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  • Physical Chemistry  (116)
  • Wiley-Blackwell  (116)
  • American Physical Society
  • PANGAEA
  • Periodicals Archive Online (PAO)
  • 1975-1979  (66)
  • 1970-1974  (50)
  • 1935-1939
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  • Wiley-Blackwell  (116)
  • American Physical Society
  • PANGAEA
  • Periodicals Archive Online (PAO)
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  • 1
    Digitale Medien
    Digitale Medien
    A flash photolysis-resonance fluorescence kinetics study of the reactions of ground-state sulfur atoms. V. Rate parameters for the reaction of S(3P)with cis-2-butene and tetramethylethylene (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 841-857 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rate parameters for the reaction of ground-state atomic sulfur, S(3P), with the olefins cis-2-butene and tetramethylethylene have been determined over a temperature range of ∽280°K. A major finding of this study was that the rate constants for both reactions showed negative temperature dependencies. When k is expressed in the form of an Arrhenius equation, this necessarily leads to negative activation energies: k1 = (4.68 ± 0.70) × 10-12 exp (+0.23 ± 0.09 kcal/mole)/RT (219°-500°K) k2 = (4.68 ± 1.70) × 10-12 exp (+1.29 ± 0.23 kcal/mole)/RT (252°-500°K) Units are cm3 molec-1s-1. When a threshold energy of 0.0 kcal/mole is assumed for reaction (2), the temperature dependence of the preexponential term has a value of T-2. Making the usual simplifying assumptions, neither collision theory nor transition state theory leads to a preexponential factor with a strong enough negative temperature dependence. A comparison of these results with those derived from studies of the reactions of atomic oxygen, O(3P), with the same olefins shows that in both studies simple bimolecular processes were being examined. Also discussed are the possible experimental and theoretical ramifications of these new results.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550050511
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  • 2
    Digitale Medien
    Digitale Medien
    The pyrolysis of 2-nitrosoisobutane and the bond dissociation energies of nitroso compounds (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 813-828 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Study of the reaction by very-low-pressure pyrolysis (VLPP) in the temperature range of 550-850°K yields for the high-pressure Arrhenius parameters \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }\,k_{\rm 1} = (15.6 \pm 0.5) - (36.0 \pm 1.0)/\theta {\rm \,(sec}^{{\rm - 1}})$$\end{document} where θ = 2.303RT in kcal/mole. These in turn yield for the high-pressure second-order recombination of tBu + NO, k-1 = (3.5 ± 1.7) × 109 1./mole·sec at 600°K. For the competing reaction l./mole·sec and E4 ≥ 4.2 kcal/mole. The bond dissociation energy DHo (tBu-NO) was determined to be (39.5 ± 1.5) kcal/mole, both from the equilibrium constant and from the activation energy of reaction (1), obtained from RRKM calculations. A ‘free-volume’ model for the transition state for dissociation is consistent with the data. A limited study of the system at 8-200 torr showed an extremely rapid inhibition by products and a very complex set of products.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550060605
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  • 3
    Digitale Medien
    Digitale Medien
    A computational modeling study of the low-temperature pyrolysis of n-alkanes; mechanisms of propane, n-butane, and n-pentane pyrolyses (1975)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 479-507 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The mechanisms of the pyrolyses of the n-alkanes C3H8, n-C4H10, and n-C5H12 at temperatures between 390 and 560°C have been studied by the construction and evaluation of sets of several hundred reactions. Rate parameter values were assigned using literature data and calculated estimates. Time-dependent numerical solutions were computed for the experimental conditions of several rate and product studies reported in the literature. The comparisons of these a priori computations with experiment show excellent agreement for propane and agreement for butane and pentane within the estimated error limits of the assigned rate parameters. These results demonstrate that the general “state of knowledge” of the mechanism of alkane pyrolysis, namely, the reactions and their rate parameters, is such that reasonable a priori predictions of experimental results can be made. Discussions of the major stepwise processes in the pyrolyses are presented, and the importance of allyl radicals in termination is demonstrated.
