radicals (R) was studied in liquid cyclohexane (RH). The Arrhenius parameters for Cl abstraction were determined in the RH-CFCl3 system versus the termination reaction between cyclohexyl radicals and competitively versus addition to C2Cl4 in the RH-CFCl3-C2Cl4 system. The two sets of results are in very good agreement and give the following Arrhenius expression for the reaction R + CFCL3 → RCl + CFCl2 (2): \documentclass{article}\pagestyle{empty}\begin{document}$$ \log {\rm }k_2 (1/{\rm mol\, sec}) = 8.95 - 7.79/\theta $$\end{document} where θ = 2.303RT in kcal/mol. Comparison with Cl-transfer data of other chloromethanes and chloroethanes shows that an increase in the C—Cl bond dissociation energy is the main cause of the reduced reactivity of CFCl3. Based on a previously developed correlation, D(CFCl2 — Cl) is estimated to be equal to 74.4 kcal/mol.
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  • 54
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    Electronic Resource
    Kinetics and dynamics of elementary gas reactions by Ian W. M. Smith, Butterworths, Wobrun, Ma, 1980. price: $72.95 (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 515-515 
    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.550130509
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  • 55
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    Electronic Resource
    The kinetics of radiation induced hydrogen abstraction by CCl3 radicals in the liquid phase: Cyclanes (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 517-526 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of gamma-radiation induced free radicals reactions in carbon tetrachloride solutions of cyclohexane, cyclooctane and cyclododecane were studied in the range of 27-190°C. The activation energies found were in the order c—C6H12 〉 c—C12H24 〉 c—C8H16, which was explained as due to their ring strain which has the same order. The following log k1 was obtained using the known Arrhenius parameters for CCl3 radical recombination:
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  • 56
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    Electronic Resource
    Photolysis of ethyl-iodide in lithium chloride glassy aqueous solutions with light, λ = 254 nm at 77 K (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 543-554 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of C2H5I in a glassy salt matrix (5M, 7.5M, 10M) of aqueous LiCl at 77 K with light of λ = 254 nm has been conducted, product analysis being by ESR and UV spectroscopy. The electrolytic medium causes the ionization of product HI, and I- concentrations can be continuously determined. During photolysis [I-] is less than the amount of C2H5I decomposed. But after photolysis thaw-freeze cycling is accompanied by progressive growth in [I-] until the yield matches the C2H5I loss, the quantum yields being 0.26, 0.20, and 0.17 for the three LiCl solutions, respectively. The quantum yield of unionized HI is unchanged, however, at around 0.36, the overall change being due to a fall in the extent to which the HI is ionized in the direct photolysis (ø = 0.22, 0.16, and 0.11). It is proposed that this is a consequence of the density increase of matrix packing as the LiCl concentration is increased so that fewer HI are in contact with the aqueous medium and cage recombination is favored.The results establish that the primary reaction is essentially exclusive: and that substantial aggregates of C2H5I exist within which HI are caged and cannot be ionized. The direct reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 2}{\rm H}_{\rm 5}{\rm I}+ h\nu \to {\rm C}_{\rm 2}{\rm H}_5^. + {\rm I}^. $$\end{document} occurs only to a trivial extent, ø; = 10-4, C2H5 arising virtually totally via \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 2}{\rm H}_{\rm 4}+ {\rm H}^. \to {\rm C}_{\rm 2}{\rm H}_5^. $$\end{document}
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    URL: http://dx.doi.org/10.1002/kin.550130604
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  • 57
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    Electronic Resource
    Steric factors in the kinetically controlled direction of elimination of secondary and tertiary esters in the gas phase. The pyrolysis of 4,4-dimethylpent-2-yl acetate (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 577-589 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis kinetics of 4,4-dimethylpent-2-yl acetate, in a static system and in a vessel seasoned with allyl bromide, have been studied in the temperature range of 300-350°C and the pressure range of 48-211 torr. The olefin products were 4,4-dimethylpent-1-ene, cis-4,4-dimethylpent-2-ene, and trans-4,4-dimethylpent-2-ene. The rate coefficient for the homogeneous unimolecular elimination of this ester is given by the following Arrhenius equation: log k(sec-1) = (12.87 ± 0.31) - (181.2 ± 3.4)kJ/mol/2.303RT. The direction of elimination of this acetate has been found to proceed to the formation of the corresponding olefin by kinetic control. The present data, together with other pyrolysis work subject to kinetic control, imply that the direction of elimination of bulky alkyl esters is determined by steric hindrance in the eclipsed cis conformation. However, further analyses reveal that if a series of esters are compared, in the case of a gradual increase of alkyl branching when adjacent to a hydrogen atom (alkyl-H interactions), the rate was determined by steric acceleration, owing to the crowding effect at the highly substituted carbon atom. Otherwise if this gradual alkyl increase in size happened to be adjacent to another alkyl substituent (alkyl-alkyl interactions), the rate was affected by steric hindrance of the eclipsed cis conformation.
