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  • Physical Chemistry  (243)
  • Wiley-Blackwell  (243)
  • Institute of Physics
  • Nature Publishing Group
  • Taylor & Francis
  • 1980-1984  (243)
  • 1960-1964
  • 1925-1929
  • 1983  (117)
  • 1982  (126)
Collection
Keywords
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  • Wiley-Blackwell  (243)
  • Institute of Physics
  • Nature Publishing Group
  • Taylor & Francis
Years
  • 1980-1984  (243)
  • 1960-1964
  • 1925-1929
Year
  • 1
    Electronic Resource
    Electronic Resource
    Formation of nitrous acid and nitric oxide in the heterogeneous dark reaction of nitrogen dioxide and water vapor in a smog chamber (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1013-1029 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dark reaction of NOx and H2O vapor in 1 atm of air was studied for the purpose of elucidating the recently discussed unknown radical source in smog chambers. Nitrous acid and nitric oxide were found to be formed by the reaction of NO2 and H2O in an evacuable and bakable smog chamber. No nitric acid was observed in the gas phase. The reaction is not stoichiometric and is thought to be a heterogeneous wall reaction. The reaction rate is first order with respect to NO2 and H2O, and the concentrations of HONO and NO initially increase linearly with time. The same reaction proceeds with a different rate constant in a quartz cell, and the reaction of NO2 and H218O gave H18ONO exclusively. Taking into consideration the heterogeneous reaction of NO2 and H2O, the upper limit of the rate constant of the third-order reaction NO + NO2 + H2O → 2HONO was deduced to be (3.0 ± 1.4) × 10-10 ppm-2-min-1, which is one order of magnitude smaller than the previously reported value. Nitrous acid formed by the heterogeneous dark reaction of NO2 and H2O should contribute significantly to both an initially present HONO and a continuous supply of OH radicals by photolysis in smog chamber experiments.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550151006
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  • 2
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of the reactions of the superoxide ion in solutions. I. Absorption spectra and interaction with solvents and cations (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1045-1056 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absorption spectra of the superoxide ion have been studied in dimethylformamide (DMF) and acetonitrile (AN). It was found that the superoxide ion existed in equilibrium with an ion pair in AN (Keq = 20M-1, Bu4N+ is the cation) and as “free” (solvated) ion in DMF. The addition of DMF caused the destruction of an ion pair in AN. The addition of the proton donors HX (water or ethanol) to the \documentclass{article}\pagestyle{empty}\begin{document}${\rm O}_{\rm 2}^{\overline {\rm .} }$\end{document} solutions in DMF and AN caused the formation of new ion pairs (Bu4N+\documentclass{article}\pagestyle{empty}\begin{document}${\rm O}_{\rm 2}^{\overline {\rm .} }$\end{document})2HX. The equilibrium constants of these ion pairs were determined in DMF and AN.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550151008
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  • 3
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of the reactions of the superoxide ion in solutions. III. Kinetics and mechanism of the reaction of the superoxide ion with ethyl acetate in dimethylformamide, acetonitrile, and their mixtures (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1063-1068 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction of the superoxide ion with ethyl acetate have been studied in DMF, AN, and their mixtures. It was shown that the rate constants depend on the ethyl acetate concentration, which indicates the formation of an intermediate in this process. Equilibrium constants for the process of the intermediate formation and the rate constants for its decay have been determined. It is concluded that aprotic solvents affect mainly the stage of the intermediate decay in this reaction.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550151010
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  • 4
    Electronic Resource
    Electronic Resource
    Kinetic and equilibrium study of gas-phase interconversions of 1,3,6-cyclooctatriene, 1,3,5-cyclooctatriene and bicyclo[4.2.0]octa-2,4-diene (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1069-1080 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase equilibrium and rate constants for the isomerizations of 1,3,6-cyclooctatriene (136COT) to 1,3,5-cyclooctatriene (135COT) [reaction (1)] and bicyclo[4.2.0]octa-2,4-diene (BCO) to 135COT [reaction (-2)] have been measured between 390 and 490 K and between 330 and 475 K, respectively. The rate constant of reaction (1) obeys the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm 1} = 10^{10.93 \pm 0.08} {\rm exp}[- (115.9 \pm 0.7{\rm kJ}/{\rm mol})/RT]{\rm s}^{ - 1}$$\end{document} The corresponding equilibrium constant is given by the van′t Hoff equation \documentclass{article}\pagestyle{empty}\begin{document}$${\rm In K}_{\rm 1}^{\rm 0} = (0.24 \pm 0.04) + (13.78 \pm 0.15{\rm kJ}/{\rm mol})/RT$$\end{document} The strain energy of the 136COT ring is calculated to be 31.7 kJ/mol, based on the known value of 37.2 kJ/mol for 135COT, and ΔHf0(298 K) for gaseous 136COT is 196.3 kJ/mol. The rate constant of reaction (-2) obeys the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm - 2}} = 10^{12.38 \pm 0.23} {\rm exp}[(- 106.9 \pm 1.5{\rm kJ}/{\rm mol})/RT]{\rm s}^{ - 1}$$\end{document} The equilibrium constant for 135COT ⇆ BCO fits the van′t Hoff equation \documentclass{article}\pagestyle{empty}\begin{document}$${\rm In K}_{\rm 2}^{\rm 0} = (- 1.20 \pm 0.02) - (0.40 \pm 0.07{\rm kJ}/{\rm mol})/RT$$\end{document} The strain energy of the BCO skeleton is calculated to be 108.3 kJ/mol, and ΔHf0(298 K) for gaseous BCO is 183.3 kJ/mol.