    Zusätzliches Material: 13 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550070402
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  • 4
    Digitale Medien
    Digitale Medien
    The kinetics of aquation and racemization of some cis- chloro-, hydroxo-, and aquabis(ethylenediamine)(amine)cobalt(III) complexes (1976)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 8 (1976), S. 573-583 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Aquation rates forcis-CoCl(en)2(A)2+ (A = 3,5-lutidine, imidazole, N-methylimidazole, benzimidazole) have been determined by halide release titration in 1.0 M HNO3 at 50-80°C. Kinetic parameters are (in the above order of A) 107k298 (sec-1), 7.4, 5.7, 1.3, 9.7; Ea (kJ/mole), 103, 101, 130, 112; log PZ (sec-1), 11.89, 11.53, 16.04, 13.58; ΔS298
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550080411
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  • 5
    Digitale Medien
    Digitale Medien
    A shock-tube study of the kinetics of reaction of hydroxyl radicals with H2, CO, CH4, CF3H, C2H4, and C2H6 (1976)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 8 (1976), S. 549-561 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Concentration-time profiles have been measured for hydroxyl radicals generated by the shock-tube decomposition of hydrogen peroxide in the presence of a variety of additives. At temperatures close to 1300°K the rate constants for the reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm OH} + {\rm RH} \to {\rm R} + {\rm H}_{\rm 2} {\rm O}$$\end{document} are found to be in the ratio 0.18:0.19:0.59:1.00:2.33:2.88 for the additives CO:CF3H:H2:CH4:C2H4:C2H6, respectively.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550080409
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  • 6
    Digitale Medien
    Digitale Medien
    Computational modeling of the mechanisms of the free radical-chain reaction of alkanes with oxygen. The oxidation of isobutane, n-butane, and isopentane (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 345-362 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A general computational method for obtaining complete solutions of time-dependent kinetic equations has been developed and applied to free radical-initiated reactions of alkanes with oxygen. The method has been applied to the low-temperature, peroxide-initiated oxidations of isobutane and isopentane. Using available independently measured and estimated values for the rate constants and activation parameters for each of the 20 proposed reaction steps for the oxidation of isobutane, the rates and products have been calculated for both the liquid phase and gas phase in the range of 100°-155°C. The calculated rates and products of oxidation agree with published experimental values. The oxidation of isopentane was examined by a 32-reaction model. The rate constants were estimated using values for the appropriate rate steps in the oxidation of n-butane and isobutane. The calculation of the oxidation rate and products agree with our experiments.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550040312
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  • 7
    Digitale Medien
    Digitale Medien
    A kinetics study of the reactions of OH with several aromatic and olefinic compounds (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 783-804 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reactions of hydroxyl radicals with eight substituted aromatic hydrocarbons and four olefins were studied utilizing the flash photolysis-resonance fluorescence technique. The rate constants were measured at 298°K using either Ar or He as the diluent gas. The values of the rate constants (k × 1012) in the units of cm3/molec. sec are (a) OH + o-xylene → products: (12.9±3.8), 20 torr He; (13.0±0.3), 20 torr Ar; (12.4±0.1), 200 torr He;(b) OH + m-xylene → products: (15.6±1.4), 3 torr Ar; (19.4±0.8), 20 torr Ar; (21.4±0.2), 20 torr He; (20.3±1.9), 200 torr Ar; (20.6±1.3), 200 Torr He;(c) OH + p-xylene → products: (8.8±1.2), 3 torr Ar; (10.1±1.0), 20 torr He; (10.5±0.6), 200 torr He;(d) OH + ethyl benzene → products: (7.50±0.38), 3 torr He; (7.06±0.26), 20 torr He; (7.95±0.28), 200 torr He;(e) OH + n-propylbenzene → products: (6.40±0.36), 20 torr He; (5.86±0.16), 200 torr He;(f) OH + isopropylbenzene → products: (7.79±0.40), 200 torr He;(g) OH + hexafluorobenzene → products: (0.221±0.020), 20 torr He; (0.219±0.016) 200 torr He;(h) OH + n-propyl pentafluorobenzene → products: (2.52±0.54), 3 torr He; (3.01±0.76), 20 torr He; (3.06±0.24), 200 torr He;(i) OH + propylene → products: (25.6±1.2), 20 torr He; (26.3±1.2), 200 torr He;(j) OH + 1-butene → products: (29.6±1.9), 3 torr He; (29.4±1.4), 20 torr He;(k) OH + cis-2-butene → products: (43.2±4.1), 3 torr He; (42.6±2.5), 20 torr He;(l) OH + tetramethylethylene → products: (56.9±1.3), 20 torr He.