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  • 58
    Electronic Resource
    Electronic Resource
    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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  • 59
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    Electronic Resource
    The kinetics and the mechanism of the thermal decomposition of bis(trifluoromethyl) trioxide. The influence of carbonmonoxide on its decomposition (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 639-649 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the thermal decomposition of CF3O3CF3 has been investigated in the pressure range of 15-599 torr at temperatures between 59.8 and 90.3°C and also in the presence of CO between 42 and 7°C. The reaction is homogeneous. In the absence of CO the only reaction products are CF3O2CF3 and O2. The rate of reaction is strictly proportional to the trioxide pressure, and is not affected by the total pressure, the presence of inert gases, and oxygen. \documentclass{article}\pagestyle{empty}\begin{document}$$ -\frac{{d[{\rm CF}_{\rm 3} {\rm O}_{\rm 3} {\rm CF}_{\rm 3}]}}{{dt}} = 2\frac{{dp}}{{dt}} = k[{\rm CF}_{\rm 3} {\rm O}_{\rm 3}{\rm CF}_{\rm 3}] $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k = 2.25 \pm 0.18 \times 10^{15} \exp (- 30,530 \pm 130\,{\rm cal}/RT)s^{ - 1} $$\end{document}The following mechanism explains the experimental results: In the presence of CO there appear CO2, (CF3OCO)2, and CF3O2C(O)OCF3 as products. With increasing temperature the amount of peroxicarbonate decreases, while the amounts of oxalate and CO2 increase. The rate of decomposition of the trioxide above a limiting pressure of about 10 torr CO is strictly first order and independent of CO pressure, total pressure, and the pressure of the products. \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d[{\rm CF}_{\rm 3} {\rm O}_{\rm 3} {\rm CF}_3]}}{{dt}} = k*[{\rm CF}_{\rm 3} {\rm O}_{\rm 3} {\rm CF}_{\rm 3}] $$\end{document} The addition of larger amounts of O2 to the CO containing system chaqnges the course of the reaction.
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  • 60
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    Electronic Resource
    The temperature coefficient of the rates in the system Cl + CH4 ⇆ CH3 + HCl, thermochemistry of the methyl radical (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 677-691 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bimolecular rate constant for the title reaction has been measured by very-low-pressure reactor techniques at 233 〈 T K 〈 338. The equilibrium constant has also been measured between 253 and 338 K. Our rate constants are in excellent agreement with recent measurements using very different techniques and reaction conditions, and the general agreement probably makes this one of the most accurately measured rateconstants. Transition state models of the reaction rule out a bent TS in favor of a TS with colinear Cl···H···C bonds. The curvature at higher temperatures (〉350 K) is quantitatively accounted for by transition state theory analysis. Tunneling is shown not to play a role. The measured values of K1 allow an experimental value of S° (CH3) to be fixed to only ±2.4 e.u. However, using known values of S° for all species gives ΔH°f298(CH3.) = 35.1 plusmn; 0.1 kcal/mol in excellent agreement with other measured values.
