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  • Physical Chemistry  (116)
  • Wiley-Blackwell  (116)
  • American Physical Society
  • PANGAEA
  • Periodicals Archive Online (PAO)
  • 2005-2009
  • 1995-1999  (50)
  • 1975-1979  (66)
  • 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
    Solvation effects on the relative basicity of propylamines (1995)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 26-30 
    Details
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Slight structural moiecular variations are known to affect different properties of compounds. In solution, different solute-solvent interactions are known also to alter the properties of numerous compounds. Quantitative structure-activity relationships (QSAR) are used regularly to analyze and predict the variations of different properties of compounds that are caused by structural variations and significant solute-solvent interactions. The relative basicities of n-propylamine, dipro;ylamine and tripropylamine were determined in nine different solvents from potentiometric titrations. QSAR that were developed from these experimental basicity values were used to evaluate the type and significance of the solute-solvent interactions. The important interactions that influence basicity variations for the propylamines studied are dipolarity-polarizability interaction between the solute and the solvent and hydrogen bonds from the propylammonium ions to basic solvents. The role of hydrogen bonds from the propylamines to acidic solvents is minor.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/poc.610080106
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  • 2
    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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  • 3
    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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  • 4
    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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  • 5
    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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  • 6
    Digitale Medien
    Digitale Medien
    A shock tube study of methyl-methyl reactions between 1200 and 2400 K (1995)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 27 (1995), S. 1179-1196 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The methyl-methyl reaction was studied in a shock tube using uv narrowline laser absorption to measure time-varying concentration profiles of CH3. Methyl radicals were rapidly formed initially by pyrolysis of various precursors, azomethane, ethane, or methyl iodide, dilute in argon. The contributions of the various product channels, C2H6, C2H5 + H, C2H4 + H2, and CH2 + CH4, were examined by varying reactant mixtures and temperature.The measured rate coefficients for recombination to C2H6 between 1200 and 1800 K are accurately fit using the unimolecular rate coefficients reported by Wagner and Wardlaw (1988). The rate coefficient for the C2H5 + H channel was found to be 2.4 (±0.5) × 1013 exp(-6480/T) [cm3/mol-s] between 1570 and 1780 K, and is in agreement with the value reported by Frank and Braun-Unkhoff (1988). No evidence of a contribution by the C2H4 + H2 channel was found in ethane/methane/argon mixtures, although methyl profiles in these mixtures should be particularly sensitive to this channel. An upper limit of approximately 1011 [cm3/mol-s] over the range 1700 to 2200 K was inferred for the rate coefficient of the C2H4 + H2 channel. Between 1800 and 2200 K, methyl radicals are also rapidly removed by CH3 + H ⇒ 1CH2 + H2. In this temperature range, the reverse reaction was found to have a rate coefficient of 1.3 (±0.3) × 1014 [cm3/mol-s], which is 1.8 times the room-temperature value. © 1995 John Wiley & Sons, Inc.
    Zusätzliches Material: 13 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550271205
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  • 7
    Digitale Medien
    Digitale Medien
    Kinetics and mechanism of the Cl + CO reaction in air (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 763-771 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Long-path FTIR spectroscopy was used to study the kinetics and mechanism of the reaction of Cl atoms with CO in air. The relative rate constants at 298 K and 760 torr for the forward direction of the reaction of Cl with 13CO and the reaction of Cl13CO with O2 were k1 = (3.4 ± 0.8) × 10-14 cm3 molecule-1 s-1 and k2 = (4.3 ± 3.2) × 10-13 cm3 molecule-1 s-1, respectively (all uncertainty limits are 2σ). The rate constant for the net loss of 13CO due to reaction with Cl in 1 atm of air at 298 K was kCl+COobs = (3.0 ± 0.6) × 10-14 cm3 molecule-1 s-1. The only observed carbon-containing product of the Cl + 12CO reaction was 12CO2, with a yield of 109 ± 18%. Our results are in good agreement with extrapolations from previous studies. The reaction mechanism and the implications for laboratory studies and tropospheric chemistry are discussed. © 1996 John Wiley & Sons, Inc.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.7
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  • 8
    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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  • 9
    Digitale Medien
    Digitale Medien
    A kinetics study of the temperature dependence of the reactions of OH(2Π) with CF3CHCl2, CF3CHClF, and CF2ClCH2Cl (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 187-197 
    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 utilized to determine the rate constants for three reactions involving the hydroxyl radical [OH(2≅)] and three halogenated C2 alkanes. The nominal temperature range covered was 250-375 K. The compounds studied and the resulting Arrhenius expressions in units of cm3/molec·sec are The error limits in these expressions are such that they include any possible systematic errors due to the presence of impurities in the halocarbon samples. Tropospheric lifetimes have been calculated for the above species by combining the above rate constant data with global seasonally and diurnally averaged hydroxyl radical concentrations.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550110210
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  • 10
    Digitale Medien
    Digitale Medien
    Very low-pressure pyrolysis of cyclobutyl cyanide. The cyano stabilization energy (1975)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 109-123 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A very low-pressure pyrolysis (VLPP) apparatus has been constructed and shown to yield kinetic data consistent with other VLPP systems. The technique has been applied to the pyrolysis of cyclobutyl cyanide over the temperature range of 833-1203°K. The reaction was found to proceed via a single pathway to yield ethylene and vinyl cyanide. If A∞ is based on previous high-pressure data for this reaction and for cyclobutane pyrolysis, then RRKM theory calculations show that the experimental unimolecular rate constants are consistent with the high-pressure Arrhenius parameters given by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}\,k_\infty ({\rm sec}^{{\rm - 1}}) = 15.0 - (57.0 \pm 1.0)/\theta $$\end{document} where θ=2.303 RT in kcal/mole. If A∞ is adjusted relative to the more recent parameters for cyclobutane pyrolysis suggested by VLPP studies, then the Arrhenius expression becomes \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log }\,k_\infty ({\rm sec}^{{\rm - 1}}) = 15.9 - (59.1 \pm 1.0)/\theta $$\end{document} The cyano group reduces the activation energy for cyclobutane pyrolysis by 6±1 kcal/mole, and on the basis of a biradical mechanism this value may be attributed to the cyano stabilization energy.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550070112
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