    Additional Material: 5 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550151011
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  • 5
    Electronic Resource
    Electronic Resource
    The azoethane-initiated thermal reaction of isobutene. Heat of formation of the 2-methyl-2-pentyl radical (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1133-1145 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The azoethane-sensitized thermal reaction of isobutene has been studied at 526-565 K. The initial concentrations of azoethane and isobutene were in the ranges of 1.40-10.5 × 10-4 and 6.78-26.6 × 10-4 mol/dm3, respectively. From the initial rates of formation of ethane and 2-methylpentane the heat of formation of the 2-methyl-2-pentyl radical was determined. The result obtained is ±Hf0(2-methyl-2-pentyl) = 0.8 ± 2.0 kcal/mol. The entropy of the radical, obtained from statistical mechanical calculations and experimentally, is S0(2-methyl-2 pentyl) = 92.8 ± 1.5 cal/mol°K. The results support the high heat of formation of the t-butyl radical suggested by different authors.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550151103
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  • 6
    Electronic Resource
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    Gas-phase thermal isomerization of hexachlorocyclopropane (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1179-1187 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase thermal isomerization of hexachlorocyclopropane to hexachloropropene at 208-283°C is first order and unaffected by changes in the surface-to-volume ratio or by the addition of iodine, tetrachloroethylene, and oxygen. The first-order rate constants fit the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log}k({\rm s}^{ - 1}) = (15.74 \pm .022) - (45,660 \pm 526)/4.576T$$\end{document} The reaction was interpreted as an unimolecular process taking place with chlorine atom migration. A comparison of the reactivities of several chlorocyclopropanes is made.
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    URL: http://dx.doi.org/10.1002/kin.550151106
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  • 7
    Electronic Resource
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    Shock-tube determination of the rate coefficient for the reaction CN + HCN → C2N2 + H (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1237-1241 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550151110
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  • 8
    Electronic Resource
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    Announcement (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1244-1244 
    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.550151112
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  • 9
    Electronic Resource
    Electronic Resource
    Pyrolysis of 5-chloropentan-2-one and 4-chloro-1-phenylbutan-1-one. Participation of the carbonyl group (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1275-1282 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates of elimination of 5-chloropentan-2-one and 4-chloro-1-phenylbutan-1-one in the gas phase have been determined in a static system, seasoned with allyl bromide, and in the presence of the chain inhibitor propene. The reactions are unimolecular and follow a first-order rate law. The working temperature and pressure ranges were 339.4-401.1°C and 46-117 torr, respectively. The rate coefficients for the homogeneous reactions are given by the following Arrhenius equations: for 5-chloropentan-2-one, log k1(s-1) = (13.12 ± 0.88) - (207.8 ± 11.0)kJ/mol/2.303RT; and for 4-chloro-1-phenylbutan-1-one, log k1(s-1) = (12.28 ± 1.09) - (185.2 ± 12.0)kJ/mol/2.303RT. The carbonyl group at the γ position of the C—Cl bond of haloketones apparently participates in the rate of pyrolysis. The five-membered conformation appears to be a favorable structure for anchimeric assistance of the C=O group in the gas-phase elimination of chloroketones.
    Additional Material: 6 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550151203
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  • 10
    Electronic Resource
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    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.
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    URL: http://dx.doi.org/10.1002/kin.550140402
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  • 11
    Electronic Resource
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    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.
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    URL: http://dx.doi.org/10.1002/kin.550140405
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  • 12
    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.
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    URL: http://dx.doi.org/10.1002/kin.550140409
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  • 13
    Electronic Resource
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    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 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The flash photolysis 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.
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    URL: http://dx.doi.org/10.1002/kin.550140408
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  • 14
    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 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550140410
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  • 15
    Electronic Resource
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    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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  • 16
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    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.
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    URL: http://dx.doi.org/10.1002/kin.550140607
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  • 17
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    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 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reaction has been investigated in the temperature range of 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.
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    URL: http://dx.doi.org/10.1002/kin.550140609
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  • 18
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    The oxidation of diethylhydroxylamine by nitrogen dioxide (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 699-710 
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    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).
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    URL: http://dx.doi.org/10.1002/kin.550140611
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  • 19
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    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 
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    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.
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    URL: http://dx.doi.org/10.1002/kin.550140707
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  • 20
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    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 
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    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.
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    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 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/kin.550140709
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    Masthead (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982) 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/kin.550140801
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  • 23
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    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 
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    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.
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    Electronic Resource
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    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 
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    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.
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    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 
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    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.
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  • 26
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    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.
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    Electronic Resource
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    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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    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.
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    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-.
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    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 
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    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.
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    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 
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    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.
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    Mechanism of the hydroxyiodination of 2-butenoic acid (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 927-932 
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    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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    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 
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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 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.
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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
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    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 
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    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.
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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 
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    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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    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 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and mechanism of 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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    Announcement (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 107-107 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Kinetics of the gas-phase reactions of OH radicals with a series of α,β-unsaturated carbonyls at 299 ± 2 K (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 75-81 
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    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 α,β-unsaturated carbonyls 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 propene of 2.52 × 10-11 cm3/molec·s, the rate constants obtained are (× 1011 cm3/molec·s: acrolein, 1.83 ± 0.13; crotonaldehyde, 3.50 ± 0.40; methacrolein, 2.85 ± 0.23; and methylvinylketone, 1.88 ± 0.14). These data, which are necessary input to chemical computer models of the NOx-air photooxidations of conjugated dialkenes, are discussed and compared with literature values.
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    Induced heterogeneity, a novel technique for the study of gas-phase reactions. Part I. Determination of the arrhenius parameters for C—C bond scission in propane (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 63-73 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that, by deliberate activation of the reaction vessel, heterogeneous reaction at the wall can be made to dominate chain termination in a complex gas-phase reaction. For a homogeneous process, characterized, as is often the case, by multiple terminations, this has the effect of simplifying the mechanism and allowing explicit solution of the relevant steady-state equations so that the rate constants of some individual steps can be evaluated without assumption as to the values of those of others.The pyrolysis of propane, in the vicinity of 500°C, has been used as an example of this approach. Enhancement of the wall activity leads to the reaction providing, almost exclusively, chain termination. As a result, rate constants for the initiation step can be directly determined. The results of this study provide the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_1 (s^{ - 1}) = 16.71 \pm 0.54 - 83400 \pm 1950{\rm cal}/{\rm mol}/2.303RT $$\end{document} In combination with current thermochemical values this result gives k-1 = 1013.40 cm3/mol·s which, in turn, implies, via the geometric mean rule, kEt-Et = 1012.9 cm3/mol·s for ethyl-ethyl recombination, in good accord with the most recent determinations and compatible with the newly proposed value of the enthalpy of formation of ethyl.The first-order wall constant k8 has been evaluated as k8〈104.2 s-1. This appears to be the first occasion on which a wall constant has been evaluated from data for a high-temperature complex gas reaction.
