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  • 1980-1984  (126)
  • 1955-1959
  • 1982  (126)
  • Physical Chemistry  (126)
  • 1
    Electronic Resource
    Electronic Resource
    Effects of buffer gases on the infrared multiphoton dissociation of C2H4DCl: A chemical clock to explore highly excited molecules (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 327-349 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Observations are reported of the effect of the buffer gases He, Ne, and CF4, in the pressure range of 0-30 torr, on the branching ratio [HCl]/[DCl] of the unimolecular decomposition The ratio R = kH/kD has been measured in high-pressure thermal decomposition (670-1100 K) and was shown to give a unique measure of the internal energy of the decomposing molecules and hence, with RRKM theory and pressure fall-off data, a time scale for their decomposition.Applying the thermal data to the photolysis leads to the conclusion that excitation and decomposition are produced by the laser spike (high intensity, 70 ns FWHM) and also at a slower rate by the larger, less intense tail (1.6 μs). Added buffer gases quench the latter, leaving the former which, from measurements of R, is shown to correspond to excitations of 115 ± 15 kcal/mol and lifetimes of ∼30 ps. No bond breaking is seen despite the high energies, in accord with theoretical expectations. The results require an enhanced rate of photon absorption by the highly excited molecules, which are about hundredfold greater than that observed for 300 K molecules. Data are also reported for C2H2F2 and the secondary multiphoton photolysis of the ethylenes produced. Effects of beam geometry and wavelength are explored.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140402
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  • 2
    Electronic Resource
    Electronic Resource
    Rate constants for the reaction of ground-state oxygen atoms with methanol from 297 to 544 KN.R.C.C. No. 19814. (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 371-379 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant for the reaction of ground-state oxygen atoms with methanol has been determined between 297 and 544 K by a phase-shift technique using mercury photosensitized decomposition of N2O to generate oxygen atoms. The relative oxygen atom concentration was monitored by the chemiluminescence from the reaction of oxygen atoms with nitric oxide. The results are accommodated by the Arrhenius expression k1 = (9.79 ± 2.71) × 1012 exp[(-2267 ± 111)/T]cm3/mol·s, where the indicated uncertainties are 95% confidence limits for 10 degrees of freedom. As an incidental part of this work, the third-body efficiency of CH3OH relative to N2O for the reaction O + NO + M → NO2 + M (M = CH3OH) was determined to be 3.1 at 298 K.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140405
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  • 3
    Electronic Resource
    Electronic Resource
    Surface oxygen bond energy, and kinetics and catalysis on perovskite oxide catalysts (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 435-438 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140409
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  • 4
    Electronic Resource
    Electronic Resource
    Temperature and third-body dependence of the rate constant for the reaction O + O2 + M → O3 + M (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 417-434 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The flash photolysis resonance fluorescence technique was used to measure the rate constants of the reaction O + O2 + M → O3 + M (M = N2, O2, Ar, and He) as a function of temperature. The results for the rate constants are given by The activation energies with N2, O2, and Ar as third bodies are equal within the experimental error, (-1370 → 340 cal/mol), and the relative third-body efficiencies at 298 K for N2, O2, Ar, and He are 1.00, 0.99, 0.69, and 0.60, respectively.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140408
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  • 5
    Electronic Resource
    Electronic Resource
    Cyclobutane production via the O3--thiolane reaction (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 439-445 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140410
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  • 6
    Electronic Resource
    Electronic Resource
    An empirical formula for gas-wall collision efficiencies in VLPP experiments (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 447-450 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140411
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  • 7
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of the gas-phase thermal reaction between bis(fluoroxy) difluoromethane CF2(OF)2 and carbon monoxide (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 647-657 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas-phase thermal reaction between CF2(OF)2 and CO has been studied in a static system at temperatures ranging between 110 and 140°C. The only reaction products were CF2O and CO2, giving the following stoichiometry: \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CF}_{\rm 2} {\rm (OF)}_{\rm 2} {\rm + 2CO = 2CF}_{\rm 2} {\rm O + CO}_{\rm 2} {\rm}\Delta n{\rm = 0}$$\end{document} The reaction is homogeneous. The rate is strictly second order in CF2(OF)2 and CO, and is not affected by the total pressure or by the presence of reaction products. Oxygen promotes a sensitized oxidation of CO and inhibits the formation of CF2O.The experimental results in the absence of oxygen can be explained by a chain mechanism similar to that proposed for the reaction between F2O and CO with an overall rate constant of \documentclass{article}\pagestyle{empty}\begin{document}$$k_1 = 1.45 \times 10^9 {\rm exp}(- 20,900/RT)L/mol \cdot s$$\end{document} From the experimental data obtained on the oxygen-inhibited reaction, the rate constant for the primary process can be calculated: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {({\rm I})} \quad {{\rm CF}_{\rm 2} ({\rm OF)}_{\rm 2} + {\rm CO} \to {\rm CF}_{\rm 2} (\mathop {\rm O}\limits^{\rm .}){\rm OF} + {\rm F}\mathop {\rm C}\limits^{\rm .} {\rm O}} \quad\quad {k_1 = 1.45 \times 10^9 {\rm exp}(- 20,900/RT)L/mol \cdot s} \\\end{array}$$\end{document} The chain length v = 2.5 is independent of the temperature. Taking for collision diameters σCF2(OF)2 = 6 Å and σCO = 3.74 Å, a value α = 5.3 × 10-3 for the steric factor is obtained.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140607
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  • 8
    Electronic Resource
    Electronic Resource
    The kinetics of the gas-phase reaction between iodine and phenylsilane and the bond dissociation energy D(C6H5SiH2—H) (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 669-677 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reaction has been investigated in the temperature range of 490-573 K. Initial reactant pressures were varied in the range of 0.2-5.2 torr (I2) and 2-20 torr (C6H5SiH3). The rate of iodine consumption, monitored spectrophotometrically, was found to obey \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d[{\rm I}_{\rm 2}]}}{{dt}} = \frac{{k_{3/2} [{\rm I}_{\rm 2}]^{{\raise0.7ex\hbox{$1$} \!\mathord{\left/ {\vphantom {1 2}}\right.\kern-\nulldelimiterspace} \!\lower0.7ex\hbox{$2$}}} [{\rm C}_{\rm 6} {\rm H}_{\rm 5} {\rm SiH}_{\rm 3}]}}{{1 + k'[HI]/[I_2]}}$$\end{document} both by initial rate and integrated equation fitting procedures. The effect of added initial HI conformed to this expression. The data are consistent with a conventional I-atom propagated chain reaction, and for the step \documentclass{article}\pagestyle{empty}\begin{document}$${\rm I}^{\rm .} + {\rm C}_{\rm 6} {\rm H}_{\rm 5} {\rm SiH}_{\rm 3} \to {\rm C}_{\rm 6} {\rm H}_{\rm 5} \mathop {\rm S}\limits^{\rm .} {\rm iH}_{\rm 2} + {\rm HI}$$\end{document} the rate constant is given by \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log}k_1 (dm^3 /mol \cdot s) = (11.52 \pm 0.08) - (76.8 \pm 0.8{\rm kJ/mol})/RT{\rm ln}10$$\end{document} From this is derived the bond dissociation energy value C6H5SiH2—H = 374 kJ/mol(88 kcal/mol). A comparison with other Si—H dissociation energy values indicates that the “silabenzyl” stabilization energy is small, ≈7 kJ/mol.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140609
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  • 9
    Electronic Resource
    Electronic Resource
    The oxidation of diethylhydroxylamine by nitrogen dioxide (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 699-710 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diethylhydroxylamine, (C2H5)2NOH, was oxidized by NO2 at 25°C in a long-path-length infrared gas cell. The measured products of the reaction were HONO and CH3CHO. The reaction scheme which explains the reaction is was oxidized by NO2, and the reaction was found to be very rapid with k1 〉 10-16 cm3/s. The products of the reaction were verified by both infrared absorption (CH3CHO, C2H5NO) and gas chromatography (CH3CHO, NO).
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140611
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  • 10
    Electronic Resource
    Electronic Resource
    Mechanism of oxidation of phenylthioacetic acids by potassium peroxodiphosphate (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 789-799 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates of oxidation of phenylthioacetic acid (PTAA) and several substituted phenylthioacetic acids by potassium peroxodiphosphate (PP) in 50% (v/v) aqueous acetic acid have been studied in detail. The rate of oxidation is expressed as \documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{- d[{\rm PP]}}}{{{\rm dt}}} = k[{\rm PP][PTAA][H}^{\rm +}]$$\end{document}An analysis of the dependence of the rate on [H+] reveals that H3P2O8- is the active oxidizing species in the oxidation. The effect of ring substituents on the rate gives a ρ+ value of -0.45 ± 0.03 (r = 0.998, s = 0.02 at 40°C), pointing to the development of an electron-deficient center in the transition state. The results are discussed in terms of a mechanism involving the rate-determining formation of an intermediate between PP and phenylthioacetic acids, followed by the decomposition of the intermediate. These kinetic results are compared with those obtained in the oxidation of phenylthioacetic acids by peroxodisulfate.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140707
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  • 11
    Electronic Resource
    Electronic Resource
    Electron transfer reactions of V(IV) with Cl(I), Br(I) and I(I). A kinetic study (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 801-811 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic study on the oxidation of V(IV) by chloramine-T (CAT) at pH 6.85 by N-bromo succinimide (NBS) in aqueous acetic acid-perchloric acid media and by N-iodo succinimide (NIS) in aqueous perchloric acid medium has been carried out. In all the systems studied the order with respect to the oxidant is unity. NBS and CAT oxidation reactions exhibited Michaelis-Menten type kinetics, and the NIS study indicated unit dependence on [substrate]. Independence on acidity has been observed in the case of CAT and NBS reactions, but NIS reactions exhibited inverse unit dependence on [acid]. Novel solvent influences have been noticed in the case of CAT reactions, but with NIS and NBS reactions retardation in the rate has been observed with an increase in the percentage of acetic acid. Plausible mechanisms consistent with the results have been postulated, and suitable rate laws in consonance with the postulated mechanisms have been derived.
