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  • Articles  (126)
  • Physical Chemistry  (126)
  • 1980-1984  (126)
  • 1955-1959
  • 1982  (126)
  • 1
    Electronic Resource
    Electronic Resource
    Effects of buffer gases on the infrared multiphoton dissociation of C2H4DCl: A chemical clock to explore highly excited molecules (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 327-349 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Observations are reported of the effect of the buffer gases He, Ne, and CF4, in the pressure range of 0-30 torr, on the branching ratio [HCl]/[DCl] of the unimolecular decomposition The ratio R = kH/kD has been measured in high-pressure thermal decomposition (670-1100 K) and was shown to give a unique measure of the internal energy of the decomposing molecules and hence, with RRKM theory and pressure fall-off data, a time scale for their decomposition.Applying the thermal data to the photolysis leads to the conclusion that excitation and decomposition are produced by the laser spike (high intensity, 70 ns FWHM) and also at a slower rate by the larger, less intense tail (1.6 μs). Added buffer gases quench the latter, leaving the former which, from measurements of R, is shown to correspond to excitations of 115 ± 15 kcal/mol and lifetimes of ∼30 ps. No bond breaking is seen despite the high energies, in accord with theoretical expectations. The results require an enhanced rate of photon absorption by the highly excited molecules, which are about hundredfold greater than that observed for 300 K molecules. Data are also reported for C2H2F2 and the secondary multiphoton photolysis of the ethylenes produced. Effects of beam geometry and wavelength are explored.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140402
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  • 2
    Electronic Resource
    Electronic Resource
    Rate constants for the reaction of ground-state oxygen atoms with methanol from 297 to 544 KN.R.C.C. No. 19814. (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 371-379 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant for the reaction of ground-state oxygen atoms with methanol has been determined between 297 and 544 K by a phase-shift technique using mercury photosensitized decomposition of N2O to generate oxygen atoms. The relative oxygen atom concentration was monitored by the chemiluminescence from the reaction of oxygen atoms with nitric oxide. The results are accommodated by the Arrhenius expression k1 = (9.79 ± 2.71) × 1012 exp[(-2267 ± 111)/T]cm3/mol·s, where the indicated uncertainties are 95% confidence limits for 10 degrees of freedom. As an incidental part of this work, the third-body efficiency of CH3OH relative to N2O for the reaction O + NO + M → NO2 + M (M = CH3OH) was determined to be 3.1 at 298 K.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140405
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  • 3
    Electronic Resource
    Electronic Resource
    Surface oxygen bond energy, and kinetics and catalysis on perovskite oxide catalysts (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 435-438 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140409
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  • 4
    Electronic Resource
    Electronic Resource
    Temperature and third-body dependence of the rate constant for the reaction O + O2 + M → O3 + M (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 417-434 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The flash photolysis resonance fluorescence technique was used to measure the rate constants of the reaction O + O2 + M → O3 + M (M = N2, O2, Ar, and He) as a function of temperature. The results for the rate constants are given by The activation energies with N2, O2, and Ar as third bodies are equal within the experimental error, (-1370 → 340 cal/mol), and the relative third-body efficiencies at 298 K for N2, O2, Ar, and He are 1.00, 0.99, 0.69, and 0.60, respectively.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140408
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  • 5
    Electronic Resource
    Electronic Resource
    Cyclobutane production via the O3--thiolane reaction (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 439-445 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140410
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  • 6
    Electronic Resource
    Electronic Resource
    An empirical formula for gas-wall collision efficiencies in VLPP experiments (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 447-450 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140411
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  • 7
