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  • Physical Chemistry  (18)
  • Wiley-Blackwell  (18)
  • American Institute of Physics
  • National Academy of Sciences
  • Nature Publishing Group
  • Periodicals Archive Online (PAO)
  • Wiley
  • 1980-1984  (18)
  • 1965-1969
  • 1982  (18)
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  • Wiley-Blackwell  (18)
  • American Institute of Physics
  • National Academy of Sciences
  • Nature Publishing Group
  • Periodicals Archive Online (PAO)
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  • 1980-1984  (18)
  • 1965-1969
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 903-917 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of the basic hydrolysis of 1-glyceryl mononitrate (1-MNG) and 2-glyceryl mononitrate (2-MNG) were investigated in CO2-free aqueous calcium hydroxide solutions. The hydrolysis reactions were carried out in a temperature-controlled reactor vessel with provision for continuous N2 sparging of the reaction mixture. Both glyceryl nitrate esters hydrolyzed via second-order reaction at 25°C. 2-MNG in calcium hydroxide solution isomerized to 1-MNG, which subsequently hydrolyzed to form NO3-. In strongly basic aqueous solutions of NaOH (30%), 2-MNG is converted to glycidol and NO3-.
    Additional Material: 6 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 977-984 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyridiniumchlorochromate (PCC) oxidizes aniline and substituted anilines except nitro anilines smoothly in chlorobenzene-nitrobenzene mixtures in the presence of dichloroacetic acid. The reaction has unit dependence on each of the aniline, PCC, and dichloroacetic acid concentrations. Electron-releasing substituents accelerate the reaction, whereas electronwithdrawing groups retard the reaction, and the rate data obey Hammett's relationship. The reaction constant ρ is -3.75. Azobenzene and p-benzoquinone have been obtained as products. The observed experimental data have been rationalized in terms of the formation of an intermediate complex involving PCC-amine undergoing a rapid decomposition to products.
    Additional Material: 4 Tab.
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  • 3
    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.
    Additional Material: 2 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 371-379 
    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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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 927-932 
    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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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 535-541 
    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.
    Additional Material: 3 Tab.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 565-583 
    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.
    Additional Material: 4 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 543-564 
    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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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 613-621 
    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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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1199-1209 
    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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