    Additional Material: 7 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140708
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  • 12
    Electronic Resource
    Electronic Resource
    Reply to “comments on ‘a smog chamber and modeling study of the gas phase NOx-air photooxidation of toluene and the cresols’” (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 813-814 
    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.550140709
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  • 13
    Electronic Resource
    Electronic Resource
    Masthead (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140801
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  • 14
    Electronic Resource
    Electronic Resource
    A dual-frequency Belousov Zhabotinskii oscillating reaction with ethyl acetoacetate as organic substrate (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 815-821 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The experimental behavior of the cerium- and manganese-catalyzed Belousov Zhabotinskii oscillating reaction with ethyl acetoacetate as organic substrate has been investigated. Under certain conditions the system displays two types of temporal oscillations. Damped highfrequency oscillations appear immediately after the addition of potassium bromate solution to complete the reaction mixture. These high-frequency oscillations may be regarded as being superimposed on an induction period of the type found in the reaction using malonic acid. After the induction period, low-frequency oscillations of the normal type are obtained. Both the high-frequency and the low-frequency oscillations can be monitored with a platinum redox or with a bromide specific ion electrode.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550140802
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  • 15
    Electronic Resource
    Electronic Resource
    Rate constants for the gas-phase reaction of OH radicals with a series of ketones at 299 ± 2 K (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 839-847 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate constants for the reaction of OH radicals with a series of ketones have been determined at 299 ± 2 K, using methyl nitrite photolysis in air as a source of hydroxyl radicals. Using a rate constant for the reaction of OH radicals with cyclohexane of 7.57 × 10-12 cm3 molecule-1 s-1, the rate constants obtained are (× 1012 cm3 molecule-1 s-1): 2-pentanone, 4.74 ± 0.14; 3-pentanone, 1.85 ± 0.34; 2-hexanone, 9.16 ± 0.61; 3-hexanone, 6.96 ± 0.29; 2,4-dimethyl-3-pentanone, 5.43 ± 0.41; 4-methyl-2-pentanone, 14.5 ± 0.7; and 2,6-dimethyl-4-heptanone, 27.7 ± 1.5. These rate constants indicate that while the carbonyl group decreases the reactivity of C—H bonds in the α position toward reaction with the OH radical, it enhances the reactivity in the β position.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550140804
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  • 16
    Electronic Resource
    Electronic Resource
    The reaction of methyl p-nitrophenyl sulfate with hydrogen peroxide anion determination of pKa of hydrogen peroxide in methanol by a kinetic spectrophotometric procedure (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 823-837 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic spectrophotometric investigation of the reaction of the hydrogen peroxide anion with methyl p-nitrophenyl sulfate in methanol solvent resulted in the evaluation of the pKa of HOOH in methanol at 25°C as 15.8 ± 0.2. Since normal kinetic procedures for the determination of the equilibrium constant K for the process CH3O- + H2O2 ⇄ CH3OH + HO2- were found to be associated with high uncertainty, another procedure was devised to establish the magnitude of K. This method is based on an analysis of the changing slopes of plots of pseudo-first-order rate constants against the total base concentration as the stoichiometric amount of hydrogen peroxide is varied. The method is applicable to any system in which anionic nucleophiles generated in situ compete with solvent anions. Such a corroboration of kinetically determined equilibrium constants is believed essential. The kinetic data allow the specific rate constant kHOO-for the reaction of methyl p-nitrophenyl sulfate with hydrogen peroxide anions to be evaluated and yield the rate constant ratio kHOO-/kMeO- = 8.8 ± 2.2. This confirms the existence of an α effect at saturated carbon in this system.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550140803
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  • 17
    Electronic Resource
    Electronic Resource
    Thiocyanate-assisted demetallation of α,β,γ,δ-tetra(p-sulfophenyl)porphinatoindium(III) in aqueous media (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 849-859 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate law for the demetallation of the title indium(III)-porphin complex in aqueous acidic thiocyanate media at 3.00M ionic strength was found to be of the form \documentclass{article}\pagestyle{empty}\begin{document}$$+ \frac{{d{\rm [H}_{\rm 4} {\rm P}^{{\rm 2} - } {\rm]}}}{{dt}} = \frac{{ab[{\rm H}^{\rm + }]^2 [{\rm NCS}^ -]^2 }}{{1 + b[{\rm H}^{\rm + }]^2 }}[{\rm InP]}_{\rm t}$$\end{document} where [H4P2-] is the concentration of the diacid product formed, [InP]t is the total concentration of all forms of indium(III)-porphin complex present, and a and b are constants. The constant a is a pseudo-third-order rate constant with the value (0.057 ± 0.005)M-2 s-1 and b has the value 0.704M-2 at 50.5°C. If the mechanism for demetallation involves ringpuckering with the attachment of two H+ ions, then 1/b can be identified with the product K1K2 for the stepwise dissociation of two protons from two ring pyrrolic nitrogen atoms of H2InP-. In the sulfonated tetraphenylporphin used for these studies the ring pyrrolic nitrogen atoms seem to be the most probable sites for protonation. If this identification is correct, the value of 1.42 ± 0.13 found for the product K1K2 shows the enormous effect that the presence of the In3+ center has on the ionization constants of these two protons. That the kinetic studies show saturation effects with respect to proton addition to InP3- may result from the fact that In3+ sits about 0.6 Å above the porphin ring.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550140805
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  • 18
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of base-catalyzed cleavage of some bicyclo[4.2.0.]octa-1,3,5-trien-7-one (benzocyclobuten-1(2H)-one) derivatives (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 893-902 
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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 cleavage of 3-hydroxybicyclo[4.2.0]octa-1,3,5-trien-7-ones in aqueous sodium hydroxide, and of the alkoxy and acetoxy analogues in methanolic sodium methoxide solution, were examined under pseudo-first-order reaction conditions. The dependence of the rate upon the basicity of the solvent, whether measured by H- or by [OR-], reflects the possible structure of the transition state. The deduced mechanism is also supported by the effects of substituents upon the reaction rate. The relative amounts of the volatile reaction products derived from o-toluic acid and from phenylacetic acid are understood in terms of the substituent effect upon the relative stabilities of the carbanions.
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    URL: http://dx.doi.org/10.1002/kin.550140808
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  • 19
    Electronic Resource
    Electronic Resource
    Kinetics of the isomerization reaction of cholest-5-en-3-one catalyzed by trichloroacetic acid in aprotic solvents of low dielectric constant (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 875-891 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The isomerization reaction of cholest-5-en-3-one has been studied in a solution of cyclohexane using trichloroacetic acid as catalyst. At the same time a general reaction scheme is proposed to be valid for all the cases assayed in which the monomer form of the acid is considered as the only effective catalyst. The experimental results agree with these hypotheses and with the calculation of the individual rate constant together with the reaction order with respect to the catalyst. Semiquantitative studies have been carried out with other catalysts and solvents, confirming the validity of the reaction scheme. The thermodynamic activation parameters have also been calculated, and a comparative study was made with the results of the evaluation of the reaction when it takes place in amphiprotic solvents. A reaction mechanism is proposed based on all the kinetic information obtained.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550140807
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  • 20
    Electronic Resource
    Electronic Resource
    Basic hydrolysis of glyceryl nitrate esters. I. 1-glyceryl and 2-glyceryl nitrate esters (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 903-917 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of the basic hydrolysis of 1-glyceryl mononitrate (1-MNG) and 2-glyceryl mononitrate (2-MNG) were investigated in CO2-free aqueous calcium hydroxide solutions. The hydrolysis reactions were carried out in a temperature-controlled reactor vessel with provision for continuous N2 sparging of the reaction mixture. Both glyceryl nitrate esters hydrolyzed via second-order reaction at 25°C. 2-MNG in calcium hydroxide solution isomerized to 1-MNG, which subsequently hydrolyzed to form NO3-. In strongly basic aqueous solutions of NaOH (30%), 2-MNG is converted to glycidol and NO3-.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550140809
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  • 21
    Electronic Resource
    Electronic Resource
    Kinetics of the gas-phase reactions of OH radicals with alkyl nitrates at 299 ± 2 K (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 919-926 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate constants for the gas-phase reactions of OH radicals with a series of alkyl nitrates have been determined at 299 ± 2 K, using methyl nitrite photolysis in air as a source of OH radicals. Using a rate constant for the reaction of OH radicals with cyclohexane of 7.57 × 10-12 cm3/molec·s, the rate constants obtained are (× 1012 cm3/molec·s): 2-propyl nitrate, 0.18 ± 0.05; 1-butyl nitrate, 1.42 ± 0.11; 2-butyl nitrate, 0.69 ± 0.10; 2-pentyl nitrate, 1.87 ± 0.12; 3-pentyl nitrate, 1.13 ± 0.20; 2-hexyl nitrate, 3.19 ± 0.16; 3-hexyl nitrate, 2.72 ± 0.22; 3-heptyl nitrate, 3.72 ± 0.43; and 3-octyl nitrate, 3.91 ± 0.80. These rate constants, which are the first reported for the alkyl nitrates, are significantly lower than those for the parent alkanes, and a formula, based on the numbers of the various types of C—H bonds in the alkyl nitrates, is derived for rate constant estimation purposes.
    Additional Material: 3 Ill.
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    Electronic Resource
    A reexamination of the pyrolysis of bis trifluoromethyl peroxide (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 933-944 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The literature results for the pyrolysis of bis trifluoromethyl peroxide are reexamined and compared with those for dimethyl peroxide. The thermochemistry yields the result that the π-bond energy in carbonyl fluoride is 96 ± 10 kcal/mol compared to 74 kcal/mol for that in formaldehyde. Thermodynamic additivity contributions are derived for the C—(F)3(O) and O—(C)(F) groups. Some conclusions are drawn in relation to the oxidation of halogeno methyl radicals and the chemistry of the atmosphere.
    Additional Material: 4 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550140812
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  • 23
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    Electronic Resource
    Mechanism of the hydroxyiodination of 2-butenoic acid (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 927-932 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aqueous iodination of trans-2-butenoic acid proceeds via hydrolysis of I2 to form HOI and I-, then rapid addition of HOI across the double bond to form the iodohydrin product. In the presence of iodate to keep iodide concentration low, the reaction proceeds at a conveniently measurable rate. The rate for the addition reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm HOI + CH}_{\rm 3} {\rm CH=\!=CHCOOH} \to {\rm CH}_{\rm 3} {\rm CH(OH)CHICOOH}$$ \end{document} is -d[C4H6O2]/dt = 5900 [H+][C4H6O2][HOI]M/s at 25.0°C when [IO3-] = 0.025M and ionic strength = 0.3. The overall rate law in the presence of iodate is \documentclass{article}\pagestyle{empty}\begin{document}$$ -d[{\rm I}_{\rm 2}]/dt = 3.2 \times 10^{ - 3} \times 10^{ - 3} [{\rm H}^{\rm + }][{\rm IO}_{\rm 3}^ -]^{0.65} [{\rm C}_{\rm 4} {\rm H}_{\rm 6} {\rm O}_{\rm 2}]^{1/2} [{\rm I}_{\rm 2}]^{1/2} M/{\rm s}$$ \end{document} where [H+] and [IO3-] are total concentrations used to prepare the solution.