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    Kinetics of the reaction: 2C2H4 → C2H5 + C2H3· heat of formation of the vinyl radical (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 83-104 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The initial rates of formation of the major products in the thermal reactions of ethylene at temperatures in the neighborhood of 800 K have been measured in the presence and absence of the additives neopentane and ethane. It has been shown that in the absence of the additive the main initiation process is while in the presence of neopentane and ethane the following additional initiation processes occur: From the ratios of the rates of formation of the major products in the presence and absence of the additive the ratios kN/k1 and kE/k1 were measured over the temperature range of 750-820 K. Taking values from the literature for kN and kE, the following value was obtained for k1: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_1 ({\rm L}/{\rm mol} \cdot {\rm s}) = 11.27 \pm 0.6 - \frac{{64,200 \pm 2000}}{{2.3RT}} $$\end{document} Previous results using butene-1 as additive were rexamined and shown to be consistent with this measurement. From this measurement the following values were derived: ΔHf(C2H3) = 63.4 ± 2 kcal/mol and D(C2H3—H) = 103 kcal/mol.
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    Masthead (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983) 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150201
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    Kinetics of benzene photochlorination (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 119-128 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An empirical approach to the kinetic investigations of photo-initiated liquid-phase chlorination of benzene is presented. Reaction order and the reaction constants for chlorine consumption and for the production of hexachlorocyclohexane isomers were evaluated from experimental data.
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    Kinetics and thermochemistry of electron attachment to SF6 (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 109-117 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermochemical analysis of the electron capture process of SF6 leads to a rate constant for the reverse process \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm SF}_6^ - \mathop \to \limits^2 {\rm SF}_6 + e^ -,k_2 = 1.5 \times 10^{13 - 31.4/\theta } {\rm s}^{{\rm - 1}} $\end{document}, where θ = 2.303RT, in kcal/mol. The electron affinity of 32±3 kcal/mol is deduced from the observed bimolecularity of the capture process down to 0.1 torr Ar bath gas and estimated entropies of SF6 and SF6-. The capture process is discussed from the view point of the formation of a metastable SF6- electron (SF6·eL-) Langevin complex which appears to have a lifetime of about 2 × 10-13 s. Curve crossing from the SF6·eL- complex to vibrationally excited (SF6-)* appears to have a normal rate and A factor. This is interpreted to indicate near-resonant coupling between the orbiting electron and the vibronic motions of SF6, together with similarity in structure of SF6 and SF6-. It is shown that the apparent slowness of thermal electron ejection from SF6- is a result of an unfavorable equilibrium constant rather than a slow rate.
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    Kinetics of oxidation of some meta- and para-substituted phenyl methyl sulfoxides by chloramine-T in buffered ethanol-water (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 129-139 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of oxidation of methyl phenyl sulfoxide by chloramine-T (CAT) has been studied in buffered ethanol-water (1:1 v/v) of pH 7.0. The reaction was found to follow no simple-order kinetics. A possible mechanism is suggested involving three rate-controlling steps: (1) the reaction between RNHCl (R = CH3C6H4SO2) and the sulfoxide, (2) the disproportionation of RNHCl, and (3) the reaction between RNCl2 and the sulfoxide. A mixed-order rate law is derived as rate/[C][SO] = k1 + Kdk2[C]/[SA]. The rate law is found to be obeyed for the meta- and para-substituted phenyl methyl sulfoxides also. The ρ value is obtained using Hammett's σ constants. The ρ values obtained for the attack of both RNHCl and RNCl2 with the sulfoxides are almost the same, showing that both are converting the sulfoxide to the same intermediate. A chlorinium ion transfer is suggested.
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    Thermal dehydration kinetics of disaccharides (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 141-149 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The vacuum decomposition of sucrose and cellobiose has been observed in the 150-250°C temperature range. The predominant decomposition product of both sugars is H2O with less than 5% CO, CO2, CH2O, CH3CHO, CH3OH, and C2H5OH formed. The detailed rates and temperature dependences suggest that with the possible exception of C2H5OH, the minor products are formed in secondary reactions of the dehydration products. Further it is shown that the so-called “melting with decomposition” of a sugar is in reality a high-temperature dissolution of the disaccharide in the eliminated water.
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    Complex rate law for the cerium(IV) oxidation of glycolic acid in the medium HClO4-Na2SO4-NaClO4 (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 417-432 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the cerium(IV) oxidation of glycolic acid have been studied in the medium HClO4—Na2SO4—NaClO4 at varying organic substrate (HL), hydrogen, and bisulfate ion concentrations at 25.0°C and ionic strength 2.0M. Under the experimental conditions used (0.03 ≤ [H+] ≤ 0.5M; 0.02 ≤ [HSO4-] ≤ 0.1M; 0.01 ≤ [HL] ≤ 0.1M) the observed pseudo-first-order rate constant kobs has been found to follow the complex expression where the values of the various constants have been estimated by a nonlinear least-squares method. According to this expression the oxidation process occurs significantly through three simultaneous pathways. Moreover three equilibria involving cerium(IV) and HSO4- (or SO42-) ions are important from a kinetic point of view, whereas only two equilibria involving the corresponding complexes with the organic substrate are predominant.
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    The pyrolysis kinetics of ethyl esters in the gas phase. The alkyl substituent effect at the acyl carbon (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 455-459 
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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 elimination of ethyl 3-methylbutanoate and ethyl 3,3-dimethylbutanoate has been studied, in a static system, over the temperature range of 360-420°C and in the pressure range of 71-286 torr. The reactions are homogeneous, unimolecular, and follow a first-order rate law. The temperature dependence of the rate coefficients is given by the following Arrhenius equations: for ethyl 3-methylbutanoate, log k1 (s-1) = (12.70 ± 0.36) - (202.5 ± 4.4) kJ/mol/2.303RT, and for ethyl 3,3-dimethylbutanoate, log k1 (s-1) = (13.04 ± 0.08) - (207.1 ± 1.0) kJ/mol/2.303RT. Alkyl substituents at the acyl carbon of ethyl esters yield very close values in rates. Consequently it is rather difficult to offer some conclusion concerning the effect of these substituents.
