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  • 1980-1984  (117)
  • 1983  (117)
  • Physical Chemistry  (117)
  • Nuclear reactions
  • 101
    Electronic Resource
    Electronic Resource
    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 
    Details
    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.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151009
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  • 102
    Electronic Resource
    Electronic Resource
    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 
    Details
    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.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151012
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  • 103
    Electronic Resource
    Electronic Resource
    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 
    Details
    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.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151013
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  • 104
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151015
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  • 105
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151103
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  • 106
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151106
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  • 107
    Electronic Resource
    Electronic Resource
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151110
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  • 108
    Electronic Resource
    Electronic Resource
    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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  • 109
    Electronic Resource
    Electronic Resource
    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
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150101
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  • 110
    Electronic Resource
    Electronic Resource
    Mechanism of acetylene-chlorine mixture explosion initiated by small additions of oxygen (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1-4 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An improved radical-chain scheme of acetylene-chlorine mixture explosion initiated by small additions of oxygen is proposed. It includes among others the three-body formation of chemically activated state (2) and describes the inhibiting effect of oxygen below the explosion limit.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150102
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  • 111
    Electronic Resource
    Electronic Resource
    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 
    Details
    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.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150704
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  • 112
    Electronic Resource
    Electronic Resource
    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
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150801
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  • 113
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of osmium(VIII)-catalyzed oxidation of D-proline and L(-)-methionine by hexacyanoferrate(III) (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 669-676 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The osmium(VIII)-catalyzed oxidation of D-proline and L(-)-methionine by alkaline hexacyanoferrate(III) has been studied spectrophotometrically. The reactions follow kinetics different from those of the oxidation of many amino acids investigated earlier, being first order in hexacyanoferrate(III) and osmium(VIII). The order in proline or methionine and OH- decreases from unity to zero at higher concentrations of proline or methionine and OH-, respectively. A mechanism consistent with the kinetic data is proposed and discussed.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150708
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  • 114
    Electronic Resource
    Electronic Resource
    Kinetics and equilibria in the system Br + t-BuO2H ⇆ HBr + t-BuO2. OH bond dissociation energy in t-BuO2-H (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 815-822 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and equilibria in the system Br + t-BuO2H ⇆ HBr + t-BuO2· have been measured in the range of 300-350 K using the very low pressure reactor (VLPR) technique. Using an estimated entropy change in reaction (1) ΔS1 = 3.0 ± 0.4 cal/mol·K together with the measured ΔG1, we find ΔH1 = 1.9 ± 0.2 kcal/mol and DHº (t-BuO2-H) = 89.4 ± 0.2 kcal/mol ΔHf·(tBuO2·) = 20.7 kcal/mol and DHº (t-Bu-O2) = 29.1 kcal/mol. The latter values make use of recent values of ΔHf·(t-Bu) = 8.4 ± 0.5 kcal/mol and the known thermochemistry of the other species. The activation energy E1 is found to be 3.3 ± 0.6 kcal/mol, about 1 kcal lower than the value found for Br attack on H2O2. It suggests a bond 1 kcal stronger in H2O2 than in tBuO2H.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150810
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  • 115
    Electronic Resource
    Electronic Resource
    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 
    Details
    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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  • 116
    Electronic Resource
    Electronic Resource
    Studies in nickel(IV) Chemistry. Kinetics of the aquacopper(II)-catalyzed oxidation of phenylhydrazine by tris(dimethylglyoximato)-nickelate(IV) in aqueous medium (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 867-880 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of electron transfer in the redox system containing phenylhydrazine (S) and tris(dimethylglyoximato)nickelate(IV), in the presence of catalytic amounts of added Cu(II)aq, have been studied in aqueous medium at an ionic strength of 0.25M in the pH range of 6.01-9.06. The kinetics exhibit pseudo-zero-order disappearance of Ni(IV) when an excess of [S]0 and small amounts of Cu(II) are present. While the pseudo-zero-order rate constants are almost linearly dependent on [S]0 at constant [Cu(II)] and pH tending to become non-linearly dependent on higher relative [S]0, they are linearly dependent on [Cu(II)] in a 20-fold range. The pH-rate profiles with low [S]0 and [Cu(II)] show a monotonic decrease in rates with increasing pH, the rates tending to attain limiting values at higher relative pH. Results are interpreted in terms of a probable mechanism involving the formation of precursor complexes of phenylhydrazine and Cu(II) species in the medium, followed by the rate-determining breakdown of the precursors with concomitant electron transfer. The hydrolyzed species of Cu(II) reacts more slowly than does the aquacopper(II). Ni(IV) does not appear to have any kinetic role in the redox system and is involved only in rapid product formation steps. The oxidation product of phenylhydrazine is 4-hydroxyazobenzene.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150903
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  • 117
    Electronic Resource
    Electronic Resource
    Sensitivity analysis in chemical kinetics by the method of polynomial approximations (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 959-987 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new approach, the method of polynomial approximations (PAM), to the sensitivity analysis in chemical kinetics is presented. The method is based on first dividing the time domain of interest into subintervals, and then, within each subinterval, using low-degree interpolation polynomials to mimic the system temporal behavior. This procedure forces all parametric dependences of the system to reside in the expansion coefficients and transforms the differential sensitivity equations into a set of algebraic ones. The major computational effort of PAM is proportional to the number of components in the system, not to the number of parameters. In addition, higher order sensitivity coefficients in PAM can be generated quite readily once first-order ones are known. The information required to divide the time domain comes from a preliminary simulation study of the system temporal behavior, which is always available in any kind of modeling studies. Typically, for an interpolation polynomial of degree 3-4, only 10-20 subintervals are needed to attain satisfactory accuracy. The application of PAM is well suited to large-scale kinetic models, especially when an inexpensive scanning of the system sensitivity behavior is desired. The extremely high computational speed of PAM in securing sensitivity informations was demonstrated by two illustrative kinetic examples. Furthermore the problem of utilizing sensitivity information to unravel the functional dependence of a species concentration upon rate coefficients, to simplify a complex reaction model, and to elucidate mechanistic details of a reaction process was examined in detail.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151003
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