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  • 24
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of the thermal decomposition of methyl isocyanate (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 945-952 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of gas-phase decomposition of methyl isocyanate have been investigated in the range of 427-548°C. Two decomposition routes are followed; the predominant one is a radical-chain process giving CO, H2, and HCN as major products, which has an order of 1.5 and an Arrhenius equation given by log k(L1/2/mol1/2·s) = (13.12 ± 0.06) - (56,450 ± 1670) cal/mol/2.303 RT. The minor route is the bimolecular formation of N,N′-dimethylcarbodiimide and CO2, which from the low activation parameters Ea = 31.6 kcal, A = 105.30 L1/2/mol1/2·s, and the reaction order of 1.57 appears to be heterogeneous.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550140813
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  • 25
    Electronic Resource
    Electronic Resource
    Masthead (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140901
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  • 26
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    Electronic Resource
    Pyridiniumchlorochromate oxidations: Studies on the kinetics and substituent effect in the oxidation of aniline in nonaqueous systems (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 977-984 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyridiniumchlorochromate (PCC) oxidizes aniline and substituted anilines except nitro anilines smoothly in chlorobenzene-nitrobenzene mixtures in the presence of dichloroacetic acid. The reaction has unit dependence on each of the aniline, PCC, and dichloroacetic acid concentrations. Electron-releasing substituents accelerate the reaction, whereas electronwithdrawing groups retard the reaction, and the rate data obey Hammett's relationship. The reaction constant ρ is -3.75. Azobenzene and p-benzoquinone have been obtained as products. The observed experimental data have been rationalized in terms of the formation of an intermediate complex involving PCC-amine undergoing a rapid decomposition to products.
    Additional Material: 4 Tab.
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  • 27
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    Quantitative treatment of the effect of counterions on ctab-catalyzed reactions of stabilized carbonium ions with cyanide ion (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1007-1015 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of stabilized carbonium ions of setoglaucin, methyl violet, and ethyl violet with cyanide ions are largely catalyzed by the cationic micelles of cetyltrimethylammonium bromide (CTAB) in aqueous media. Added counterions (anions in this case) have strong inhibitory effects on the CTAB-catalyzed reactions in the following order: N3- 〉 NO3- 〉 Br- 〉 Cl- 〉 F- 〉 no salt. The inhibitory effects of the counterions have been attributed to the exchange between added anions and reagent (CN-) in the micellar media. The data have been analyzed by the model schemes, and mathematical formulations were developed. Various parameters associated with the exchange process, such as equilibrium exchange constant, number of surfactant molecules per substrate molecule, number of added anions, and a factor related to the binding of additives to the catalytic micellar aggregates, have been evaluated.
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  • 28
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    Kinetics and mechanisms of oxidation of organic compounds by silver(II) species. Part VI: Iminodiacetic acid and N-methyliminodiacetic acidFor Part V, see C. Baiocchi and E. Mentasti, Trans. Metal Chem., 5, 259 (1980). (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1017-1032 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and mechanism of oxidation of iminodiacetic acid and N-methyliminodiacetic acid by aquasilver(II) and Ag(II)-2,2′-bipyridine complexes has been investigated. The results are discussed with reference to the active reaction pathways, the equilibrium quotient of the title reactions, the protolytic equilibria which involve the oxidizing complex, and the intrinsic self-exchange rates of the oxidants.
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  • 29
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    Electronic Resource
    Analysis of the unimolecular reaction N2O5 + M ⇌ NO2 + NO3 + M (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 399-416 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Recent experimental results on the thermal decomposition of N2O5 in N2 are evaluated in terms of unimolecular rate theory. A theoretically consistent set of fall-off curves is constructed which allows to identify experimental errors or misinterpretations. Limiting rate constants k0 = [N2] 2.2 × 10-3 (T/300)-4.4 exp(-11,080/T) cm3/molec·s over the range of 220-300 K, k∞ = 9.7 × 1014 (T/300)+0.1 exp(-11,080/T) s-1 over the range of 220-300 K, and broadening factors of the fall-off curve Fcent = exp(-T/250) + exp(-1050/T) over the range of 220-520 K have been derived. NO2 + NO3 recombination rate constants over the range of 200-300 K are krec,0 = [N2] 3.7 × 10-30 (T/300)-4.1 cm6/molec2·s and krec,∞ = 1.6 × 10-12 (T/300)+0.2 cm3/molec·s.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550140407
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  • 30
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    The kinetics and mechanisms of the gas-phase unimolecular eliminations of halogeno esters. Participation of the carbomethoxy group (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 381-397 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas-phase elimination of several chloroesters were determined in a static system over the temperature range of 410-490°C and the pressure range of 47-236 torr. The reactions in seasoned vessels, and in the presence of a free-radical inhibitor, are homogeneous, unimolecular, and follow a first-order law. The temperature dependence of the rate coefficients is given by the following Arrhenius equations: for methyl 3-chloropropionate, log k1(s-1) = (13.22 ± 0.07) - (231.5 ± 1.0) kJ/mol/2.303RT; for methyl 4-chlorobutyrate, log k1(s-1) = (13.31 ± 0.25) - (221.5 ± 3.4) kJ/mol/2.303RT; and for methyl 5-chlorovalerate, log k1(s-1) = (13.12 ± 0.25) - (221.7 ± 3.2) kJ/mol/2.303RT. Rate enhancements and lactone formation reveal the participation of carbonyl oxygen of the carbomethoxy group. The order COOCH3-5 〉 COOCH3-6 〉 COOCH3-4 in assistance is similar to the sequence of group participation in solvolysis reactions. The partial rates for the parallel eliminations to normal dehydrohalogenation products and lactones have been estimated and reported. The present results lead us to consider that an intimate ion-pair mechanism through participation of the carbomethoxy group may well be operating in some of these reactions.
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  • 31
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    Electronic Resource
    Estimation of rate constants from growth and decay data (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 517-534 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Many experiments in chemical kinetics are initiated by a fast pulse, such as electric discharge, shock wave, flash lamp, or laser. After this pulse one observes the production and subsequent decay of a reactive intermediate. One then postulates a mechanism and adjusts the associated rate constants so as to minimize the difference between the results of the experiment and the prediction of the mechanism. The parameters to be estimated are usually strongly correlated, so that it is not possible to determine them separately. These estimated parameters are of little value unless we can also estimate statistically valid confidence limits for them. The difficulties are discussed which frequently arise in estimating parameters and confidence limits for a kinetic mechanism which is widely used in interpreting laser excitation and fluorescence measurements, that is, first-order production and decay. These difficulties, and methods for dealing with them, are illustrated with realistic data. The estimation problem is particularly ill conditioned when the production and loss rates are nearly equal. In some experimental systems this can be avoided, but in others it is inevitable.
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  • 32
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    Electronic Resource
    Differential method for the determination of the order of reaction and the rate constants (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 535-541 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is proposed whereby the orders and rate constants for processes obeying the rate law -dA/dt = kAn may be determined. The method is illustrated in two ways. First, simulated data for processes of various orders are treated, and the treatment is shown to be capable of reproducing orders and rate constants to a high degree of accuracy. The factors affecting the accuracy with which n and k can be determined are considered. These are inaccuracy in the determination of concentration values, irregularity of the time intevals between concentration determinations, and the length of those time intervals. It is shown that if concentrations are determined at times that are close together, the effect of the other two factors is small, but if the time intervals are made longer, the errors due to the other two factors affect the calculated values of n and k much more seriously. Second, the method was applied to two homogeneous reactions, of which one was first-order and one was second order, and three heterogeneous reactions, of which one was found by the original workers to be first order, one to be zero order, and one to vary between zero and first order, depending on the initial pressure. The present method gives results in agreement with these conclusions and reproduces the rate constants to within ±5% in all cases.
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  • 33
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    Electronic Resource
    F-to-HF reactions. VIII. Nonthermal complications for the CHF3/C3F6/C2F6 moderated nuclear recoil system (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 565-583 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Results are reported from moderated nuclear recoil 18F experiments with the 273 K CHF3/C3F6/C2F6 system. Although the measurement sensitivity is only about ±12%, there is no evidence to support the occurrence of nonthermal F-to-HF reactions at 95 mol % C2F6 moderator concentration.
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    Quantized RRK theory of unimolecular reaction rates (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 543-564 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The main difference between the simple RRK theory and the better based but more complex RRKM theory is explained. Starting from the premise that the classical versus quantum mechanical estimation of the density of states is the major source of the difference, earlier attempts to incorporate the quantum effects in an effective value for the number of oscillators s are noted. By examining the expression for the RRKM rate coefficient it is found that a single effective s value will generally not suffice, but a much better representation of the quantum effects can be obtained if it is recognized that the problem inherently contains two different effective s values. A theory based on this analysis is constructed. It reproduces RRKM results to much improved accuracy, removing difficulties found earlier with single-s-value theories.
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    Very low-pressure pyrolysis (VLPP) of pentynes. III. Pent-2-yne. Heat of formation and resonance stabilization energy of the 3-methylpropargyl radical (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 613-621 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal unimolecular decomposition of pent-2-yne has been studied over the temperature range of 988-1234 K using the technique of very low-pressure pyrolysis (VLPP). The main reaction pathway is C4—C5 bond fission producing the resonance-stabilized 3-methylpropargyl radical. There is a concurrent process producing molecular hydrogen and penta-1,2,4-triene presumably via the intermediate formation of cis-penta-1,3-diene. The 1,4-hydrogen elimination from cis-penta-1,3-diene is the rate-determining step in the molecular pathway. This is supported by an independent VLPP study of cis- and trans-penta-1,3-diene. RRKM calculations show that the experimental rate constants for C—C bond fission are consistent with the following high-pressure rate expression at 1100 K: \documentclass{article}\pagestyle{empty}\begin{document}$$\log k_1 = \left({s^{ - 1}} \right) = \left({16.0 \pm 0.3} \right) - \left({72.6 \pm 2.0} \right)/\theta $$\end{document} where θ = 2.303RT kcal/mol and the A factor was assigned from the results of shock-tube studies of related alkynes. The activation energy leads to ΔHf,3000[CH3C≡CĊH2] = 70.3 and DH3000[CH3CCCH2—H] = 87.4 kcal/mol. The resonance stabilization energy of the 3-methylpropargyl radical is 10.6 ± 2.5 kcal/mol, which is consistent with previous results for this and other propargylic radicals.