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    Thermochemistry and kinetics of the reaction of methyl mercaptan with iodine (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 433-453 
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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 reaction CH3SH + I2 has been studied spectrophotometrically over the temperature range of 476-604 K. It was found that the reaction undergoes H abstraction by I at ≤575 K, leading to the formation of MeSI and followed by a secondary reaction which leads to the formation of MeSSMe: Taking into consideration the effect of reaction (2), the equilibrium constant K1 (554 K) has been evaluated to be 0.025 ± 0.004. This value was combined with the estimated values S2980 (CH3SI, g) = 73.7 ± 1.0 eu and 〈ΔCp1,5540〉 = 0.87 ± 0.3 eu to obtain ΔH1,2980 = 4.03 ± 0.73 kcal/mol. This yields ΔHf2980 (CH3SI, g) = 7.16 ± 0.73 kcal/mol when combined with known thermochemical values for CH3SH, HI, and I2. A kinetic study was vitiated by the concurrent heterogeneous reaction of MeSH and I2 at lower temperatures and the rather complicated chemistry occurring at elevated temperatures. However, attempts at measuring rate constants at 554 K lead to a lower limit of ΔHf2980 (CH3S·, g) ≥ 29.5 ± 2 kcal/mol when an estimated value of A = 1010.8 ± 0.2 L/mol·s for the reactionc is used. DH2980 (CH3S-I) is estimated to be 49.3 ± 1.7 kcal/mol. The bond strengths of some divalent sulfurs and the reaction mechanisms are discussed. A crude estimate of DH0(H-CH2SH) = 96 ± 1 kcal has been obtained from the kinetic data.
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    Electron transfer to trans-dihydroxotetraoxoosmate(VIII). II. Kinetics of the oxidation of dimethylsulfoxide in aqueous alkaline media (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 881-890 
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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 oxidation of dimethylsulfoxide by oxohydroxoosmate(VIII) complex ions in alkaline media follow pseudo-first-order disappearance in Os(VIII). The values of the observed pseudo-first-order rate constant are linearly dependent on initial dimethylsulfoxide concentrations in a fortyfold range, and increase with increasing [OH-], leveling off at higher relative [OH-]. The results are interpreted in terms of outer sphere interactions involving dimethylsulfoxide and various species of the Os(VIII) complex. The more nucleophilic dihydroxotetraoxoosmate(VIII) ion reacts about 50 times faster than the trihydroxotrioxoosmate(VIII) species.
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    Erratum (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 941-941 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    High-temperature determination of the rate coefficient for the reaction H2 + CN → H + HCN (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 915-923 
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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 coefficient of the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$(2){\rm H}_2 {\rm CN} \to {\rm H} + {\rm HCN}$$\end{document} has been determined in the temperature range of 2700-3500 K using a shock tube technique. C2N2—H2—Ar mixtures were heated behind incident shock waves and the early-time CN history was monitored using broad-band absorption spectroscopy. The rate coefficient providing the best fit to the data was \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm k = (7}{\rm .5}_{ - 2.0}^{{\rm + 2}{\rm .5}} {\rm)} \times {\rm 10}^{{\rm 13}} {\rm cm}^3 /{\rm mol} \cdot {\rm s} $$\end{document} in good agreement with extrapolations of previously published low-temperature results.
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    The reaction of cyclopentyl radicals with carbon tetrachloride (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 905-913 
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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 azocyclopentane in the presence of cyclopentane-carbon tetrachloride mixtures has been investigated in the gas phase. Product analysis data have been used to determine the Arrhenius parameters for the reactions \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {(4)_C - {\rm C}_5 {\rm H}_{9.} + {\rm CCl}_4 \to _C - {\rm C}_5 {\rm H}_9 + {\rm CCl}_{3.} } \hfill & {k_4 = 10^{9.0 \pm 0.6} {\rm exp}[- (10.3 \pm 1.0){\rm kcal}/{\rm mol}/{\rm RT}]} \hfill \\ {(6){\rm CCl}_{3.} + _C - {\rm C}_5 {\rm H}_{10} \to {\rm CCl}_3 {\rm H} + _C - {\rm C}_5 {\rm H}_{9.} } \hfill & {k_6 = 10^{8.4 \pm 0.4} {\rm exp}[- (10.0 \pm 0.7){\rm kcal}/{\rm mol}/{\rm RT}]} \hfill \\ \end{array}$$\end{document} The rate data for chlorine atom abstraction from CCl4 by the cyclopentyl radical were compared with available data for other alkyl radicals in both the gas and the solution phases. The results indicate that the rate constant for chlorine atom abstraction in the gas phase is fairly insensitive to the nature of the attacking alkyl radical and that the activation energy for a secondary radical is about 4 kcal/mol higher than the corresponding reaction in the solution phase.
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    Masthead (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Kinetics and mechanism of the cerium (IV) oxidation of α-Hydroxycycloalkanecarboxylic acids and cyclic alcohols in acidic perchlorate media (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 925-940 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Ce(IV) oxidation of the five-, six-, and seven-membered ring α-hydroxycycloalkanecarboxylic (C5, C6, and C7) acids to the corresponding cyclic ketones has been studied in acidic perchlorate media. The data may be interpreted in terms of a mechanism which involves fast preequilibrium complexation steps between Ce(IV) and the hydroxy acids, yielding two complexes which differ only by a proton. Complexation is followed by rate-determining decarboxylation to an intermediate (free radical?), which reacts quickly with another Ce(IV) to give products. Of the two proposed complexes, the protonated one is virtually unreactive. The C7 ring acid is oxidized more rapidly than the C6 acid, which, in turn, is oxidized faster than the C5 acid.For comparison, the oxidation of the five-, six-, and seven-membered ring cyclic alcohols to the corresponding cyclic ketones by Ce(IV) in acidic perchlorate was also studied. The order of reactivity is cyclopentanol 〉 cycloheptanol 〉 cyclohexanol. The differences in observed reactivities between the hydroxy acids and the cyclic alcohols are explained in terms of differences in transition state structure.The stepwise hydrolysis constants of Ce(IV) leading to Ce(OH)3Plus; and Ce(OH)22+ were determined. In the case of the hydroxy acids, evidence is in favor of Ce(OH)3+ as the reactive ceric species in aqueous acidic perchlorate media.
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    Masthead (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    A Mass-spectrometric study of propionaldehyde oxidation in the negative temperature coefficient region (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 997-1012 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of propionaldehyde has been investigated in a 1-L Pyrex reactor at total pressures of 50-120 torr and temperatures 553-713 K. Detection of reactants and products was principally by molecular beam mass spectrometry, although certain species could only be measured by gas-chromatographic analysis. At 553 K the yield of water was ∼83% of the propionaldehyde consumed, leading to the conclusion that OH is the principal chain carrier near the beginning of the negative temperature coefficient region. Many oxygenated organics (CH2O, CH3CHO, C2H5OH, C2H5O2H, CH3O2H) and C2H4 are formed during the oxidation process. These oxidation products are consistent with the important role of O2 addition to C2H5 radicals at 553 K followed by subsequent reactions of the C2H5O2 radical. As the temperature is increased, the product concentrations smoothly change to a much simpler distribution in which C2H4, H2O2, and CO are the dominant products.