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  • 61
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    The thermal decomposition of 4-methyl-3,6-dihydro-2H-pyran (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 729-733 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of the title compound has been studied in the gas phase in the temperature range of 584-634 K. The decomposition was found to be a first-order homogeneous process yielding 2-methylbuta-1,3-diene and formaldehyde. The rate constants obtained at 11 temperatures within the quoted range fitted the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}k/({\rm s}^{ - 1}) = 14.619 \pm 0.030 - (209.48 \pm 0.35)\,{\rm kJ}\,{\rm mol}^{ - 1} /RT\,\ln \,10 $$\end{document} The decomposition is probably unimolecular and concerted.
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  • 62
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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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  • 63
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    Kinetics and mechanism of the thermal decomposition of cyclopentyl cyanide (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 755-770 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of cyclopentyl cyanide has been investigated in the temperature range of 905-1143 K using both conventional stirred-flow reactor and very low-pressure pyrolysis (VLPP) techniques. The results from both techniques are consistent. The main primary processes are HCN elimination to form cyclopentene: and ring fragmentation to form vinyl cyanide plus propylene and ethylene plus cyanopropenes: Under the experimental conditions cyclopentene undergoes further decomposition to cyclopentadiene plus hydrogen. There is evidence for conversion of some of the reactant to a solid residue, presumably polymer. From the stirred-flow reactor results the following Arrhenius expressions were obtained: log k1(s-1) = (12.8 ± 0.3) - (65.6 ± 1.3)/θ and log k2(s-1) = (16.0 ± 0.3) - (80.0 ± 1.1)/θ, where θ = 2.303RT kcal/mol. Application of RRKM theory shows that the VLPP experimental rate constants are consistent with high-pressure Arrhenius parameters given by log k1(s-1) = (12.8 ± 0.3) - (67.8 ± 2.5)/θ for HCN elimination, and log k4(s-1) = (16.3 ± 0.3) - (80.1 ± 2.0)/θ for the sum of the ring fragmentation pathways. The rate parameters for HCN elimination are in good agreement with previous VLPP studies of alkyl cyanides and with theoretical predictions. The difference in activation energies for the ring opening of cyclopentane and cyclopentyl cyanide is reasonably close to the established value for the cyano stabilization energy. This supports the assumption of a biradical mechanism.
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  • 64
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    Analytical solution of vibrational-rotational energy transfer in the dissociation and relaxation of N2, Br2, and CO at high temperature (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 789-798 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An approximate analytical solution of relaxation in a low-pressure system with exponential transition probabilities is given for vibrational-rotational energy transfer in the dissociation of diatomics. The main assumption is that the rotational degrees of freedom are in thermal equilibrium at all times, and that the barrier to dissociation in the vibrational-rotational plane is linear and asymmetric. The theory is applied to high-temperature dissociations of N2, Br2, and CO in excess argon, with satisfactory agreement with available experimental data.
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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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    Minor products and initiation rate in the chain pyrolysis of propaneThis paper summarizes a part of the dissertation submitted by C. Juste for the degree of Docteur-Ingénieur, Nancy, France, 1980. (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 855-864 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: With a continuous jet-stirred tank reactor operating at small space time (0.05-1.2 s) the kinetics of the formation of six minor products (ethane, isobutane, butene-1, 2,3-dimethyl-butane, 4-methylpentene-1, and 1,5-hexadiene) are studied during the pyrolysis of propane, at small extents of reaction and over the temperature range of 600-780°C. The experimental results are in agreement with the free radical mechanism proposed by Jezequel, Baronnet, and Niclause for this reaction. They show that the two most important termination processes are The measured rates of formation of the minor products are consistent with the quasi-identical values estimated by Jezequel and co-workers (between 475 and 505°C) and by Allara and Edelson (between 510 and 560°C) for kinetic parameters (A1 ≃ 1016.65 s-1 and E1 ≃ 84.7 kcal/mole) of the chain initiation process
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    The infrared chemiluminescent reaction of Cl atoms with H2CO (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 325-332 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction Cl + H2CO → HCl + HCO has been studied at 295 K. Chlorine atoms were produced via the infrared laser induced dissociation of CCl3F, using a pulsed CO2 TEA laser. Using HCl infrared chemiluminescence as the diagnostic, we find the rate constant to be 7.4 ± 0.7 × 10-11 cm3/molecule sec, in good agreement with several recent studies. An evaluation of TEA laser photolysis as a technique for the generation of chlorine atoms is made, and the relationship of this experiment to recent theories of infrared laser induced chemistry is discussed.