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    URL: http://dx.doi.org/10.1002/kin.550140603
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  • 36
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    Chemiluminescence simulation method for the evaluation of the termination rate constant for 2-cyanopropyl peroxy and α-phenyl-ethyl peroxy radicals (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 641-646 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An iterative method has been devised for the simulation of chemiluminescence data during the oxidative decomposition of αα′ azobisisobutyronitrile in the presence of ethylbenzene. From this simulation the cross termination rate constant of the two types of peroxy radicals present has been estimated.
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    URL: http://dx.doi.org/10.1002/kin.550140606
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    The liquid-phase reaction of CCl3 radicals with primary alcohols (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 659-668 
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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 gamma-radiation-induced free-radical reactions in carbon tetrachloride solutions of ethanol and n-pentanol were studied in the range of 0.05-0.80M and 25-170°C. The rate constant for the reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CCl}_{\rm 3} + {\rm R} - CH_2 - {\rm OH}\mathop \to \limits^{k1} {\rm CHCl}_{\rm 3} + {\rm R} - {\rm CH} - {\rm OH}$$\end{document} was found as \documentclass{article}\pagestyle{empty}\begin{document}$$k1(M^{- 1} \cdot s^{- 1}) = 10^{8.6 \pm 0.4} \exp - (\frac{{9900 \pm 600{\rm cal}}}{{RT}})$$\end{document} The activation energy is larger by 0.8 kcal/mol than for secondary alcohols, while the A1 factors are about the same.
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    Ozone-isoprene reactions: Product formation and aerosol potential (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 955-975 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dark-phase experiments between isoprene and O3 are discussed. UNC outdoor chamber experiments have shown that in high-concentration systems of isoprene and O3 (5 ppm C and 1 ppm) approximately 75% of the reacted carbon can be observed in the product formation of HCHO, CO, methacrolein, methylvinylketone, methylglyoxal, acetaldehyde, and propylene. Mechanisms were developed which gave reasonable fits to dark-phase chamber experiments of MACR, MVK, isoprene, and O3. Experimental data and modeling results were used to generate O3 rates of attack on MVK and MACR. An isoprene-O3 rate of 1.67 × 10-2 ppm-1·min-1 was used and is consistent with other rates reported in the literature. Dark isoprene-O3 systems appear to form homogeneously nucleated aerosol. Most of these particles appear and remain at diameters well below the optical cutoff region (0.3-0.5 μm), as opposed to the particles from similar α-pinene-O3 systems, which also form at smaller sizes but then grow into the optical size range (0.5 μm). Lower concentrations of α-pinene and O3 (0.2 ppm C and 0.12 ppm) still generated substantial aerosol, but by comparison, rapid CN nucleation was not observed during a similar side-by-side system of isoprene and O3.
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  • 39
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    Kinetics and mechanism of reaction of p-methoxystyrene and tetracyanoethylene. I. Evidence for competitive 1,2- and 1,4-cycloadditions (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 985-996 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Time-resolved absorption spectra for a reaction mixture of p-methoxystyrene and tetracyanoethylene (TCNE) are found to have a band maximum at 325 nm which is assigned to the 1,4-cycloadduct. The reaction in chloroform at 15, 20, and 25°C is followed by the charge-transfer band at 600 nm. The 1,4-cycloadduct, besides the so far known 1,2-cycloadduct and EDA complex, is taken into account to derive the rate equation for the EDA complex that is a linear second-order differential equation. The rate constants for the elementary steps involved in the reaction are obtained. The 1,4-cycloaddition has an activation entropy of -63 J/K·mol for the cycloreversion and a reaction constant ρ of -4.7, both of which indicate the polar transition state. On the other hand, activation entropy of the 1,2-cycloaddition is 73 J/K·mol more negative than that of the 1,4-cycloaddition, supporting the zwitterionic mechanism for the 1,2-cycloaddition.
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    URL: http://dx.doi.org/10.1002/kin.550140904
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  • 40
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    Kinetics and mechanisms of the reaction of acetylene with cyclohexa-1,3-diene and the decomposition of bicyclo[2.2.2]-octa-2,5-diene in the gas phase (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 997-1005 
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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 acetylene (A) with cyclohexa-1,3-diene (CHD) has been studied between 450 and 592 K. The pressures of A ranged from 25 to 112 torr and those of CHD from 8 to 62 torr. The reaction yields only ethene (E) and benzene (B) instead of bicyclo[2.2.2]octa-2,5-diene (BOD), the product that is expected for a 1,4,1′,2′ addition of the Diels-Alder type. It is first order with respect to each reagent. The rate constant (in L/mol·s) is given by \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} k = - (27,150 \pm 120)/4.576T + (7.49 \pm 0.05)$$\end{document} The thermal decomposition of BOD has also been studied. In the ranges of 354-435 K and 0.5-6 torr, the reaction is first order and results in the formation of equal amounts of B and E as the reaction of A with CHD does. Its rate constant (in s-1) is given by \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} k_d = - (32,520 \pm 40)/4.576T + (14.06 \pm 0.02)$$\end{document} The following consecutive reactions are proposed for the reaction between A and CHD: where BOD is the primary product that is too unstable to be detected. This implies that the rate constant k is equal to ka. The reaction mechanisms and the strain energy in BOD are discussed.
    Additional Material: 3 Ill.
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  • 41
    Electronic Resource
    Electronic Resource
    Reaction of hot H atoms with CDCl3 (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1105-1112 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Energetic hydrogen atoms generated by photolysis of HBr or HI react with CDCl3 by abstracting either a deuterium atom (1) or a chlorine atom (2): The integral probability of reaction (2) has been measured for several defined initial translational energies of H*, and the phenomenological threshold energy is 31 ± 14 kJ/mol. For initial translational energies in the range of 66-121 kJ/mol, the ratio of the integral probabilities of Cl abstraction and of D abstraction, when normalized to equal numbers of Cl and D atoms, is 2.4 ± 0.3. The interpretation of the integral reaction probabilities in terms of the excitation functions of reactions (1) and (2) is discussed. Measurements of the moderating effect of CO2 on reactions (1) and (2) show that CDCl3 is slightly more effective than CO2 as a moderator of H atoms in the energy range of 90-30 kJ/mol.
    Additional Material: 3 Ill.
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  • 42
    Electronic Resource
    Electronic Resource
    F-to-HF reactions. IX. Nonthermal complications for the CH4/C3F6/C2F6 moderated nuclear recoil system (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1165-1182 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Results are reported from moderated nuclear recoil 18F experiments with the CH4/C3F6/C2F6 mixture system. At a 99.5% confidence level measurement precision of ±3.4%, non-thermal F-to-HF reactions are phenomenologically suppressed at C2F6 moderator concentrations in the range of 95.0-99.95 mol-%. Effectively equilibrium reaction conditions can be established in well-designed experiments of this type.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550141102
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  • 43
    Electronic Resource
    Electronic Resource
    An ftir study of the reaction between nitrogen dioxide and alcohols (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1199-1209 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction 2NO2 + ROH = RONO + HNO3 (R = CH3 or C2H5) has been studied using the FTIR method at reactant pressures from 0.1 to 1.0 torr at 25°C. The termolecular rate constant for the forward reaction was determined to be (5.7 ± 0.6) × 10-37 cm6/molec2·s for CH3OH and (5.7 ± 0.8) × 10-37 cm6/molec2·s for C2H5OH, that is, d[RONO]/dt = k[NO2]2[ROH]. The corresponding equilibrium constants were measured as 1.36 ± 0.06 and 0.550 ± 0.025 torr-1, respectively. These results are consistent with those of a previous study based on the NO2 decay measurements at reactant pressures from 1 to 10 torr.
    Additional Material: 5 Ill.
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  • 44
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    Electronic Resource
    Kinetic and mechanistic studies of oxidation of arginine, histidine, and threonine in alkaline medium by N-chloro-N-sodio-p-toluenesulfonamide (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1183-1197 
    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 arginine, histidine, and threonine by chloramine-T (CAT) have been investigated in alkaline medium at 35°C. The rates are first order in both [CAT] and [amino acid] and inverse fractional order in [OH-] for arginine and histidine. The rate is independent of [OH-] for threonine. Variation of ionic strength and addition of the reaction product, p-toluenesulfonamide, or Cl- ions had no effect on the rate. A decrease of the dielectric constant of the medium by adding methanol decreased the rate with arginine, while the rates increased with histidine and threonine. The solvent isotope effect was studied using D2O. (kobs)D2O/(kobs)H2O was found to be 0.55 and 0.79 for arginine and histidine, respectively. The reactions were studied at different temperatures, and activation parameters have been computed. The oxidation process in alkaline medium, under conditions employed in the present investigations, has been shown to proceed via two paths, one involving the interaction of RNHCl (formed rapidly from RNCl-), with the amino acid in a slow step to form monochloroamino acid, which subsequently interacts with another molecule of RNHCl in a fast step to give the products, p-toluenesulfonamide (RNH2), and the corresponding nitrile of the amino acid (R'CN). The other path involves the interaction of RNCl- with the amino acid in a similar way to give RNH2 and R'CN. Mechanisms proposed and the derived rate laws are consistent with the observed kinetics. The rate constants predicted using the derived rate laws, as [OH-] varies, are in excellent agreement with the observed rate constants, thus justifying these rate laws and hence the proposed mechanistic schemes.
    Additional Material: 3 Ill.
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  • 45
    Electronic Resource
    Electronic Resource
    Anomalous kinetic hydrogen isotope effect in the oxidation of formate by bromine: Tunneling via an intermediate (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1211-1218 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rates of oxidation of XCOO- (X = H, D) by Br2 in acid aqueous media were measured between 274 and 332 K. The derived Arrhenius parameters for both reactions \documentclass{article}\pagestyle{empty}\begin{document}$$\log k_{\rm H} (M^{- 1} {\rm s}^{{\rm - 1}}) = (11.18 \pm 0.10) - (14.33 \pm 0.13)/\theta $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log k_{\rm D} (M^{- 1} {\rm s}^{{\rm - 1}}) = (13.77 \pm 0.13) - (17.62 \pm 0.04)/\theta $$\end{document} where θ = 4.575T × 10-3 kcal/mol, with (kH/kD)298K = 2.85, reveal a primary isotope effect, but the difference (ED - EH) = 3.29 kcal/mol and the ratio AD/AH = 91 fall beyond the limits imposed by semiclassical transition-state theory, suggesting tunneling or a multiple-stage mechanism. However, it can be shown that either tunneling in a single step or a three-step, internal return mechanism can be ruled out as alternative models, since both require unreasonable kinetic parameters to fit the data. The simplest scheme accounting for the present observations involves tunneling in the decomposition of a charge transfer complex in equilibrium with the reactants.