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    Studies in nickel(IV) chemistry. Kinetics of electron transfer from dimethyl sulfoxide to oxohydroxonickel(IV) in aqueous acid medium (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 945-958 
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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 decomposition of “oxohydroxonickel(IV)” [Ni(IV)] with concomitant intramolecular electron transfer to produce hexaaquanickel(II) and dioxygen in aqueous acid solutions show pseudo-first-order dissappearance of the Ni(IV). The pseudo-first-order rate constants for the acid decomposition (kad) satisfy \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm ad}} = k_{\rm d} {\rm K}_{{\rm MH}} [{\rm H}^ +]/(1 + {\rm K}_{{\rm MH}} [{\rm H}^ +])$$\end{document} where KMH and kd refer to the equilibrium protonation constant and the decomposition constant of the protonated species of the Ni(IV) respectively. The values of KMH and kd in aqueous medium at 45°C and μ = 2.0M are 25.5 ± 1M-1 and (1.7 ± 0.1) × 10-5 s-1, respectively.The kinetics of the intermolecular electron transfer from dimethyl sulfoxide (DMSO) to the Ni(IV), producing Ni(H2O)62+ and dimethyl sulfone as products, have been investigated by monitoring the formation of Ni(H2O)62+. The pseudo-first-order rate constants for the electron transfer kobs are linearly dependent on [DMSO]0 or [H+], attaining limiting values at higher relative [DMSO]0 or [H+], in accordance with \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm obs}} = \frac{{[{\rm DMSO}]_0 }}{{1 + K_{{\rm MH}} [{\rm H}^ +]}}\left({\frac{{k_{1{\rm x}} K_{1{\rm c}} }}{{1 + K_{1{\rm c}} [{\rm DMSO}]_0 }} + \frac{{k_{2{\rm x}} K_{2{\rm c}} }}{{1 + K_{2{\rm c}} [{\rm DMSO}]_0 }}} \right)$$\end{document} where K1c and K2c represent the formation constants of the precursors involving DMSO and the unprotonated and one-protonated Ni(IV) species, respectively, and k1x and k2x are the corresponding decomposition rate constants of the precursors. The values of K2c and k2x are (2.3 ± 0.1) × 104M-1 and 19 ± 1 s-1, respectively, at 45°C and μ = 1.0M. Results are interpreted in terms of probable mechanisms involving (1) a rate-determining decomposition of the protonated Ni(IV) followed by rapid product formation steps, and (2) precursor complex formation between DMSO and the unprotonated or the protonated species of the Ni(IV) followed by rate-determining decomposition with electron transfer.
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    Kinetics of the reaction between methane and iodine from 830 to 1150 K in the presence and absence of oxygen (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1031-1043 
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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 of methyl iodide was determined by radiochemical methods and by massspectroscopic analyses in mixtures of Ar-CH4-I2 and Ar—CH4—I2—O2, heated by a reflected shock wave to temperatures of 830-1150 K. The rate of formation of CH3I was consistent with the chain mechanism \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} {\rm I} + {\rm CH}_4 \to {\rm CH}_3 + {\rm HI} \\ {\rm CH}_3 + {\rm I}_2 \to {\rm CH}_3 {\rm I} + {\rm I} \\ \end{array}$$\end{document} where the indicated rate constant for reaction between I and CH4 is given by k2(cm3/mol · s) = 1014.17 exp(-32.9 ± 0.8 kcal/mol/RT). No effect on the reaction rate by the presence of O2 was detected. However, in one experiment at 1097 K with 3.86 mol % O2 the formation of CH2O was indicated by the mass-spectroscopic analysis, presumably from the reaction of O2 with CH3.
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    Kinetics and mechanism of the reactions of the superoxide ion in solutions. II. The kinetics of protonation of the superoxide ion by water and ethanol (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1057-1062 
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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 constants for the protonation of “free” (that is, solvated) superoxide ions by water and ethanol are equal to 0.5-3.5 ×10-3M-1·s-1 in DMF and AN at 20º. It has been found that the protonation rates for the ion pairs of \documentclass{article}\pagestyle{empty}\begin{document}${\rm O}_{\rm 2}^{\overline {\rm .} }$\end{document} with the Bu4N+ cation are much slower than those for “free” \documentclass{article}\pagestyle{empty}\begin{document}${\rm O}_{\rm 2}^{\overline {\rm .} }$\end{document}. It is suggested that the effects of aprotic solvents on the protonation rates of \documentclass{article}\pagestyle{empty}\begin{document}${\rm O}_{\rm 2}^{\overline {\rm .} }$\end{document} are mainly due to the fact that the proton donors form solvated complexes of different stability in these solvents.
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    Method for the measurement of diffusion coefficients of labile gas-phase species: The diffusion coefficient of O(3P) in He at 294 K (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1081-1097 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dispersion of a pulse of O(3P) atoms in flowing helium has been analyzed by a modification of Taylor's method in order to determine the diffusion coefficient. Atoms of O(3P) were produced in a flowing stream of helium by a pulsed microwave discharge of molecular oxygen. After traversing a known length of the flow tube, the arrival time distribution of the O(3P) atoms was obtained using a mass spectrometer. The value obtained for D0 at 294 K, where D0 = D[He], is (2.40 ± 0.06) × 1019 cm-1 ·s-1, which corresponds to a diffusion coefficient of (731 ± 18) cm2/s at 1 torr. In addition to D0, analysis of the arrival time distributions gives an estimate of the mean flow velocity for O atoms in helium. There was no significant difference between the value of the velocity found this way and that obtained from the mean bulk gas flow measurement. Thus for this system there is no evidence for a chromatographic effect for O(3P) atoms on the walls of the flow tube.