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    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 
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    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.
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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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    An indirect measurement of the absolute rate constant of the self-reaction of tert-butoxy radicalsPublication No. 251 from the Photochemistry Unit. (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 433-444 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No reliable rate constant is available for the self-reaction of tert-;butoxy radicals. We have set up a competition between hydrogen abstraction and self-reaction of tert-butoxy radicals in a flash photolysis electron spin resonance study to extract this information. Experimental values of hydrogen abstraction product radical concentrations under various hydrogen donor concentrations were then compared with theoretically calculated values with different values of 2k4 to obtain the best fit. Hydrogen donors such as cyclopentane, anisole, methyl tert-butyl ether, and methanol were chosen for the study. A value of (1.3 ± 0.5) × 109M-1 sec-1 for the rate constant of the self-reaction of tert-butoxy radicals has been determined at 293°K.
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    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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  • 72
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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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    Modeling of biological reactions (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 913-923 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cell membranes consist of lipid bilayers in which proteins are embedded. Many cell functions are carried out at the cell boundary which interface with water. Here we describe the response to an anesthetic of a lipid bilayer and of an enzyme separately. While both systems are markedly affected by anesthetics at appropriately high concentrations, the result at the clinical concentrations seems best explained as principally an effect on the protein somewhat accentuated by its presence in the lipid bilayer. Thus the lipoprotein complex seems to have the properties of the protein alone, except with somewhat greater induced sensitivity due to the lipid matrix in which it is immersed.
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    Comparison of the kinetics of cathodic H2 evolution from the unhydrated H3O+ ion and its hydrated form H9O4+: Frequency factor effects and modes of activation (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 925-944 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Experiments are described in which the kinetics of cathodic hydrogen evolution from the unhydrated H3O+ ion in pure CF3SO3- H3O+ are compared with those from an aqueous solution of CF3SO3H where the proton is mainly in a fully hydrated state as H9O4+. From the acid hydrate, which exists mainly as the ionic compound CF3SO3-H3O+, rates of H2 evolution at Ni, Pt, and Hg electrodes, measured at a given overpotential or expressed as exchange current densities, are between about 3.5 and 20 times slower than those from the same electrolyte in dilute (1.0M) aqueous solution. Allowing for the concentration differences in these two types of system and double-layer effects, the rate constants are between about 9.4 and 216 times smaller for the reaction from H3O+ than from H9O4+ at the above electrodes.The evaluation of apparent heats of activation for H2 evolution from the two types of proton sources allows ratios of real frequency factors to be calculated for discharge from H3O+ and H9O4+. These data have a bearing on the theoretical conclusions regarding proton discharge mechanisms and show that frequency factor effects can be as important as activation energy differences in determining the rates of proton discharge from different proton sources.The results are discussed in terms of current ideas about electron and proton transfer in electrochemical reactions, the state of hydration of H+, and the role of discharge from paired CF3SO3- and H3O+ ions. In particular, the molecular mechanics of discharge of the proton from the molecular ion H3O+ can be different from that from the fully hydrated H+ ion where many more HO- vibrational and librational modes can be involved in the process of activation of the H9O4+ entity.
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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.
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    URL: http://dx.doi.org/10.1002/kin.550130709
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    Temperature dependence of rate constants for the reaction of atomic oxygen with hydrogen chlorideNRCC No. 19482. (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 945-956 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A phase-shift method has been used to determine the rate constant for the reaction of ground state oxygen atoms with HCl over the temperature range of 330-600 K. Oxygen atoms were generated by modulated mercury photosensitized decomposition of N2O, and monitored by the chemiluminescence from their reaction with NO. After correction for diffusion of oxygen atoms from the viewing zone, the rate constants can be represented by the Arrhenius equation k1 = (3.06 ± 1.43) × 1012 exp[(-3160 ± 184)/T] cm3/mol·s. The indicated uncertainties are 95% confidence limits for 15 degrees of freedom. Also, the third-body efficiency of HCl relative to N2O in the reaction O + NO + M ← NO2 + M was determined to be 1.9 ± 0.2 over the temperature range of 298-360 K.