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  • 46
    Electronic Resource
    Electronic Resource
    Reaction between U(IV) and H2O2 in hydrochloric acid medium (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1219-1229 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetic investigations on the reaction between U(IV) and H2O2 have been carried out at different acidities in chloride medium at an ionic strength of 2M. The observed bimolecular rate constant has been found to be dependant on [H+]-1.3. The activation energy of the overall reaction has been found to vary from 13.4 ± 0.7 to 18.0 ± 0.8 kcal/mol in the range of acidity from 0.3 to 1.5M. The results have been explained on the basis of three parallel rate-controlling reactions involving unhydrolyzed species of U(IV) and hydrolyzed species UCl(OH)2+ and UO2+. The values of the rate constants for these three reaction paths have been found to be of the order of 3.95, 5.59 × 103, and 1.49 × 105M-1 min-1, respectively.
    Additional Material: 4 Ill.
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  • 47
    Electronic Resource
    Electronic Resource
    Masthead (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140601
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  • 48
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    Electronic Resource
    Very low-pressure pyrolysis (VLPP) of penta-1,3-dienes. Kinetics of the unimolecular 1,4-hydrogen elimination from cis-penta-1,3-diene (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 623-629 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal unimolecular reactions of cis- and trans-penta-1,3-diene (c-PTD and t-PTD) have been studied over the temperature range of 1002-1235 K using the technique of very low-pressure pyrolysis (VLPP). c-PTD decomposes via 1,4-hydrogen elimination analogous to that previously reported for cis-but-2-ene. RRKM calculations incorporating a six-center transition state show that the experimental rate constants are consistent with the following high-pressure rate expression at 1100 K: \documentclass{article}\pagestyle{empty}\begin{document}$$\log k_\infty = \left({s^{ - 1}} \right) = \left({13.0 \pm 0.6} \right) - \left({64.5 \pm 2.0} \right)/\theta $$\end{document} where θ = 2.303RT kcal/mol, and the A factor was assumed to be the same as that for cis-but-2-ene. The activation energy is in excellent agreement with that obtained for cis-but-2-ene. t-PTD also undergoes decomposition by H2 elimination presumably via the prior rapid isomerization to c-PTD the results are in exact agreement with those for c-PTD.
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  • 49
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    Electronic Resource
    Kinetics and mechanism of Rh(III) catalyzed oxidation of styrene, stilbene and phenylacetylene by acid periodate (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 631-639 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of Rh(III) catalyzed oxidative cleavage of styrene, stilbene, and phenylacetylene by periodate have been investigated in the presence of HClO4 in aqueous acetic acid medium. The kinetic orders are completely dependent on the nature of unsaturation. In the cases of styrene and stilbene the reactions are first order in the oxidant and Rh(III), zero order with respect to the substrate, and independent of [H+], whereas in the case of phenyl acetylene the reaction is zero order with respect to the oxidant and first order with respect to the substrate and Rh(III). The reaction is independent of [H+] in the range of 0.01-0.05M studied. A mechanism involving higher Rh(V) species has been postulated in the case of styrene as well as stilbene, and metal ion catalyzed hydration has been postulated in case of phenylacetylene. The influence of the solvent has been investigated, and a comparative analysis of the kinetic orders of styrene and stilbene is made with those of phenylacetylene.
    Additional Material: 6 Tab.
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  • 50
    Electronic Resource
    Electronic Resource
    Masthead (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140701
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  • 51
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    Laser magnetic resonance spectroscopy of ClO and kinetic studies of the reactions of ClO with NO and NO2 (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 711-732 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Far-infrared rotational transitions in ClO(X2∏3/2, υ = 0) have been observed using laser magnetic resonance (LMR) with an optically pumped spectrometer. Five observed transitions at wavelengths between 444 and 713 µm have been compared with values predicted with spectroscopic constants from the literature. LMR detection of ClO has been used to study its reactions with NO and NO2 in a discharge flow system under pseudo-first-order conditions for ClO. The measured rate constants are k(ClO + NO) = (7.1 ± 1.4) × 10-12 exp[(270 ± 50)/T] cm3/molec·s for the temperature range of 202 〈 T 〈 393 K; k(ClO + NO2 + M) = (2.8 ± 0.6) × 10-33 exp[(1090 ± 80)/T] cm6/molec2·s (M = He, 250 〈 T 〈 387 K), (3.5 ± 0.6) × 10-33 exp[(1180 ± 80)/T] (M = O2, 250 〈 T 〈 416 K), and (2.09 ± 0.3) × 10-31 (M = N2, T = 297 K). All measurements were made at low pressures, between 0.6 and 6.6 torr. These results are compared with those from other studies.
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  • 52
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    Electronic Resource
    A completely inorganic oscillating system of the Belousov-Zhabotinskii type (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 735-738 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An inorganic compound, NaH2PO2, has been found to generate temporal chemical oscillations in Belousov-Zhabotinskii type reactions when it is substituted for the organic reducing material. Gaseous products were removed by a constant flow of nitrogen carrier gas. Periodic Br2 evolution was measured polarographically.
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  • 53
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    Electronic Resource
    The thermal decomposition of fluorinated esters. III. Esters without β hydrogen atoms (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 739-747 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas-phase decomposition of methyl trifluoroacetate and 2,2,2-trifluoroethyl trifluoroacetate, two esters without β hydrogen atoms, have been investigated, and a comparative study was carried out on methyl acetate. All these compounds are thermally much more stable than fluorinated esters with β hydrogens, decomposing at temperatures some 150°C above the latter by a completely different mechanism involving partly heterogeneous radical chains. The marked difference in behavior between the two types of fluorinated ester confirms that none of them decomposes by hydrogen fluoride elimination, but that those with β hydrogen atoms follow the normal ester decomposition route. The fluorinated esters examined here decompose in a manner generally similar to methyl acetate, but the presence of fluorine in the molecule brings about an extreme sensitivity to surface conditions.
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  • 54
    Electronic Resource
    Electronic Resource
    Oscillatory behavior during the oxygen oxidation of ascorbic acid (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 749-759 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oscillatory phenomenon was observed in aqueous solution during the oxidation of ascorbic acid by oxygen. Even though the exact number and amplitude of the oscillations could not be exactly duplicated for each and every run, such factors as temperature, concentration of ascorbic acid, cupric ions, and pH affecting the oscillatory behavior were studied, and those regions where oscillations occurred were delineated. A mechanism consistent with the oscillatory behavior is proposed and discussed.
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  • 55
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    Electronic Resource
    New aspects of the mechanism for the thermal hydrocracking of indan and tetralin (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 761-780 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal cracking of indan and tetralin in the gas phase was carried out in a flow reactor at 500°C and 8 MPa pressure in the presence of hydrogen and nitrogen. The primary reactions are ring cracking and dehydrogenation, regardless of the nature of the second component. Ring cracking, however, is strongly enhanced by the presence of hydrogen. This enhancement becomes less significant with increasing concentration of the hydrocarbon in the gaseous reaction mixture and also with a decreasing ratio of hydrogen to hydrocarbon. At hydrocarbon concentrations larger than approximately 0.5 g·mol/L and H2-to-HC molar ratios of 1 or lower, conversion rates are almost equal in hydrogen and in nitrogen. Ring cracking exhibits different kinetic behavior in nitrogen than in excess of hydrogen. This illustrates the occurrence of two complementary cracking mechanisms, each of which can dominate in certain concentration ranges. The H2-initiated ring cracking is gradually transformed into a hydrogen-donor mechanism as the leading reaction scheme when the concentration of indan or tetralin is increased.
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  • 56
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    Electronic Resource
    Kinetics of the reactions of OH radicals with n-alkanes at 299 ± 2 K (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 781-788 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate constants for the reaction of OH radicals with a series of n-alkanes have been determined at 299 ± 2 K, using methyl nitrite photolysis in air as a source of OH radicals. Using a rate constant for the reaction of OH radicals with n-butane of 2.58 × 10-12 cm3 molecule-1s-1, the rate constants obtained are (X1012 cm3 molecule-1 s-1): propane 1.22 ± 0.05, n-pentane 4.13 ± 0.08, n-heptane 7.30 ± 0.17, n-octane 9.01 ± 0.19, n-nonane 10.7 ± 0.4, and n-decane 11.4 ± 0.6. The data for propane, n-pentane, and n-octane are in good agreement with literature values, while those for n-heptane, n-nonane, and n-decane are reported for the first time. These data show that the rate constant per secondary C - H bond is ∽40% higher for  - CH2 -  groups bonded to two other  - CH2 -  groups than for those bonded to a  - CH2 -  group and a  - CH3 group.
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  • 57
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    Electronic Resource
    Experimental investigation of chamber-dependent radical sources (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1071-1103 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: While environmental chamber data have been widely used to generate and validate computer models of the chemistry occurring in polluted atmospheres, the effects of the chambers on the gas-phase chemistry being studied have been poorly characterized. In order to investigate such chamber effects, a series of NOx - air irradiations, with trace levels of organics present to monitor OH radical concentrations, have been carried out in four different environmental chambers (ranging in volume from ∼100 to 40,000 L) at varying temperatures, humidities, pressures, and reaction conditions. In addition, a number of control experiments have been carried out to validate the technique for measuring OH radical levels in these irradiations. The data show that unknown sources of OH radicals are present in all of the chambers studied. The data are consistent with the presence of two distinct radical sources: (1) the photolysis of initially present HONO, whose importance increases with increasing NO2/NO concentration ratios, but which is a minor contributor to the overall radical flux after 30-60 min of irradiation, and (2) a constant (for these NOx - air irradiations) radical source which dominates beyond approximately the first 60 min of irradiation. The radical input rates, after the first ∽30-60 min of irradiation, are independent of the NO concentration, increase with increasing temperature, humidity, and NO2 concentration, are proportional to light intensity, and are dependent on the chamber employed. Although the exact nature of this radical source is still undetermined, results of experiments reported here allow a number of possible mechanisms to be ruled, out, and these are discussed.