    Zusätzliches Material: 15 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550100802
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  • 8
    Digitale Medien
    Digitale Medien
    A flash photolysis-resonance fluorescence kinetics study of ground-state sulfur atoms: I. Absolute rate parameters for reaction of S(3P) with O2(3Σ). (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 367-382 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The flash photolysis-resonance fluorescence technique has been used to measure the reaction of ground-state sulfur atoms with molecular oxygen as a function of both temperature and total pressure. The most suitable source of S(3P) for this study was found to be COS in the presence of CO2, as a diluent gas and with the photolysis flash filtered so as to remove all radiation of wavelengths below 1650 Å. Under these conditions, it was found that over the temperature range of 252-423°K the rate data could be fit to a simple Arrhenius-type equation of the form \documentclass{article}\pagestyle{empty}\begin{document}$$k_1 = (2.24 \pm 0.27) \times 10^{ - 12} {\rm exp}\left({\frac{{{\rm - 0}{\rm .00} \pm {\rm 0}{\rm .10 kcal/mole}}}{{RT}}} \right)$$\end{document} Units are cm3 molec-1 s-1. The small A-factor for this reaction, the lack of any pressure dependence, and the direct observation of the production of O(3P) with increasing reaction time suggest that the S(3P) atom attacks the O2(3Σ) molecule end-on forming SOO which rapidly falls apart to form SO (3Σ) and O(3P).
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550040402
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  • 9
    Digitale Medien
    Digitale Medien
    A flash photolysis resonance fluorescence kinetics study of ground-state sulfur atoms. III. Rate parameters for reaction of S(3P) with ethylene episulfide (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 149-153 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Absolute rate constants for the reaction of S(3P) with ethylene episulfide were measured over a C2H4S concentration range of 5, a total pressure of 20-200 tort, and a flash intensity range of ˜4. Over this range of variables, the bimolecular rate constant was found to be invariant. Because of limitations imposed by the physical properties of the reactant C2H4S, temperature variations were necessarily held to the range 298-355°K. The bimolecular rate constant was found to be invariant over this limited temperature range, having a value of (4.47 ± 0.26) × 10-11 cm3 molec.-1 sec-1. The possible influence of this reaction in studies of the S(3P)-ethylene system are discussed.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550050113
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  • 10
    Digitale Medien
    Digitale Medien
    Combination and disproportionation reactions of allylic radicals with ethyl, propyl, and t-Butyl Radicals (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1055-1069 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 1-Methylallyl, 1,1-dimethylallyl, 1,2-dimethylallyl, 1,3-dimethylallyl, 1,1,2-trimethylallyl, and 1-ethylallyl radicals have been generated in the gas phase at 20 ± 1°C by addition of H atoms, formed by Hg(63P1) photosensitization of H2, to appropriate dienes. Their combination reactions with ethyl radicals have been studied and the relative reactivities of the reaction centers in each allylic radical determined. Similar measurements have been made for some combination reactions of n-propyl, i-propyl, and t-butyl with 1-methylallyl and 1,1,2-trimethylallyl radicals. The more substituted reaction centers are found to be the less reactive. In addition the self-combination and disproportionation of 1-methylallyl radicals has been investigated, as has cross disproportionation of each allylic radical with ethyl. The results establish a general pattern of reactivity for these radicals, which is interpreted primarily in terms of the effects of steric interaction during reaction.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550111004
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