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    Nonlinear structure-reactivity correlations. The hydrolysis of 2,4,6-trinitrophenyl acetate catalyzed by general bases (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1099-1110 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hydrolysis of 2,4,6-trinitrophenyl acetate was studied in the presence of several carboxylic bases and tertiary amines. Carboxylic bases pyridine and imidazole react as nucleophilic catalysts, while 2,4-dimethyl and 2,4,6-trimethyl pyridine react as general-base catalysts. The nonlinear structure-reactivity correlations (log kcat versus log kOH and log kcat versus pK of the leaving group) for the series of aryl acetates are discussed, and it is suggested that there is a change in transition-state structure along the series.
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    Continuous-wave CO2 laser-induced dehydrochlorination of 1,1,1-trichloroethane. A hot-tube radical-chain reaction with a molecular mechanism (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1119-1123 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No ABSTRACT.
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    Kinetic study of the reactions of the hydroxyl radical with ethane and propane (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1111-1118 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate coefficients for the reactions of the hydroxyl radical with ethane (k1, 297-300 K) and propane (k2, 297-690 K) were measured using the flash photolysis-resonance fluorescence technique. The rate coefficient data were fit by the following temperature-dependent expressions, in units of cm3/molecule·s: k1(T) = 1.43 × 10-14T1.05 exp (-911/T) and k2(T) = 1.59 × 10-15T1.40 exp (-428/T). Semiquantitative separation of OH-propane reactivity into primary and secondary H-atom abstraction channels was obtained.
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    Methyl thiirane: Kinetic gas-phase titration of sulfur atoms in SX OY systems (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1127-1132 
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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 SO + SO →l S + SO2(2) was studied in the gas phase by using methyl thiirane as a titrant for sulfur atoms. By monitoring the C3H6 produced in the reaction \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm S} + {\rm CH}_3\hbox{---} \overline {{\rm CH\hbox{---}CH}_2\hbox{---} {\rm S}} \to {\rm S}_2 + {\rm C}_3 {\rm H}_6 (7) $\end{document}, we determined that k2 ≃ 3.5 × 10-15 cm3/s at 298 K.
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    Effects of ring strain on gas-phase rate constants. 2. OH radical reactions with cycloalkenes (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1161-1177 
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    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 cycloalkenes have been determined at 298 ± 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 isoprene of 9.60 × 10-11 cm3 molecule-1 s-1, the rate constants obtained were (X 1011 cm3 molecule-1 s-1): cyclopentene 6.39 ± 0.23, cyclohexene 6.43 ± 0.17, cycloheptene 7.08 ± 0.22, 1,3-cyclohexadiene 15.6 ± 0.5, 1,4 cyclohexadiene 9.48 ± 0.39, bicyclo[2.2.1]-2-heptene 4.68 ± 0.39, bicyclo[2.2.1] 2,5 heptadiene 11.4 ± 1.0, and bicyclo[2.2.2] 2 octene 3.88 ± 0.19. These data show that the rate constants for the nonconjugated cycloalkenes studied depend on the number of double bonds and the degree of substitution per double bond, and indicate that there are no obvious effects of ring strain energy on these OH radical addition rate constants. A predictive technique for the estimation of OH radical rate constants for alkenes and cycloalkenes is presented and discussed.
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    Recombination rates of chlorine atoms in flash photolysis of chlorine molecules (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1235-1236 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/kin.550151109
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    Chemical dynamics via molecular beam and laser techniques, by R. B. Bernstein. No publisher supplied (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1243-1243 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/kin.550151111
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    Catalytic isomerization of 1-hexene on hy zeolite (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1249-1274 
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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 of 1-hexene on 70/80 mesh HY zeolite was studied at 200°C. The observed reaction products are formed via a variety of processes including double bond shift, cis-trans isomerization, skeletal rearrangement, cracking, hydrogen transfer, polymerization, cyclization, and coke formation. By applying the time-on-stream theory, the products have been classified as primary, secondary, or both, according to their OPE curves on product selectivity plots. 2-Ethyl-1-butene, which is present as an impurity in the feed, is found to react about 30 times faster than 1-hexene. Both 2-hexenes and 3 hexenes are formed primarily from 1-hexene, while 3 methyl 2 pentenes and 3-methyl-1-pentene formed from 2-ethyl-1-butene. The ratio of the initial rate of deprotonation to that of hydrogen shift in these reactions is ∼15 and ∼100, respectively. All products of skeletal rearrangement are observed to be secondary. Cracking products are produced mainly from precoke, which is also the source of hydrogen in the formation of paraffins. A detailed reaction network along with its associated mechanisms are presented and discussed.
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    Kinetics and mechanism of photochemical reactions of peroxomonosulfate in the presence and absence of 2-propanol (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1301-1310 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photochemical decomposition of peroxomonosulfate (PMS) in the presence and absence of 2-propanol at 25°C was found to obey an overall first-order rate - d[PMS]/dt = kφ[PMS]. In the absence of 2-propanol, the quantum yield ≤ for the decomposition of PMS was found to depend upon the concentration of PMS at [PMS] 〉 2 × 10-M, and is independent of concentration at [PMS] 〉 2 × 10-2M. The quantum yield in the presence of 2-propanol was found to be 3.03 at [PMS] = 1 × 10-2M and 4.45 at higher concentrations of PMS. In the pH range of 2-9.0 the quantum yield was found to be independent of pH, and the overall rate constant kφ was found to be 6.49 × 10-3 s-1 and 1.68 × 10-3 s-1, respectively, in the presence and absence of isopropanol. A suitable chain mechanism is proposed and explained.
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    Kinetics and mechanism of the decomposition of N-brominated alanine in aqueous solution (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1321-1328 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aqueous bromine reacts with alkyl-sidechain amino acids through a series of steps resulting in the formation of the corresponding alkyl aldelydes and nitriles. The kinetics and the mechanism of the interaction of bromine with alanine are examined. The products and the rates of this reaction are dependent in a complex way on the initial reactant concentration and pH. Acetaldeyde production is favored at low bromine-to-alanine ratios, low bromine concentrations, and pH values above 6. The first-order rate constant for the formation of acetaldelyde from alanine under these conditions is k4 = 1.98 × 1015 e-22,500/RT min-1. At higher concentration the nitrile is formed through a bromoimine intermediate. Under most conditions the nitrile appears to form from a catalyzed decomposition of the bromoimine which is too fast to be followed by the methods used in this study. However, residual amounts of the bromoimine decay by a slower first-order mechanism. The rate constant for this slower reaction in the case of alanine at pH 6.8-6.9 and alanine concentrations of 1 × 10-4M is k6 = 1.75 × 105 e-10,400/RT min-1.