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  • 58
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    Kinetics and mechanism of the oxidation of halotoluenes by acidic hexacyanoferrate(III) (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1113-1124 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of halotoluenes by hexacyanoferrate(III) in aqueous acetic acid containing perchloric acid (0.5M) at 50°C gave the corresponding aldehyde as the major product, and a small amount of polymeric material. The order with respect to each of the reactants - substrate, oxidant, and acid - was found to be unity. Increasing proportions of acetic acid increased the rate of the reaction. The reaction was influenced by changes in temperature, and the activation parameters have been evaluated. The Hammett plot yielded a ρ+ value of -1.8. A kinetic isotope effect kH/kD = 6.0 has been observed. The pathway for the conversion of the halotoluenes to the products has been mechanistically visualized as proceeding through the benzylic radical intermediate, formed in the rate-determining step of the reaction. The radical undergoes rapid conversion to the products.
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  • 59
    Electronic Resource
    Electronic Resource
    Masthead (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550141101
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  • 60
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    Electronic Resource
    Spectra of propylperoxy radicals and rate constants for mutual interaction (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1125-1138 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The flash photolyses of azo-n-propane and azoisopropane in the presence of oxygen have been studied by kinetic spectroscopy. The transient absorption spectra observed in the region of 210-290 nm are assigned to the n-propylperoxy and isopropylperoxy radicals. For the n-propylperoxy radical, εmax = 1148 ± 29 L/mol cm at 242.5 nm and for the isopropylperoxy radical, εmax = 1273 ± 75 L/mol cm at 240 nm. The rate constants for the mutual reactions (7) 2RO2· → products were measured to be k7 = (2.0 ± 0.2) X 108 L/mol s for the n-propylperoxy radical and k7 = (7.8 ± 2.2) X 105 L/mol s for the isopropylperoxy radical.
    Additional Material: 4 Ill.
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    Masthead (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140101
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    Rate constants for the gas-phase reactions of O3 with selected organics at 296 K (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 13-18 
    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 ethene, propene, 1-hexene, 1-heptene, styrene, o-, m-, and p-cresol, o- and m-xylene, benzylchloride, acrylonitrile, and trichloroethene have been determined at 296 ± 2 K. The rate constants ranged from 〈5 × 10-21 cm3 molecule-1 s-1 for m-xylene to 2.16 × 10-17 cm3 molecule-1 s-1 for styrene, with those for ethene, propene, and 1-hexene being in excellent agreement with literature data.
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    Absolute rate constants for the reactions between amino and alkyl radicals at 298 K (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1-12 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absolute rate constants for the reactions of NH2 radicals with ethyl, isopropyl, and t-butyl radicals have been measured at 298 K, using a flash photolysis-laser resonance absorption method. Radicals were generated by flashing ammonia in the presence of an olefin. A new measurement of the NH2 extinction coefficient and oscillator strength at 597.73 nm was performed. The decay curves were simulated by adjusting the rate constants of both the reaction of NH2 with the alkyl radical and the mutual interactions of alkyl radicals. The results are k(NH2 + alkyl) = 2.5 (±0.5), 2.0 (±0.4), and 2.5 (±0.5) × 1010 M-1·s-1 for ethyl, isopropyl, and t-butyl radicals, respectively. The best simulations were obtained when taking k(alkyl + alkyl) = 1.2, 0.6, and 0.65 × 1010M-1·s-1 for ethyl, isopropyl, and t-butyl radicals, respectively, in good agreement with literature values.
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  • 64
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    Flash photolysis of biacetyl in gas phase. Rate constants of reactions between methyl and acetyl radicals (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 35-42 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The flash photolysis of biacetyl produces CO, C2H6, and CH3COCH3 as main products, and in small amounts CO2, C2H4, and CH3CHO. The rate constants of reactions (2) and (3) \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {(1)} {2{\rm CH}_3 \to {\rm C}_2 } \\ \end{array}{\rm H}_6 $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {(2)} {{\rm CH}_3 + {\rm CH}_3 {\rm CO} \to {\rm CH}_3 {\rm COCH}_3 } \\ \end{array} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {(3)} {2{\rm CH}_3 {\rm CO} \to {\rm CH}_3 {\rm COCOCH}_3 } \\ \end{array} $$\end{document} of thermally equilibrated radicals were calculated from the amounts of products: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} k_2 = (2.98 \pm 0.17){\rm 10}^{{\rm 10}} {\rm dm}^{\rm 3} /{\rm mol} \cdot {\rm s} \\ k_3 = (2.43 \pm 0.14){\rm 10}^{{\rm 10}} {\rm dm}^{\rm 3} /{\rm mol} \cdot {\rm s} \\ \end{array} $$\end{document}.
    Additional Material: 1 Ill.
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    The kinetics of isotope exchange reactions: Use of initial rates to measure isotope effects on carbon acid ionization (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 19-34 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Multistep hydrogen isotope exchange reactions, such as the íonization of a carbon acid via a carbanion intermediate in a protic solvent, when conducted using an isotopic tracer to monitor the exchange, have the unusual feature that their rate-determining steps always refer to the transfer of the tracer isotope and never to the isotope present in macroscopic amounts. This property of these reactions is discussed and rationalized using a free energy versus reaction coordinate diagram. It is further shown that this property does not invalidate a commonly used method of measuring kinetic isotope effects on carbon acid ionization in which rates of incorporation of tritium tracers into RH and RD substrates are compared, despite the fact that tritium transfer is rate determining in both exchanges, but it is valid only if initial rate measurements are used. When the comparison is made in a protio solvent, e.g., H2O, the portion of the initial reaction which may be used depends strongly on the magnitude of the isotope effect. It ranges from less than 1% tritium incorporation for large isotope effects to 10% or more for isotope effects near unity. On the other hand, when a deuterated solvent, e.g., D2O, is used, the range of validity of the method for large isotope effects is extended dramatically.
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  • 66
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    Vibrational energy transfer from chemically activated 1,4-cyclohexadiene (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 43-53 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal isomerization of cis, anti, cis-tricyclo[3.1.0.02,4] hexane was used to produce highly vibrationally excited 1,4-cyclohexadiene. The competition between unimolecular decomposition of the energized diene (to benzene and hydrogen) and collisional stabilization was studied using the parent compound, SF6, CO2, N2, and He as quenching gases. Quenching efficiencies decreased in the order given above. By applying RRKM theory to the isomerization and decomposition reactions, it was possible to calculate the step size in a stepladder model of the deactivation of cyclohexadiene. The step sizes 〈ΔE〉 deduced (at 528 K and in units of kJ/mol) were: parent compound and SF6, 7; CO2, 5; N2, 4; He, 2. The study confirmed the utility of this unimolecular chemical activation system for energy transfer studies.
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    Kinetics of the sulfodeacylation of 2,4,6,2′,6′-pentamethylbenzophenone, a process comprising successive first-order reactions occurring by two alternative routes (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 55-62 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mesityl 2,6-xylyl ketone in 89.8% (w/w) sulfuric acid undergoes cleavage to give mesitylenesulfonic acid, xylenesulfonic acid, and carbon dioxide as final products. The reaction has been analyzed in terms of a series of first-order reactions. Of the two possible reaction paths available it was shown that fission at the mesityl group is responsible for about 98.5% of the overall initial reaction at 25°C.
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  • 68
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    Masthead (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140201
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  • 69
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    Mechanism of HTO formation in gaseous tritium mixtures (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 77-90 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanisms for the conversion of molecular tritium gas to tritiated water are examined for tritium mixtures with (1) oxygen and nitrogen, (2) oxygen and argon, and (3) water and helium, for which previous experimental data exist. By analyzing results of these experiments in light of the radiation chemistry involved in a mixture of tritium and other gases, an understanding of the conversion mechanisms is reached. The formation of H and/or OH free radicals as intermediate species is of particular significance in the formation of HTO in that these radicals initiate a number of reactions which lead to the formation of water. These reactions are analyzed in terms of steady-state kinetics to obtain predictive models which can be judged against the experimental observations. For the three experimentally observed mixtures, model agreement is found to be within a factor of 2-3.
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    Intramolecular isotopic effect in the pyrolysis of ethyl-2d1 chloride (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 63-75 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of deuterated ethyl chloride CH2DCH2Cl was studied in a static system in the pressure range of 0.1-26 torr, and the Arrhenius expression for the overall decomposition at the high-pressure limit and in the temperature range of 670-1100 K was found to be \documentclass{article}\pagestyle{empty}\begin{document}$$ k_\infty = 10^{13.33 \pm 0.10} \exp [(- 57,200 \pm 500){\rm cal/mol/}RT]{\rm}s^{- 1} $$\end{document}The intramolecular isotopic effects were first examined in the pressure range of 0.1-26 torr at 837 K, and the branching ratio kH/kD was found to decrease with increasing pressure. The RRKM-theory calculations describe the experimental data well.The intramolecular isotopic effect was also examined in the temperature range of 728-926 K, and the branching ratio at the high pressure limit was given by the expression \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{\rm H} /k_{\rm D} = (1.44 \pm 0.05)\exp [(1500 \pm 50){\rm cal/mol/}RT] $$\end{document} when kH and kD are the rate constants for the HCl and DCl channels of elimination.The Arrhenius A factors obtained at the high-pressure limit together with the temperature-dependent expression of the branching ratio provided additional experimental data for an assignment (fine-tuned) of the vibrational frequencies of both activated complexes involved in the thermal decomposition of CH2DCH2Cl. The evaluated vibrational frequencies were then used in the RRKM calculations describing the pressure dependence of the intramolecular isotopic effect. The RRKM calculations and the experimental data were in good agreement, supporting the choice of vibrational frequencies for both the activated complexes as well as the transition-state model.
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    URL: http://dx.doi.org/10.1002/kin.550140108
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    Chemistry in mixtures of Kr with Ar and He illuminated with Kr resonance radiation (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 93-130 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The formation and destruction of excited rare-gas dimers have been studied using resonance optical excitation of high-pressure gas mixtures containing Kr. From an analysis of the resulting emission, 19 reaction rate coefficients have been inferred. It is concluded that atom-atom interchange processes play a major role in rare-gas eximer formation, and that stepwise relaxation down the eximer vibrational ladder is less important than multistep relaxation due to atom-atom exchange in the excited eximer.