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    Quasi-classical trajectory calculations on the H + O2 reaction (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 957-975 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Quasi-classical trajectory calculations have been performed on the H + O2 system. Significant reaction probabilities are obtained when the initial energy is in rotation or vibration, or a combination of the two, but not when the initial energy is in translation. The opacity function shows a bimodal dependence on the impact parameter, with a small peak at 0.9 Å 〈 b 〈 1.5 Å and a very prominent peak at 2.5 Å 〈 b 〈 3.3 Å. The product scattering angles and product energy distributions also depend on b and to a limited extent on the initial energy distribution.The observations can be largely interpreted in terms of the nature of the motion on the potential energy surface, while the effects of rotational energy on the reaction follow qualitatively from statistical phase-space theory.
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    The dynamics of formation of vibrationally excited HF in reactions of O (21 D2) atoms with partially fluorinated alkanes (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 977-999 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The nascent vibrational energy distributions of the HF† formed in the reactions of a series of partially fluorinated alkanes (RFH; RF = CH2F, CHF2, CF3, C2F5, C3F7, and C7F15) with electronically excited oxygen atoms O(21D2) have been determined by measuring the appearance times of stimulated emissions from various vibration-rotation transitions in a grating-tuned optical cavity. The vibrational energy contents of the HF formed in these reactions were found to be considerably greater than statistically expected. These reactions are believed to occur via vibrationally excited short-lived α;-fluorinated alcohols (RFOH†), formed by insertion of the O(21D2) atoms into C—H bonds. The observation of nonstatistical energy partitioning in the above reactions is in clear contrast to the result obtained from the O(21D2) + CF3CH3 reaction that produces the β-fluorinated alcohol CF3CH2OH, from which the HF product carries a near statistical vibrational energy distribution. A mechanism for HF† formation in these very exothermic reactions is presented.
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    Electron transfer between trans-dihydroxotetraoxoosmate(VIII) and thiosulfate. A kinetic study in aqueous alkaline media (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1001-1010 
    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 thiosulfate to tetrathionate by trans-dihydroxotetraoxoosmate(VIII) in aqueous alkaline media have been studied. The oxidation follows a rate expression \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d[{\rm Os(VIII})]}}{{dt}} = k3{\rm K}_{OS} {\rm K}_2 [{\rm S}_2 {\rm O}_3^{2 - }][{\rm Os(VIII})](1 + {\rm K}_{os} {\rm K}_2 [{\rm S}_2 {\rm O}_3^{2 - }])^{ - 1} $$\end{document} where KOs is the formation constant of trans-dihydroxotetraoxoosmate (VIII), and K2 and k3, respectively, represent the formation constants of the intermediate complex involving Os(VIII) and S2O32- and its decomposition constant. The KOs, K2, and k3 values have been computed to be (19.5 ± 3) dm3/mol, (6.12 ± 0.5) and (3.32 ± 0.3) × 10-1 dm3/mol s at 303 K, and I = 0.32 mol/dm3, respectively. The rate law is consistent with a mechanism envisaging the equilibrium formation of an intermediate complex involving Os(VIII) and S2O32-, followed by a rate-determining decomposition of the complex with concomitant electron transfer.
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    Study of the HNO + HNO and HNO + NO reactions by intracavity laser spectroscopy (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1041-1050 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Flash photolysis of CH3CHO and H2CO in the presence of NO has been investigated by the intracavity laser spectroscopy technique. The decay of HNO formed by the reaction HCO + NO → HNO + CO was studied at NO pressures of 6.8-380 torr. At low NO pressure HNO was found to decay by the reaction HNO + HNO → N2O + H2O. The rate constant of this reaction was determined to be k1 = (1.5 ± 0.8) × 10-15 cm3/s. At high NO pressure the reaction HNO + NO → products was more important, and its rate constant was measured to be k2 = (5 ± 1.5) × 10-19 cm3/s. NO2 was detected as one of the products of this reaction. Alternative mechanisms for this reaction are discussed.