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of the gas-phase thermal reaction between bis(fluoroxy) difluoromethane CF2(OF)2 and carbon monoxide (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 647-657 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas-phase thermal reaction between CF2(OF)2 and CO has been studied in a static system at temperatures ranging between 110 and 140°C. The only reaction products were CF2O and CO2, giving the following stoichiometry: \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CF}_{\rm 2} {\rm (OF)}_{\rm 2} {\rm + 2CO = 2CF}_{\rm 2} {\rm O + CO}_{\rm 2} {\rm}\Delta n{\rm = 0}$$\end{document} The reaction is homogeneous. The rate is strictly second order in CF2(OF)2 and CO, and is not affected by the total pressure or by the presence of reaction products. Oxygen promotes a sensitized oxidation of CO and inhibits the formation of CF2O.The experimental results in the absence of oxygen can be explained by a chain mechanism similar to that proposed for the reaction between F2O and CO with an overall rate constant of \documentclass{article}\pagestyle{empty}\begin{document}$$k_1 = 1.45 \times 10^9 {\rm exp}(- 20,900/RT)L/mol \cdot s$$\end{document} From the experimental data obtained on the oxygen-inhibited reaction, the rate constant for the primary process can be calculated: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {({\rm I})} \quad {{\rm CF}_{\rm 2} ({\rm OF)}_{\rm 2} + {\rm CO} \to {\rm CF}_{\rm 2} (\mathop {\rm O}\limits^{\rm .}){\rm OF} + {\rm F}\mathop {\rm C}\limits^{\rm .} {\rm O}} \quad\quad {k_1 = 1.45 \times 10^9 {\rm exp}(- 20,900/RT)L/mol \cdot s} \\\end{array}$$\end{document} The chain length v = 2.5 is independent of the temperature. Taking for collision diameters σCF2(OF)2 = 6 Å and σCO = 3.74 Å, a value α = 5.3 × 10-3 for the steric factor is obtained.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140607
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  • 8
    Electronic Resource
    Electronic Resource
    The kinetics of the gas-phase reaction between iodine and phenylsilane and the bond dissociation energy D(C6H5SiH2—H) (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 669-677 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reaction has been investigated in the temperature range of 490-573 K. Initial reactant pressures were varied in the range of 0.2-5.2 torr (I2) and 2-20 torr (C6H5SiH3). The rate of iodine consumption, monitored spectrophotometrically, was found to obey \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d[{\rm I}_{\rm 2}]}}{{dt}} = \frac{{k_{3/2} [{\rm I}_{\rm 2}]^{{\raise0.7ex\hbox{$1$} \!\mathord{\left/ {\vphantom {1 2}}\right.\kern-\nulldelimiterspace} \!\lower0.7ex\hbox{$2$}}} [{\rm C}_{\rm 6} {\rm H}_{\rm 5} {\rm SiH}_{\rm 3}]}}{{1 + k'[HI]/[I_2]}}$$\end{document} both by initial rate and integrated equation fitting procedures. The effect of added initial HI conformed to this expression. The data are consistent with a conventional I-atom propagated chain reaction, and for the step \documentclass{article}\pagestyle{empty}\begin{document}$${\rm I}^{\rm .} + {\rm C}_{\rm 6} {\rm H}_{\rm 5} {\rm SiH}_{\rm 3} \to {\rm C}_{\rm 6} {\rm H}_{\rm 5} \mathop {\rm S}\limits^{\rm .} {\rm iH}_{\rm 2} + {\rm HI}$$\end{document} the rate constant is given by \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log}k_1 (dm^3 /mol \cdot s) = (11.52 \pm 0.08) - (76.8 \pm 0.8{\rm kJ/mol})/RT{\rm ln}10$$\end{document} From this is derived the bond dissociation energy value C6H5SiH2—H = 374 kJ/mol(88 kcal/mol). A comparison with other Si—H dissociation energy values indicates that the “silabenzyl” stabilization energy is small, ≈7 kJ/mol.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140609
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  • 9
    Electronic Resource
    Electronic Resource
    The oxidation of diethylhydroxylamine by nitrogen dioxide (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 699-710 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diethylhydroxylamine, (C2H5)2NOH, was oxidized by NO2 at 25°C in a long-path-length infrared gas cell. The measured products of the reaction were HONO and CH3CHO. The reaction scheme which explains the reaction is was oxidized by NO2, and the reaction was found to be very rapid with k1 〉 10-16 cm3/s. The products of the reaction were verified by both infrared absorption (CH3CHO, C2H5NO) and gas chromatography (CH3CHO, NO).
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140611
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  • 10
    Electronic Resource
    Electronic Resource
    Mechanism of oxidation of phenylthioacetic acids by potassium peroxodiphosphate (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 789-799 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates of oxidation of phenylthioacetic acid (PTAA) and several substituted phenylthioacetic acids by potassium peroxodiphosphate (PP) in 50% (v/v) aqueous acetic acid have been studied in detail. The rate of oxidation is expressed as \documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{- d[{\rm PP]}}}{{{\rm dt}}} = k[{\rm PP][PTAA][H}^{\rm +}]$$\end{document}An analysis of the dependence of the rate on [H+] reveals that H3P2O8- is the active oxidizing species in the oxidation. The effect of ring substituents on the rate gives a ρ+ value of -0.45 ± 0.03 (r = 0.998, s = 0.02 at 40°C), pointing to the development of an electron-deficient center in the transition state. The results are discussed in terms of a mechanism involving the rate-determining formation of an intermediate between PP and phenylthioacetic acids, followed by the decomposition of the intermediate. These kinetic results are compared with those obtained in the oxidation of phenylthioacetic acids by peroxodisulfate.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140707
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