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    Gas-phase thermolysis of sulfur compounds. Part III: n-butyl 2-propenyl sulfide (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 131-142 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of n-butyl 2-propenyl sulfide has been investigated in a static system in the initial pressure range of 50-350 torr. The reaction was found to be homogeneous and first order. The rate coefficients are given by the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ k{\rm}(s^{- 1}) = 10^{11.42 \pm 0.28} \exp [(- 155 \pm 3){\rm kJ/mol/}RT] $$\end{document} between 262 and 293°C. The rate of the reaction remains unchanged in the presence of cyclohexene as radical inhibitor. The main reaction products were propene and a trimer of n-butyl thioaldehyde. The results are interpreted in terms of a molecular mechanism involving a cyclic six-centered transition state. This mechanism is supported by the pyrolysis of 1,1-dideutero-n-butyl 2-propenyl sulfide at 281°C. The kinetic deuterium isotope effect had a value of 2.7 ± 0.2. Nuclear magnetic resonance and mass spectroscopic analysis of the reaction products showed the deuterium to be distributed as expected from the proposed reaction mechanism.
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  • 73
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    A novel wall reaction of OH (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 153-159 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A moderately fast second-order reaction between OH and atomic hydrogen, which occurred on the halocarbon-coated or acid-washed walls of a standard discharge-flow apparatus, has been investigated using epr spectroscopy. The reaction that occurred in a halocarbon-coated flowtube was found to be unusual in that it produced a reactive product, namely, atomic oxygen.
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    Kinetics and mechanism of Os(VIII)-catalyzed hexacyanoferrate(III) oxidation of α amino acids in alkaline medium (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 143-151 
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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 Os(VIII)-catalyzed oxidation of glycine, alanine, valine, phenylalanine, isoleucine, lycine, and glutamic acid by alkaline hexacyanoferrate(III) reveal that these reactions are zero order in hexacyanoferrate(III) and first order in Os(VIII). The order in amino acid as well as in alkali is 1 at [amino acid] ≤2.5 × 10-2M and [OH-] ≤1.3 × 10-M, but less than unity at higher concentrations of amino acids or alkali. The active oxidizing species under the experimental conditions is OsO4(H2O) (OH)-. The ferricyanide is merely used up to regenerate the Os(VIII) species from Os(VI) formed during the reaction. The structural influence of amino acids on the reactivity has been discussed. The amino acids during oxidation are shown to be degraded through intermediate keto acids. The kinetic data are accommodated by considering the interaction between the conjugate base of the amino acids and the active oxidizing species of Os(VIII) to form a transient complex in the primary rate-determining step. The catalytic effect of hexacyanoferrate(II) has been rationalized.
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    Kinetics and mechanism of the amine exchange reactions of 2-aminopyridine derived Schiff-base ligands and their copper(II) complexes (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 161-172 
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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 product analyses of the amine exchange reactions of two 2-aminopyridine derived Schiff-base ligands and their monomeric bischelate and dimeric copper(II) complexes have been studied. The Schiff-base ligands investigated underwent amine exchange reactions with n-butyl, cyclohexyl, t-butyl amines. The coordination of the Schiff-base ligands to copper(II) rendered the amine exchange reactions slower. With n-butyl and cyclohexyl amines, parallel first- and second-order terms on their concentrations are observed for the amine exchange reactions of copper(II) bischelates and dimer. The kinetic data favor a mechanism involving a rate-limiting elimination of 2-aminopyridine from a diaminoacetal intermediate in preference to a scheme in which a dissociation of the complexes into free ligands and Cu(II) may precede the amine exchange. The steric factors influence the amine exchange reactions of Cu(II) bischelates with the bulkier amines reacting slower as given by the order t-butylamine (3.3 ± 0.3 × 10-3 dm3/mol·s) 〈 cyclohexylamine (0.2 ± 0.03 dm3/mol·s) 〈 n-butylamine (2.2 ± 0.2 dm3/mol·s). The bulkiness of the t-butyl group and the constraints imposed by the changes in the coordination geometry of Cu(II) on amine exchange not only render the reactions of Cu(II) bischelates slower but also make the formation of the mixed adduct ([N-(5-methyl)-2-pyridyl salicylaldimine][N-t-butyl salicylaldimine] Cu(II)) more favored.
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    URL: http://dx.doi.org/10.1002/kin.550140206
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  • 76
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    Gas-phase chlorine-initiated photooxidation of methanol and isopropanol (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 173-182 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of CH3OH/Cl2/air, CH3OH/Cl2/NO2/air, and (CH3)2CHOH/Cl2/NO2/air at 28 ± 2°C was studied using the long-path FTIR method. The primary reactions of methanol and isopropanol with Cl atoms were α-hydrogen abstraction (100%), and α hydrogen (85%), and α-hydrogen abstraction (15%), respectively. The failure to detect hydroxyalkyl-peroxy nitrates suggested that the oxygen addition to α-hydroxy radicals is not important. From the product distribution an upper limit of the ratio of oxygen addition to CH2OH and CH3CHOH was estimated to be about 6 and 7%, respectively. The oxygen addition ratio to (CH3)2COH was very low. The reaction mechanism is also discussed.
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  • 77
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    Kinetics of the reaction of C2H5O2 with NO at 295 K (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 183-194 
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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 C2H5O2 with NO in helium carrier gas at 295 K with [He] = 1.6 × 1017 cm-3 has been studied using a gas flow reactor sampled by a mass spectrometer. Because no parent molecular ion or suitable fragment ion produced by C2H5O2 could be detected, the reaction was followed by measuring the formation of NO2. In so doing, account had to be taken of the small amount of HO2 known to be present in the reaction mixture, which also leads to NO2 on reaction with NO. The rate coefficient for the total reaction of C2H5O2 with NO was found to be (8.9 ± 3.0) × 10-12 cm3/s, and the path which produces NO2 was found to account for at least 80% of all C2H5O2.
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    Nucleophilic character of the tert-butyl radical. Absolute rate constants for the reactions with substituted toluenes (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 195-200 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decay of photochemically generated tert-butyl radicals is studied at 48°C in 11 m- and p-substituted toluenes by time-resolved electron spin resonance spectroscopy. It is governed by the second-order self-termination perturbed by a pseudo-first-order reaction of the radical with the toluenes. The first-order lifetimes yield the rate constants kA for hydrogen transfer from toluenes to tert-butyl. Substituent effects on the rate constants confirm the nucleophilic character of the radical.
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  • 79
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    Masthead (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140301
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  • 80
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    Kinetics and energetics of the criegee intermediate in the gas phase. I. The criegee intermediate in ozone-alkene reactions (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 201-224 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chemistry and energetics of the Criegee intermediate, a primary product of the ozonolysis of alkenes, are discussed in terms of recent ab-initio calculations and laboratory studies. The experimental observations in O3-alkene systems can be rationalized on the basis of a general mechanism: where the
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    The mechanism of O3-aldehyde reactions (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 237-249 
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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 mechanism is proposed for gas-phase O3-aldehyde reactions. Certain aspects of the new mechanism may be applicable also to O3-aldehyde reactions in solution. The proposed mechanism involves initiation by addition of O3 across the aldehydic C=O bond. The initiation process and the subsequent chemistry together represent an exact analogue of the Criegee mechanism for O3-alkene reactions.
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    Kinetics and energetics of the criegee intermediate in the gas phase. II. The criegee intermediate in the photooxidation of formaldehyde, in alkyldioxy disproportionation and O + oxoalkane addition reactions (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 225-236 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase kinetics and energetics of the Criegee intermediate, deduced from studies of O3-alkene systems, suggest that a hydroxy-substituted Criegee intermediate probably participates in the photooxidation of formaldehyde. In contradistinction, the existing evidence suggests that the Criegee intermediate and its isomers are probably not involved in alkyldioxy disproportionation reactions. In the case of O + oxoalkane addition reactions, the Criegee intermediate and its isomers are discussed in terms of a complex equilibrium: .