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    Substituent effects on the kinetics of the cerium(IV) oxidation of mandelic acids in sulfate media. Anomalous kinetic behavior of the methoxy derivative (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1029-1040 
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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 the cerium(IV) oxidation of p-nitro and p-methoxymandelic acids have been investigated in H2SO4-MHSO4 (M+ = Li+, Na+, K+) and H2SO4-MClO4 (M+ = H+, Na+) mixtures at a constant total electrolyte concentration of 2.00 mol/dm3. The oxidation of p+nitromandelic acid proceeds through two [H+]-independent paths, as was also observed for some substituted mandelic acids studied previously. The kinetic behavior of the p-methoxy derivative differs from that of the other mandelic acids in that (1) the oxidation occurs via two [H+]-dependent paths, (2) the reaction rate is anomalously high, (3) the activation enthalpy and entropy of the overall process are markedly lower. It provides strong support to the suggestion that a different mechanism is operative. The substituent effects and the reaction mechanism are discussed.
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    Kinetic studies of the reaction of C2H5 with O2 at 295 K (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1011-1028 
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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 between C2H5 and O2 at 295 K has been studied with a flow reactor sampled by a mass spectrometer. With helium as the carrier gas the rate coefficient was found to increase from (1.2 ± 0.3) × 10-12 to (3.6 ± 0.9) × 10-12 cm3/s as [He] was increased from 2 × 1016 to 3.4 × 1017 cm-3. The importance of has been determined from a knowledge of the initial C2H5 concentration together with a measurement of the C2H4 produced in reaction (5). F, the fraction of the C2H5 radicals removed by path (5), was found to decrease from 0.15 to 0.06 as [He] increased from 2 × 1016 to 3.4 × 1017 cm-3. The rate coefficient for reaction (5) was found to be independent of [He] and to have a value of (2.1 ± 0.5) × 10-13 cm3/s. The variation in F reflects the fact that k1b increases as [He] increases. These observations are taken as evidence for a direct mechanism for C2H4 production and a collision-stabilized route for C2H5O2 formation. Calculations indicate that the high-pressure limit for reaction (1b) is ∼4.4 × 10-12 cm3/s and that in the polluted troposphere the branching ratio for reactions (1b) and (5) will be ∼l20.
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    Unimolecular activation-deactivation: Impulsive collision theory (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1051-1070 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A theory of collisional energy transfer based on microcanonical relaxation in the limit of infinitesimal collision lifetimes is developed. In distinction to the recently formulated ergodic collision theory the potential energy is now frozen due to the short time scale, and only kinetic energy is available for redistribution. As a consequence, the rate of energy transfer is decreased, and agreement with experimentally based estimates generally improved.
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    Comments on “A smog chamber and modeling study of the gas phase NOx-air photooxidation of toluene and the cresols” (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1101-1103 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550131009
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    Addition of hot hydrogen atoms to 1-butene in the gas phase and dissociation of excited butyl radicals (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1071-1083 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of hot hydrogen atoms originating from 253.7- and 228.8-nm photolyses of hydrogen sulfide with 1-butene was investigated. Of the hydrogen atoms undergoing addition a substantial part undergoes it in a first collision (37 and 48% at 253.7 and 228.8 nm, respectively) yielding highly excited butyl radicals. The ratio of nonterminal to terminal addition is 0.5 and practically does not depend on the energy of the hydrogen atoms over the range of 15-33 kcal/mol. Comparing the results of 229- and 254-nm photolyses of hydrogen sulfide with those of 313- and 334-nm photolyses of hydrogen iodide with the use of the decomposition rate constants of n-butyl radicals calculated by the RRKM methods, the conclusion is reached that the hydrogen atom from H2S photodissociation has 90-95% of the available energy.