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    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 
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    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.
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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 
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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 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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    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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    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 
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    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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    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 
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    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 
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    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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    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 
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    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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    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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    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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    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.
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    Reaction of hot H atoms with CDCl3 (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1105-1112 
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    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.
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    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 
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    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.
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    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 
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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 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.
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    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 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of oxidation of 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.
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    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 
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    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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    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 
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    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.
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    A novel kinetic and mechanistic study of the oxidation of pinacol by acid bromate - homogeneous catalysis of maganous ions (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 307-321 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed kinetic study of the Mn(II)-catalyzed and -uncatalyzed oxidation of pinacol by bromate has been carried out in aqueous acetic acid media containing Hg(II) ions. The uncatalyzed reaction exhibits 1.5 order that is, 0.5 order in [pinacol] and 1.0 in [bromate]. A decrease in k1 by increasing [bromate] has been accounted for due to the formation of Br2O5, which is inactive toward reduction. Mn(II)-catalyzed oxidation follows first order in [oxidant], 0.5 order in [manganous ion], and variable order with respect to [pinacol]. At lower [pinacol] (0.005-0.025M) the order is 0.5, but at higher concentration (0.03-0.15M) it becomes negative (-1.0). These observations can be accounted for qualitatively by the formation of 1:1 and 1:2 Mn(II)-pinacol complexes of which only 1:1 is active toward bromate oxidation. At higher [pinacol] the ratio of 1:2 and 1:1 complexes reached 98.2. All reactions were accelerated with acidity, and the rate constant follows the h0 function. Participation of H2O in the rate-limiting step and a free-radical mechanism were proposed for the manganous-ion-catalyzed reaction, whereas for the uncatalyzed reaction this was not true. The effects of NaClO4, Na4P2O7, and the dielectric constant of the media are also in accordance with the proposed mechanism.
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    Mechanism and thermochemistry of oxidation of HCl and HBr at high temperatures. The heat of formation of HO2 (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 341-380 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using currently available thermochemical and kinetic data and estimation methods to analyze the thermochemistry and the kinetic parameters of the elementary reactions involved in the oxidation of HCl and HBr, reaction mechanisms are proposed which account for the previously reported reaction products, the rate law, and the kinetic data. For oxidation of HCl, two competitive pathways, the radical initiation by hydrogen abstraction and the fourcenter reaction pathway, were invoked to account for the observations. In the oxidation of HBr one must invoke a fast surface reaction of the type \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm H}_2 {\rm O}_2 + {\rm HBr}({\rm S}) \to 2{\rm H}_2 {\rm O} + {\rm Br}_2 ({\rm g}) $$\end{document} to account for the reaction.
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    Masthead (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983) 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Investigation of the thermal isomerization of 1α,25-dihydroxycholecalciferolGeneric name is calcitriol. by nuclear magnetic resonance spectroscopy (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 381-395 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This investigation of the kinetics and thermodynamics of the thermal isomerization reaction of 1α,25-dihydroxycholecalciferol, the physiologically active metabolite of vitamin D3, is based on the simultaneous determinations of 1α,25-(OH)2D3 and its previtamin analog by nuclear magnetic resonance spectroscopy which distinguishes these compounds from possible impurities. The kinetics at different temperatures are used to obtain the activation parameters for the sigmatropic [1,7] thermal interconversion process which is shown to be compatible with a reaction that is unimolecular and concerted. The nature of the transition state of the activated complex, the reaction energetics, and the relative stabilities of 1α,25-(OH)2D3 and vitamin D3 are discussed.
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    The kinetics and mechanisms of elementary NF2 reactions with O and N atoms (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 399-415 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A combined EPR-LMR spectrometer with a fast-flow system has been used to investigate the kinetics and mechanisms of NF2 reactions with O and N atoms at 298 K. The overall rate constants of these reactions are: k0 = (2.8 ± 0.4) × 10-11 cm3/s and kN = (5.7 ± 0.8) × 10-11 cm3/s. The stoichiometry of the reactions with respect to O, N, NF2, F, and NO has been determined. The statistical theory of bimolecular reactions has been used for interpretation of the results obtained.
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    Kinetics of the thermal gas-phase dimerization of hexafluoropropene (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 537-546 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reversible thermal gas-phase dimerization of hexafluoropropene to the four isomeric cyclobutanes has been studied by pressure change and by gas-liquid chromatographic analysis in the temperature range of 645-708 K with initial pressures of olefin from 802 to 4820 mm Hg. The reaction was accurately second order at low conversions of olefin to dimers, and at higher conversions it gave a very good fit to the rate equation for opposing second- and first-order reactions. The rate constants for the dimerization, calculated from initial rates of reaction, yielded the least-mean-squares Arrhenius equation (95% confidence limits): \documentclass{article}\pagestyle{empty}\begin{document}$$ \log _{10} (k_2 /{\rm dm}^3 {\rm mol}^{ - 1} s^{ - 1}) = (5.93 \pm 0.40) - (131.8 \pm 9.5)k{\rm J\,\,mol}^{{\rm - 1}}/RT\ln \,10 $$\end{document} where k2 is defined by \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{ - 1/2{\rm d}[{\rm C}_3 {\rm F}_6]}}{{dt}} = \frac{{{\rm d}[c - {\rm C}_6 {\rm F}_{12}]}}{{dt}} = k_2 [{\rm C}_3 {\rm F}_6]^2 $$\end{document} Studies carried out in a packed vessel showed no evidence of heterogeneity. The rate constants found in this work are in excellent agreement with those found at lower pressures by Atkinson and Tsiamis, and the combined results give the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ \log _{10} (k_2 /{\rm dm}^{\rm 3} {\rm mol}^{{\rm - 1}} {\rm s}^{{\rm - 1}}) = (6.47 \pm 0.21) - (138.6 \pm 2.7){\rm kJ\,mol}^{{\rm - 1}} {\rm /}RT\ln 10 $$\end{document}
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    Studies in nickel(IV) chemistry. Kinetics of the Cu(II) ion-mediated acid decomposition of tris(dimethylglyoximato) nickelate(IV) in aqueous acidic medium (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 521-536 
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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 Cu(II) ion-mediated acid decomposition of tris (dimethylglyoximato)nickelate(IV), Ni(dmg)32- (dmg2- = dimethylglyoximate dianion), are reported in aqueous medium in the range of 3.6 ≤ pH ≤ 6.6 at 35°C and μ = 0.57 M. The pseudo-first-order rate constants of the disappearance of Ni(IV) kobs(M) satisfy the equation \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{{\rm obs(M)}} = k_{ad} + k_{dec(M)} $$\end{document} where kad refers to the pseudo-first-order rate constants for the proton-assisted decomposition of the Ni(IV) complex determined independently and is a function of [H+], and kdec(M) to that for the Cu(II) ion-mediated route and is a function of [H+] and [Cu2+]. Both kobs(M) and kdec(M) are found to increase with increasing [Cu(II)]0, tending to attain limiting values at higher relative [Cu(II)]0. At low [Cu(II)]0 the kdec(M) is found to register a decrease with increasing pH in the pH range of 3.6-4.4, then an increase in the range of 4.4-5.76, and again a decrease in the range of 5.76-6.6. Results on the Cu(II) ion-mediated acid decomposition are interpreted in terms of a probable mechanism involving pH-dependent adduct formation equilibria involving the one-protonated and the two-protonated species of Ni(IV) and the various species of Cu(II) ion in the media, followed by rate-determining acid decomposition of the adduct(s) to give Ni(II) aq. and Cu(dmgH)2. While the two-protonated Ni(IV) complex apparently reacts about five orders of magnitude faster than the one-protonated species, the aquacopper(II) reacts about two orders of magnitude slower than the hydroxoaquacopper(II).
