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  • Electronic Resource  (16)
  • Physical Chemistry  (16)
  • 1
    Electronic Resource
    Electronic Resource
    A reevaluation of low temperature experimental rate data for the reactions of O atoms with methane, ethane, and neopentane (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 59-82 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The experimental data for the reactions of oxygen atoms with methane, ethane, and neopentane at temperatures below ca. 600 K have been reexamined. In the case of CH4 and C2H6 reactions, detailed computer models have been assembled to test the assumptions regarding stoichiometries that were made in the original studies in order to derive elementary rate coefficients from the experimentally observed reaction rates. It was found in both cases that the measurements are especially sensitive to secondary reactions not taken into account and impurities in the reagent alkane. Because the original reports did not include sufficient experimental details, it is not now possible to correct their results quantitatively. However, it appears, qualitatively, that the values for the O + CH4 and O + C2H6 rate coefficients were overestimated by factors of approximately 2 to 3 in the 250-400 K temperature range, with the error increasing as T decreases. Although the experimental results for the O + neopentane reaction are not as sensitive to the same kinds of complications, a comparison of the low-temperature measurements with those for the O + ethane reaction suggests that the previously recommended rate coefficients, based on the data of Herron and Huie, are probably also too high by a factor of 2 to 3.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180107
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  • 2
    Electronic Resource
    Electronic Resource
    Predicting the preexponential temperature dependence of bimolecular metathesis reaction rate coefficients using transition state theory (1989)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 909-922 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermochemical kinetics formulation of conventional transition state theory for bimolecular reactions allows for a separate contribution from each degree of freedom (translation, rotation, vibration, etc.) in the activated complex to the entropy and heat capacity of activation, and thus to the preexponential terms in the Arrhenius rate expression, k = ATn exp(-B/T). The number of vibrations and (possibly hindred) internal rotations varies depending on the nature of the reaction: atom + diatom, diatom + linear polyatom, etc. The temperature exponent n can be evaluated explicitly for each type of reaction if the harmonic oscillator-rigid free rotor approximation is valid for the reagents and activated complex and if the contribution from tunneling is small. Various reaction types are examined successively, and n is evaluated for each case. The possible contributions of other factors (vibrational anharmonicity, hindered internal rotation, tunneling, “looseness” of activated complex) to the value of n are also considered.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550211004
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  • 3
    Electronic Resource
    Electronic Resource
    A shock tube study of the reaction of the hydroxyl radical with H2, CH4, c-C5H10, and i-C4H10 (1989)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 485-498 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of the hydroxyl radical, OH, with several reactants have been studied near 1200 K in shock tube experiments in which UV absorption was used to monitor the OH concentration. The values of the rate coefficients were found to be 2.7 × 1012, 2.6 × 1012, 2.8 × 1013, and 1.26 × 1013 cm3/mol-s for the reactions of OH with hydrogen, methane, cyclopentane, and isobutane, respectively. These measured values are compared with previous experimental results and transition-state theory calculations.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550210702
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  • 4
    Electronic Resource
    Electronic Resource
    A shock tube study of the reactions of the hydroxyl radical with several combustion species (1991)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 23 (1991), S. 1075-1094 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of the hydroxyl radical, OH, with several organic species of interest in combustion chemistry have been studied near 1200 K and 1 atm in shock tube experiments in which UV absorption was used to monitor the OH concentration. Rate coefficients were measured for the reactions of OH with 2,3-dimethylbutane, isooctane, neooctane, ethylene, propylene, acetylene, formaldehyde, methanol, and ethanol. The values were found to be (in units of 1012 cm3/mol-s): 21, 22, 18, 2.6, 9.6, 0.28, 12, 5.2, and 5.3. These measured values are compared with previous experimental results and, where appropriate, transition-state theory calculations.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550231203
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  • 5
    Electronic Resource
    Electronic Resource
    Shock tube study of OH reactions with linear hydrocarbons near 1100 K (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 79-87 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of the hydroxyl radical with several linear hydrocarbon species occurring in combustion chemistry have been considered at temperatures near 1100 K and 1 atmosphere in shock tube experiments. The OH density was monitored using 310 nm UV absorption of the A2Σ+ (SINGLEBOND) X 2Π transition. Rate coefficients for the reaction of OH with ethane (8.37 × 10-12 cm3 molecule-1 s- 1; 970 K), hexane (2.18 × 10-11; 962 K), heptane (3.34 × 10-11, 1186 K), octane (4.42 × 10-11; 1078 K), nonane (4.55 × 10-11; 1097 K), and decane (5.64 × 10-11; 1109 K) have been determined. These values are compared with previous experimental results and transition state theory calculations. © 1996 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.2
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  • 6
    Electronic Resource
    Electronic Resource