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  • 86
    Electronic Resource
    Electronic Resource
    Erratum (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1105-1105 
    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.550131010
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  • 87
    Electronic Resource
    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.550130101
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  • 88
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550130103
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  • 89
    Electronic Resource
    Electronic Resource
    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 
    Details
    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.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130105
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  • 90
    Electronic Resource
    Electronic Resource
    H + HOONO2 → products: Temperature-dependent rate constant (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1163-1174 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absolute reaction rate constant of the title reaction was measured in a stirred-flow reactor under H-atom-rich conditions at seven temperatures from 226 to 315 K. Carbon monoxide was added to convert any OH radicals produced back to H atom by way of the reaction OH + CO → H + CO2. The reaction rate constants were essentially constant between 248 and 315 K: (k ± 2σ) = (2.46 ± 0.35) × 10-14 cm3/s. At temperatures lower than 248 K, the measured rate constant became larger at lower temperatures, possibly due to heterogeneous effects. An hypothesis is advanced that may explain the surprisingly slow rate constant that is virtually independent of temperature, but more experiments are required to determine the dynamical reaction pathway.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550131107
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  • 91
    Electronic Resource
    Electronic Resource
    Mechanistic details of the Belousov-Zhabotinsky oscillations IV. Sensitivity analysis (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1175-1189 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The sensitivity of the period of the Belousov-Zhabotinsky oscillations to the rate constants and initial conditions of our previously proposed mechanism is computed by the technique recently developed for this purpose and shown to be valid in our analysis of the Oregonator. The principal rate-controlling steps for the determination of the period are found to be the enolization and bromination of malonic acid. Dependence of the period on initial conditions qualitatively agrees with available experimental data, except for the hydrogen ion, where a large discrepancy exists. It is suggested that this may be due to deficiencies in the organic reactions in the mechanism, or to a hydrogen-ion catalyzed bromination mechanism for malonic acid. Other components of the mechanism, which participate in characterizing the period and amplitude of the oscillations, are discussed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550131108
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  • 92
    Electronic Resource
    Electronic Resource
    O(3P) + HOONO2 → products: Temperature-dependent rate constant (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1151-1161 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reaction was studied in a stirred-flow reactor at six temperatures ranging from 228 to 297 K and for pressures near 2 torr. The experiments were performed under O-atom-rich conditions, and the HOONO2 concentration was monitored with a modulated molecular-beam mass spectrometer. O-atom concentrations were measured by titration with NO2 and by monitoring the portion of O2 dissociated in the microwave discharge. A weighted least-squares analysis gives (k ± 1σ) = (7.0 ± 12.2) × 10-11 exp(-3369 ± 489/T) cm3/s, where the uncertainties are 1 standard deviation (six temperatures) the covariance was σAB = 5.97 × 10-8. Due to the possible presence of systematic errors, the uncertainty in the rate constant could be as great as a factor of 2 over the entire temperature range.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550131106
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  • 93
    Electronic Resource
    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.550131201
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  • 94
    Electronic Resource
    Electronic Resource
    Erratum (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1215-1215 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No. Abstract.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550131111
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  • 95
    Electronic Resource
    Electronic Resource
    On the kinetics of the transition metal catalyzed decomposition of secondary hydroperoxides (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1191-1202 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general mechanism was proposed for the title reactions which describes the kinetics of hydroperoxide decomposition as well as product accumulation throughout the whole reaction period in an analytical form. The following catalytic steps were included: where the deactivation takes place as a result of radical-catalyst interaction inside the cage. The resulting equations give satisfactory description of the literature data in the case of various catalysts and hydroperoxides.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550131109