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    Kinetics of the gas-phase reaction between iodine and monogermane and the bond dissociation energy D(H3Ge—H)A preliminary account of this work has appeared in [1] (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 547-560 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reaction has been investigated in the temperature range of 403-446 K. Monoiodogermane and di-iodogermane together with hydrogen iodide were the main products, although at high conversions at least one other product was formed. GeH3I is clearly the primary product. Initial rates were found to obey the rate law \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{{\rm d[I}_{\rm 2} {\rm]}}}{{{\rm dt}}} = \frac{{k[{\rm I}_{\rm 2}]^{1/2} [{\rm GeH}_{\rm 4}]}}{{1 + k'[{\rm HI}]/[{\rm I}_2]}} $$\end{document} over a wide range of initial iodine and monogermane pressures. Secondary reactions (of GeH3I with I2) affect the subsequent kinetics, although at sufficiently high initial reactant ratios ([GeH4]0/[I2]0 ≥ 100) an integrated rate equation fits the data with the same rate constants as the initial rate expression.The observed kinetics are consistent with an iodine atom abstraction chain mechanism, and for the step \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm I}^{\rm .} + {\rm GeH}_4 \mathop {\hbox to 24pt{\rightarrowfill}} {\hskip-16pt ^{{\rm1}}}{\hskip1em} {\rm \dot GeH}_{\rm 3} + {\rm HI} $$\end{document} log k1 (dm3/mol·s) = (11.03 ± 0.13) - (52.3 ± 1.0 kJ/mol)/RT ln 10 has been deduced. From this the bond dissociation energy D(GeH3—H) = 346 ± 10 kJ/mol (82.5 kcal/mol) is obtained. The significance of this value, together with derived values for Ge-Ge and Ge-C bond strengths, is discussed.
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    The kinetics and mechanism of thermal decomposition of alkyl isocyanates (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 609-618 
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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 gas-phase decomposition of ethyl, isopropyl, and t-butyl isocyanates have been studied in the temperature range of 380-530°C. t-Butyl isocyanate decomposes almost exclusively by a unimolecular route to isobutene and HNCO, but in EtNCO and i-PrNCO this route competes with a free-radical chain which produces CO, CH4, and HCN or CH3CN. In i-PrNCO, however, the chain process is very rapidly inhibited by the propene formed in the parallel unimolecular route. A minor heterogeneous bimolecular decomposition in each case gives rise to carbon dioxide and a carbodiimide. Mechanisms and trends in the alkyl isocyanates from methyl through t-butyl are discussed.
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    The gas-phase reaction of hydrazine and ozone: A nonphotolytic source of OH radicals for measurement of relative OH radical rate constants (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 619-629 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The homogeneous gas-phase reaction of N2H4 with O3 in air atmospheric pressure has been used to generate OH radicals in the dark, allowing the determination of relative OH radical rate constants for compounds which photolyze rapidly. This technique was first validated by determining the OH radical rate constant ratios for n-butane/cyclohexane and methanol/dimethyl ether, both of which are in excellent agreement with the literature values. The rate constant for the reaction of OH radicals with methyl nitrite at 300 ± 3 K was then determined relative to those for the reaction of OH radicals with n-hexane and dimethyl ether. The resulting rate constant of 1.8 × 10-13 cm3/molecule·s is about seven times lower than those of previous measurements which employed a different nonphotolytic relative rate method.
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    Couloamperometry. A fast kinetic technique for halogenations. I. Bromination rate constants of highly reactive enol ethers (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 855-866 
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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 couloamperometric apparatus has been designed to extend the range of this kinetic technique to the measurement of very high rate constants, 108M-1s-1, by using TFCR-EXSEL conditions (TFCR - very low reactant concentration; EXSEL - salt excess), which give half-lives of a few seconds for very fast second-order reactions. Very low faradaic currents, in the nanoampere range for halogens, corresponding to very low reactant concentrations of 10-8-10-9M, are measured selectively by compensating the eddy currents, principally the residual and the induced currents. When the electroactive species is bromine, the concentration is demonstrated to be linearly related to the limiting reduction current in the very low concentration range. The upper limit of this technique for bromination is at present 3 × 108M-1s-1. The method is applied to the kinetic study of highly reactive enol ethers EtO-C(R) = CH-R′, where R and R′ are H or Me. A value of 2.2 × 108M-1s-1 is obtained for kBr2, the rate constant for free bromine addition to EtO-CH = CH2, by extrapolating the kinetic bromide ion effects to [Br-] = 0. An α-methyl effect (kα-Me/kH)EtO of 15 is found; this is a small decrease in the methyl effect compared to the marked increase in the double bond reactivity. For the enol acetate MeCOO-CH = CH2, whose rate constant is 6 × 102M-1s-1, (kα-Me/kH)OCOMe is 21. The dependence of substituent effects on reactivity is discussed in terms of the Hammond effect on the transition state position and of charge delocalization by group G of olefins G-CH = CH2.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150902
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