    Further studies on the dissociation of HBr behind shock wavesThis work was supported by the U.S. Air Force under Contract No. F04701-72-C-0073. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 425-444 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Previously reported shock tube studies of the dissociation of HBr in the temperature range of 2100-4200°K have been extended to lower temperatures (1450-2300°K) in pure HBr. The course of reaction was followed by monitoring the radiative recombination emission in the visible spectrum from Br atoms. The results imply that, in the lower range of temperatures, the activation energy of dissociation, E in the expression AT-2e-E/RT, can be approximated by the HBr bond energy (88 kcal/mole). It was also found that, in this temperature range, the rate of HBr dissociation is sensitive to the Br2 dissociation rate and the HBr + Br exchange rate. When these rates were adjusted to bring computed reaction profiles into agreement with experimental ones, it was found that the higher-temperature data could also be fitted reasonably well with an HBr dissociation activation energy of 88 kcal/mole, contrary to the conclusions of our previous work, which favored an activation energy of 50 kcal/mole. The “best value” for k1Ar, the rate coefficient for HBr dissociation in the presence of Ar as chaperone, appears to be 1021.78 ± 0.3 T-2 10-88/θ cc/mole sec, where θ = 2.3 RT/1000; that for k1HBr, is 1022.66T-210-88/θ. A detailed review is given of the rate coefficients for the other pertinent reactions in the H2-Br2 system, viz., Br2 dissociation and reactions of HBr with H and Br.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050312
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  • 7
    Electronic Resource
    Electronic Resource
    A shock tube study of the reaction of the hydroxyl radical with propane (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1557-1566 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate coefficient for the reaction of the hydroxyl radical, OH, with propane has been measured at 1220 K in shock tube experiments, and a value of (1.58 ± 0.24) × 1013 cm3/mol s was obtained. This measured value is compared with previous experimental results and a transition-state theory calculation.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550161209
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  • 8
    Electronic Resource
    Electronic Resource
    The O + NH3 reaction: A review (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 319-362 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Experimental data for the reaction of O atoms with NH3 have been reviewed with particular attention to the possible effects of secondary reactions on the deduced rate coefficient. A reaction mechanism was assembled and computer calculations carried out to simulate several sets of experiments. The sensitivity of the calculations to uncertainties in the various rate coefficients was assessed. Transition-state theory calculations were carried out on the rate coefficient k1 for the O + NH3 → OH + NH2 reaction. These studies suggest that the reaction stoichiometry is dependent on temperature, initial reagent ratios, and extent of reaction; that available data are not sufficient to determine whether the initial step is H-atom abstraction (producing OH and NH2 radicals) or O-atom addition (producing an NH3O* complex): and that the low temperature values of k1 (T ≤ 400 K) are not consistent with values deduced at higher temperatures if the reaction proceeds by H-atom abstraction. Taking all the evidence into account, it is recommended that the expression 1.1 × 103 T2.1 exp(-2620/T) L mol-1 s-1 be used for k1 until more definitive experimental measurements are made at low temperatures.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550190406
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  • 9
    Electronic Resource
    Electronic Resource
    Chemical kinetics of hydrogen halide lasers. 1. The H2—Cl2 systemThis work was supported by the U.S. Air Force under Contract No. F04701-68-C-0200 (1969)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 551-569 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed kinetic model of the HCl chemical laser produced by the flash photolytically initiated H2—Cl2 explosion is described, and the results of computer calculations on such a system are discussed. It is shown that currently accepted values of the various rate constants, supplemented in a few cases by reasonable estimates of previously unmeasured rate constants, are adequate to approximate the observed laser behavior of this system. It is also shown that the chemistry of such a system is extremely complex, and exhibits a high degree of coupling between one reaction and another; therefore, great care is required to extract kinetic data from the optical behavior of such laser systems. It is further argued that different hydrogen halide lasers may behave quite differently from each other, depending on the relative magnitudes of the various rate constants involved.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550010606
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  • 10
    Electronic Resource
    Electronic Resource
    The use of transition-state theory to extrapolate rate coefficients for reactions of oh with alkanes (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1339-1362 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is described for extrapolating existing experimental data on the reactions of OH radicals with alkanes to higher temperatures using conventional transition-state theory. Expressions are developed for the estimation of the structural properties of the activated complex necessary for calculating ΔS± and ΔH±. The vibrational frequencies and internal rotations of the activated complex are given by those of the reacting alkane or the analogous alcohol and a set of additional internal modes that is the same for all OH + alkane reactions considered. Differences between primary, secondary, and tertiary hydrogen attack are discussed, and the validity of representing the activated complexes of all OH + alkane reactions by a fixed set of vibrational frequencies and other internal modes is evaluated. Calculations are presented for the reaction of OH with CH4, C2H6, C3H8, n-C4H10, i-C4H10, c-C4H8, c-C5H10, c-C6H12, (CH3)2CHCH(CH3)2, (CH3)3CCH(CH3)2, (CH3)4C, and (CH3)3CC(CH3)3, and the results are compared with experiments.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550141206
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