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  • 96
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of the aquation of pentaaqua (trichloroacetato-O)-chromium(2+) ion (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1203-1213 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the aquation of (H2O)5Cr(O2CCCl3)2+ have been examined at 35-55°C and 1.00M ionic strength with [H+] = 0.01-1.00M. The reaction follows the rate equation -d ln [Crtotal]/dt = (a[H+]-1 + b + c[H+])/(1 + d[H+]), where [Crtotal] is the stoichiometric concentration of the complex. At 45°C a = (1.41 ± 0.03) × 10-7M/s, b = (1.66 ± 0.02) × 10-5 s-1, c = (7.0 ± 0.8) × 10-5M-1·S-1 and d = 2.3 ± 0.3M-1. Two mechanisms consistent with this rate law are discussed, with evidence being presented in favor of an ester hydrolysis mechanism involving steady-state intermediates. Equilibrium and activation parameters were determined.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550131110
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  • 97
    Electronic Resource
    Electronic Resource
    INO thermodynamic properties and ultraviolet spectrum (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1227-1233 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The equilibrium I2(g) + 2NO(g) = 2INO(g) has been studied at room temperature by ultraviolet absorption spectroscopy. The equilibrium constant has been measured as Kp = (2.7 ± 0.3) × 10-6 atm-1 at 298 K. Third-law calculations lead to ΔH°f,298 (INO) = 120.0 ± 0.3 kJ/mol. The relative absorption spectrum of INO has been measured between 225 and 300 nm. Quantitative measurements gave ∊(λmax = 238 nm) = (1.79 ± 0.5) × 104 L/mol·cm and ∊(410 nm) = 234.7 ± 21 L/mol·cm.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550131203
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  • 98
    Electronic Resource
    Electronic Resource
    Nonisothermal kinetic analysis of the chemiluminescence from tetramethyl-1,2-dioxetane (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1217-1226 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A computerized method is given for the evaluation of Arrhenius parameters which describe the chemiluminescent decomposition of tetramethyl-1,2-dioxetane. The parameters were determined in several solvents by linear regression methods and the equation ln ln \documentclass{article}\pagestyle{empty}\begin{document}$ [(\sum\nolimits_0^\infty I - \sum\nolimits_0^t I)/(\sum\nolimits_0^\infty I - \sum\nolimits_0^t I - \sum\nolimits_0^{t + \Delta t} I)] = \ln\, (A_1 \Delta t) - E_1 /RT$\end{document}, where I refers to photons counted by increments of Δt, and E1 and A are the first-order Arrhenius parameters. The average of E1 and log A1 (s-1) from this method from six runs in CCl4 with initial concentrations of 4.9 × 10-5-8.45 × 10-4M were 27.21 ± 0.88 kcal/mol (113.7 ± 3.7 kJ/mol) and 13.88 ± 0.50, respectively. Simulated curves of chemiluminescence versus time were obtained with the use of a computer program and an auxiliary plotter.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550131202
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  • 99
    Electronic Resource
    Electronic Resource
    The kinetics of propylene oxide reaction with certain alkylamino alcohols in the presence of basic catalysts (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1243-1249 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for direct reactions of propylene oxide with certain aminoisopropanols in the presence of basic catalysts were studied at a temperature of 363-383 K. This reaction was found to be of the first order in propylene oxide, amino alcohol and catalyst. The observed kinetics are consistent with a termolecular mechanism.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550131205
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  • 100
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of reactions between aromatic olefins and hydroxyl radicals (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 1235-1242 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates of the reactions of hydroxyl radicals (OH) with styrene, α-methylstyrene, and β-methylstyrene have been measured by irradiating mixtures of these aromatic olefins and NO in an environmental chamber at 298 K. Experimental conditions were used whereby the competition of ozone with OH in oxidizing the hydrocarbons could be considered negligible. The rate constant values, obtained by a relative method using isooctane as reference hydrocarbon, are: styrene (5.3 ± 0.5) × 10-11 cm3/molec·s, α-methylstyrene (5.3 ± 0.6) × 10-11 cm3/molec·s, and β-methylstyrene (6.0 ± 0.6) × 10-11 cm3/molec·s. A simplified kinetic treatment of the experimental data shows that styrene and β-methylstyrene are stoichiometrically converted to benzaldehyde, suggesting that OH attack occurs only on the aliphatic moiety of the aromatic olefins. Benzaldehyde was observed to undergo consecutive oxidation by OH, and its maximum formation yield was about 60%. A reaction mechanism is proposed where the primary rate-determining OH attack leads to the formation of 1-hydroxy-2-phenyl-2-ethenyl radicals, from which benzaldehyde is formed through fast intermediate reactions.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550131204
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