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140303
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  • 83
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    Electronic Resource
    Kinetics of the thermal reactions of bicyclo[4.2.2]deca-3,7-diene and endo-and exo-5-vinylbicyclo[2.2.2]oct-2-ene in the gas phase (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 251-257 
    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 reactions of bicyclo[4.2.2]deca-3,7-diene (BDD) and endo- and exo-5-vinylbicyclo[2.2.2]oct-2-ene (endo- and exo-VBO) have been studied in the gas phase. The temperature range was 459-526 K for BDD, 476-563 K for endo-VBO, and 513-578 K for exo-VBO. The initial pressures were varied from 2 to about 40 torr. These compounds isomerize to cis-1,2,4a,5,8,8a-hexahydronaphtalene (HHN) and into each other, and decompose to 1,3-butadiene (BD) + cyclohexa-1,3-diene (CHD). The reactions are homogeneous and first order. Their rate constants (in s-1) are given by: where the superscripts represent the reagents and the subscripts the products. The heats of formation and the entropies of endo-VBO, exo-VBO, and BDD are estimated.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140305
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  • 84
    Electronic Resource
    Electronic Resource
    Heterogeneous reactions of sulfur dioxide with carbonaceous particles (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 269-277 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of adsorption of SO2 on a prototype carbonaceous surface was measured at low pressure in a flow reactor. The measured rate indicates a maximum atmospheric loss of SO2 by heterogeneous reaction of 1%/h for a particle density of 100 μg/m3. The capacity of carbon particles to adsorb SO2 is limited at ∼1 mg SO2 g-1 C. NO2 has no effect on the rate of SO2 adsorption or the saturation behavior.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140307
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  • 85
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    Electronic Resource
    Kinetics and mechanism of the addition of 1,3-butadiene to cyclohexa-1,3-diene in the gas phase (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 259-267 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal reactions of 1,3-butadiene (BD) with cyclohexa-1,3-diene (CHD) have been studied in a static system between 437 and 526 K. The pressures of BD and CHD were varied from 61 to 397 torr and from 50 to 93 torr, respectively. The percentages of consumed BD and CHD were always kept lower than 14%. The reactions - in the order of importance - are All the reactions are homogeneous and of the first order with respect to the reagents. Their rate constants (in L/mol·s) are given by \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} \log _{10} k_{{\rm HHN}} = - (25,370 \pm 70)/4.576T + (7.02 \pm 0.03) \\ \log _{10} k_{{\rm KNDO}} = - (24,840 \pm 50)/4.576T + (6.58 \pm 0.02) \\ \log _{10} k_{{\rm BDD}} = - (25,530 \pm 50)/4.576T + (6.61 \pm 0.02) \\ \log _{10} k_{{\rm EXO}} = - (26,760 \pm 50)/4.576T + (7.06 \pm 0.02) \\ \end{array} $$\end{document} A thermochemical analysis of a biradical mechanism is in agreement with these results.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140306
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  • 86
    Electronic Resource
    Electronic Resource
    Shock-initiated decomposition of tetramethylgermane and the reaction of methyl radicals with toluene (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 279-289 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The shock-initiated decomposition of tetramethylgermane (1078-1242 K) has been found to involve successive elimination of methyl radicals with the rate constant k1 for the first step given by \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_{\rm 1} {\rm}(s^{- 1}) = {\rm}(17.00 \pm 0.35) - (77.0 \pm 1.9)\theta {\rm kcal/mol} $$\end{document} In the presence of excess toluene the products were CH4 (major), C2H4, and C2H6. Results relevant to the reaction of methyl radicals with toluene compared to methyl radical recombination are discussed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140308
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  • 87
    Electronic Resource
    Electronic Resource
    Masthead (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140401
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  • 88
    Electronic Resource
    Electronic Resource
    The thermal decomposition of fluorinated esters. II. The effect of γ-substitution (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 291-297 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase kinetics of thermal decomposition of ethyl difluoroacetate, pentafluoropropionate, and hepatfluorobutyrate have been studied. The normal ester decomposition route to ethylene plus carboxylic acid is taken in each case, but the fluorinated acids decompose rapidly at the temperatures used. The primary decompositions are homogeneous and unimolecular, and the three Arrhenius equations are \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} \log k{\rm}({\rm CF}_2 {\rm HCO}_2 {\rm Et}){\rm}({\rm s}^{- 1}) = (12.81 \pm 0.39) - (46,740 \pm 1290){\rm cal/mol/2}{\rm .303}RT \\ \log k{\rm}({\rm C}_2 {\rm F}_5 {\rm CO}_{\rm 2} {\rm Et}){\rm}({\rm s}^{- 1}) = (12.16 \pm 0.32) - (43,760 \pm 970){\rm cal/mol/2}{\rm .303}RT \\ \log k{\rm}({\rm C}_3 {\rm F}_7 {\rm CO}_{\rm 2} {\rm Et}){\rm}({\rm s}^{- 1}) = (12.29 \pm 0.13) - (43,880 \pm 370){\rm cal/mol/2}{\rm .303}RT \\ \end{array} $$\end{document} The postulate of a slightly electron-rich γ carbon in six-center ester transition states is supported by the higher rates and lowered activation energies observed when increasingly electron-withdrawing fluorinated groups are linked to this center. The stabilization is reflected in a ρ constant of +0.30. The results are compared with previous work on α substitution in fluorinated esters.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140309
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  • 89
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    Electronic Resource
    Specialist periodical reports. Gas kinetics and energy transfer, volume 4, edited by P. G. Ashmore and R. J. Donovan, The Royal Society of Chemistry, London, 1981. Pp. VI + 242 (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 325-326 
    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.550140311
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  • 90
    Electronic Resource
    Electronic Resource
    Disproportionation reactions between CF2H and C2H5 radicals in the gas phase (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 299-323 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The disproportionation and combination reactions between CF2H and C2H5 radicals have been studied in the gas phase from room temperature to 70°C. For the pathway which yields CF2H2 + C2H4, relative to CF2HC2H5, Δ = 0.072 ± 0.019. The competing reaction channel that produces CF2 + C2H6 is approximately four times as efficient, with Δ = 0.265 ± 0.038. With CF2D radicals an isotope effect for the CF2 + C2H5D reaction pathway was observed with Δ ≅ 0.2.
    Additional Material: 7 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140310
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  • 91
    Electronic Resource
    Electronic Resource
    Study of ethylene oligomerization (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 357-370 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study was made of the oligomerization of ethylene, initiated by the thermal decomposition of azoethane and azo-isopropane at low temperatures, where the polymerization equilibria are shifted somewhat in the direction of the formation of products with longer carbon chains. The findings supported the picture acquired from a study of the propionaldehyde-ethylene system. Also under these conditions the oligomerization proceeds via addition between the ethylene and radicals, followed by isomerization and decomposition of the longer radicals, with a tendency to yield propylene and longer olefins. At the lower temperatures the decomposition of radicals with shorter carbon chain becomes less important in comparison with their addition reactions and, in spite of the otherwise identical mechanism, this leads to a different product distribution.
    Additional Material: 11 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550140404
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  • 92
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    Electronic Resource
    Base-catalyzed isomerization of phenylpropenes (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 351-356 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The prototropic rearrangement of 3-phenyl-1-propenes to the corresponding 1-phenyl-1-propenes was investigated in basic media utilizing 0.1M sodium ethoxide in absolute ethanol at 81°C. It was found that the effect of substituents on the rate of such isomerizations follows the order: p-NO2 〉 o-Cl 〉 m-Cl ≥ m-F 〉 p-Br 〉 o-CH3 〉 m-CH3 〉 m-CH(CH3)2 〉 p-CH(CH3)2 ≥ p-C(CH3)3 〉 o-OCH3. This is consistent with first-order kinetics and “BSE1” mechanism. Quantitative treatment in terms of Hammett's equation showed a straight line, with a slope (p value) of +2.25. An increase in the strength of the base was also found to cause an increase in the rate of isomerization.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550140403
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  • 93
    Electronic Resource
    Electronic Resource
    Masthead (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140501
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  • 94
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    Electronic Resource
    Kinetics and mechanism of the oxidation of n-acetyl l-cysteine by 2,6-dichloroindophenol in methanol-water medium (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 451-456 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The principal reactants interact in a molar ratio of 2:1 forming dihydroindophenol and the corresponding disulfide. The order of reaction is unity with respect to each reactant, namely, N-acetyl L-cysteine and indophenol. The rate shows an inverse linear relation with hydroxyl ions. It is not influenced by the variation in the initial concentration of indophenol. The rate increases on adding the salts possessing a cholinergic effect and the neutral electrolytes, as well as on increasing the dielectric constant of the medium. The products, namely, N-acetyl L-cystine (disulfide) and the leuco dye, do not influence the rate. A low energy and a highly negative entropy of activation (4.11 kcal/mol and -60.49 e.u., respectively) suggest the formation of an outer sphere complex as the rate-determining step.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550140502
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  • 95
    Electronic Resource
    Electronic Resource
    The reaction of O(3P) with H2O2 (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 471-478 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant for the reaction of O(3P) with H2O2 was measured as a function of temperature and the [H2O2]0/[O]0 ratio. The numerical solution of the appropriate rate equations was used to arrive at a mechanism which adequately describes our results and the rather divergent data in the literature. A recommended expression for the temperature dependence of the absolute rate constant is presented from consideration of the available experimental data.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550140504
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  • 96
    Electronic Resource
    Electronic Resource
    Direct detection of CF2 and computer modeling of its appearance in the fluorination of CH2F2 (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 457-469 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The branched chain reaction between CH2F2 and F2 is studied in a miniature tubular reactor having a diameter of 1.1 mm. The gases at the end of the tube expand into a low-pressure chamber and are analyzed by molecular beam detection. The branching intermediate CF2 is detected directly at low ionization energies. An approximate quantitative reaction model for the fluorination of CH2F2 is proposed and discussed. The influence of the unknown rate constants in this scheme on the course of the reaction is examined. For the most reasonable set of rate constants the unknown rate constant for the branching reaction CF2 + F2 → CF3 + F at 550 K is found to be log k = 10.7 [cm3/mol·s].
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550140503
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  • 97
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    Electronic Resource
    A kinetic study of the reaction between formic acid and HoBr (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 479-485 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction between formic acid and HOBr in strongly acid aqueous media was studied by absorption spectrophotometry at 298 K. Bromine, the monitored species, displays a transient behavior, gradually rising up to a maximum and then decaying with first-order kinetics. Reaction rates, expressed as R = -dCBr2/dt, depend on the concentrations of HCOOH (0.1-1.4M), HOBr (0.3-1.5 × 10-3 M), and H+ (0.1-1.0M). The mechanism with k1 =1.04 ± 0.20M-1· s-1, k3 = 20.2M-1, quantitatively accounts for all observations within experimental error.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140505
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  • 98
    Electronic Resource
    Electronic Resource
    Reaction of hydrogen atoms and O2(1Δg) (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 487-497 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of atomic hydrogen with O2(1Δg) has been investigated as a function of temperature, using a fast discharge-flow apparatus equipped for EPR detection of free radical species. The rate constant for the overall reaction was measured as (1.46 ± 0.49) × 10-11 exp(-4000 ± 200 cal/mol/RT) cm3/s. Evidence is presented which suggests that the reaction occurs principally via abstraction, H + O2(1Δg) → OH + O, rather than via physical quenching, H + O2(1Δg) → H + O2(X3Σg-).
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140506
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  • 99
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    Electronic Resource
    Laser-induced chemical kinetics: Absolute rate constants for the reactions Ċ2F2 + Br2 → C2F5Br + Ḃr and n-Ċ3F7 + Br2 → n-C3F7Br + Ḃr (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 499-506 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate constants at room temperature for the metathesis reaction have been measured under VLPP conditions: k1 = (2.0 ± 0.5) × 108M-1·s-1, k2 = (3.0 ± 0.7) × 108M-1·s-1. The radicals were generated through collisionless infrared-multiphoton decomposition of the corresponding iodides by irradiation from a high-power CO2-TEA laser. The reaction of Ċ2F5 and Ċ3F7 with \documentclass{article}\pagestyle{empty}\begin{document}$$\mathop {\rm N}\limits^{\rm .} {\rm O}_{\rm 2} $$\end{document} are briefly discussed in relation to the reaction of Ċ3 with \documentclass{article}\pagestyle{empty}\begin{document}$$\mathop {\rm N}\limits^{\rm .} {\rm O}_{\rm 2} $$\end{document}, which had been measured previously.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140507
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  • 100
    Electronic Resource
    Electronic Resource
    Rate constants for the reaction of OH radicals with a series of alkanes and alkenes at 299 ± 2 K (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 507-516 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using methyl nitrite photolysis in air as a source of hydroxyl radicals, relative rate constants for the reaction of OH radicals with a series of alkanes and alkenes have been determined at 299 ± 2 K. The rate constant ratios obtained are: relative to n-hexane = 1.00, neopentane 0.135 ± 0.007, n-butane 0.453 ± 0.007, cyclohexane 1.32 ± 0.04; relative to cyclohexane = 1.00, n-butane 0.341 ± 0.002, cyclopentane 0.704 ± 0.007, 2,3-dimethylbutane 0.827 ± 0.004, ethene 1.12 ± 0.05; relative to propene = 1.00, 2-methyl-2-butene 3.43 ± 0.13, isoprene 3.81 ± 0.17, 2,3-dimethyl-2-butene 4.28 ± 0.21. These relative rate constants are placed on an absolute basis using previous absolute rate constant data and are compared and discussed with literature data.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550140508
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