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  • 101
    Electronic Resource
    Electronic Resource
    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
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550111004
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  • 102
    Electronic Resource
    Electronic Resource
    Very low-pressure pyrolysis (VLPP) of hex-1-ene. Kinetics of the retro-ene decomposition of a mono-olefin (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1071-1080 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal unimolecular decomposition of hex-1-ene has been investigated over the temperature range of 915-1153 K using the technique of very low-pressure pyrolysis (VLPP). The reaction proceeds via the competitive pathways of C3-C4 fission and retro-ene elimination, with the latter dominant at low temperatures and the former at high temperatures. This behavior results in an isokinetic temperature of 1035 K under VLPP conditions (both reactions in the unimolecular falloff regime). RRKM calculations, generalized to take into account two competing pathways, show that the experimental unimolecular rate constants are consistent with the high-pressure Arrhenius parameters given by log k1 (sec-1) = (12.6 ± 0.2) -(57.7 ± 1.5)/θ for retro-ene reaction, and log k2 (sec-1) = (15.9 ± 0.2) - (70.8 ± 1.0)/θ for C-C fission, where θ = 2.303 RT kcal/mol. The A factors were assigned from the results of a recent shock-tube study of the decomposition in the high-pressure regime, and the activation energies were found by matching the RRKM calculations to the VLPP data. The parameters for C-C fission are consistent with the known thermochemistry of n-propyl and allyl radicals. A clear measure of the importance of the molecular pathway in the decomposition of a mono-olefin has been obtained.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550111005
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  • 103
    Electronic Resource
    Electronic Resource
    Pyrolytic production of Se (3P) from carbon diselenide. II. Rate of CSe2 decay (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1109-1130 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrolytic decay of carbon diselenide was monitored by ultraviolet absorption spectroscopy in reflected shock waves in the temperature range of 1600-2600°K. The temperature dependence of the absorption coefficient of CSe2 at 2308 Å was determined and was used to provide kinetic information along with a deconvolution procedure which accounted for and removed systematic distortions of the fast time-resolved absorbance profile. For temperatures of 1600-2600°K and argon densities of 1.5-7.0 × 10-5 mol/cm3 dilute (1.0-9.0 × 10-9 mol/cm3) CSe2 pyrolyzed with measured first-order decay rates in the range of log10 k1 (sec-1) = 3.0-5.7; at midrange (2100°K and 4.3 × 10-5 mol/cm3 in Ar) k1 ≈ 3 × 104 sec-1. The decay probably occurs via a unimolecular low-pressure process, first order in both CSe2 and Ar, for which k2 ± 109 cm3/mol·sec at 2100°K. The deconvoluted data yield Arrhenius activation energies of 53.2 kcal/mol under second-order treatment, but the activation energy is less reliable than the general magnitude of the rate constant. A comparison of CSe2 with other molecules which are isoelectronic in their valence shells (CO2, CS2, OCS, and N2O) is made.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550111009
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  • 104
    Electronic Resource
    Electronic Resource
    Protons and ions involved in fast dynamic phenomena, edited by P. Laszlo, Elsevier Scientific Publishing Company, Amsterdam and New York, 1978. 466 pp. Price: $69.50 (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1135-1136 
    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.550111012
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  • 105
    Electronic Resource
    Electronic Resource
    The reaction of methoxy radicals with nitric oxide and nitrogen dioxide (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1183-1196 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By allowing dimethyl peroxide (10-4M) to decompose in the presence of nitric oxide (4.5 × 10-5M), nitrogen dioxide (6.5 × 10-5M) and carbon tetrafluoride (500 Torr), it has been shown that the ratio k2/k2′ = 2.03 ± 0.47: CH3O + NO → CH3ONO (reaction 2) and CH3O + NO2 → CH3ONO2 (reaction 2′). Deviations from this value in this and previous work is ascribed to the pressure dependence of both these reactions and heterogeneity in reaction (2). In contrast no heterogeneous effects were found for reaction (2′) making it an ideal reference reaction for studying other reactions of the methoxy radical. We conclude that the ratio k2/k2′ is independent of temperature and from k1 = 1010.2±0.4M-1 sec-1 we calculate that k2′ = 109.9±0.4M-1 sec-1. Both k2 and k2′ are pressure dependent but have reached their limiting high-pressure values in the presence of 500 Torr of carbon tetrafluoride. Preliminary results show that k4 = 10.9.0±0.6 10-4.5±1.1/ΘM-1 sec-1 (Θ = 2.303RT kcal mole-1) and by k4 = 108.6±0.6 10-2.4±1.1/ΘM-1 sec-1: CH3O + O2 → CH2O + HO2 (reaction 4) and CH3O + t-BuH → CH3OH + (t-Bu) (reaction 4′).
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550111105
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  • 106
    Electronic Resource
    Electronic Resource
    Masthead (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979) 
    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.550111201
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  • 107
    Electronic Resource
    Electronic Resource
    A computational algorithm for the Green's function method of sensitivity analysis in chemical kinetics (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1237-1248 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The recent interest in numerical modeling of chemical kinetics has generated the need for proper analysis of the system sensitivities in such models. This paper describes the logic for a program developed by the authors to implement the Green's function method of sensitivity analysis in complex kinetic schemes. The relevant equations and numerical details of the algorithm are outlined, two flow charts are provided, and some special programming considerations are discussed in some detail. Computer storage and computational time considerations are also treated. Finally, applications of sensitivity information to understanding complex kinetic system behavior and analyzing experimental results are suggested.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550111203
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  • 108
    Electronic Resource
    Electronic Resource
    Neighboring olefinic double-bond participation in gas phase pyrolysis of some alkenyl chlorides (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1279-1286 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-Chloro-1-butene, 5-chloro-1-pentene, and 6-chloro-1-hexene have been shown to decompose, in a static system, mainly to hydrogen chloride and the corresponding alkadienes. In packed and unpacked clean Pyrex vessels the reactions were significantly heterogeneous. However, in a vessel seasoned with allyl bromide these reactions were homogeneous, unimolecular, and follow a first-order law. The working temperature range was 389.6-480.0°C and with a pressure range of 53-221 Torr. The rate constants for the homogeneous reactions were expressed by the following Arrhenius equations: 4-chloro-1-butene: logk(sec-1) = (13.79 ± 0.17) - (223.8 ± 2.1)kJ/mole/2.303RT; 5-chloro-1-pentene: logk(sec-1) = (14.25 ± 1.20) - (238.4 ± 12.7)kJ/mole/2.303RT; and 6-chloro-1-hexene: logk(sec-1) = (12.38 ± 0.22) - (209.6 ± 2.9)kJ/mole/2.303RT. The olefinic double bond has been found to participate in the rate of dehydrohalogenation of 4-chloro-1-butene. The insulation of the CH2=CH in chlorobutene by one or two methylene chains to the reaction center does not indicate neighboring group participation. The three-membered conformation is the most favored structure for anchimeric assistance of the double bond in gas phase pyrolysis of alkenyl chlorides. The heterolytic nature of these eliminations is also supported by the present work.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550111207
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  • 109
    Electronic Resource
    Electronic Resource
    The kinetics of the gas-phase thermal isomerization and decomposition of Trans- and Cis-1,2-Bis(trifluoromethyl)-1,2,3,3-tetrafluorocyclopropane (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1287-1296 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas-phase thermal isomerization between trans- and cis-1,2-bis(trifluoromethyl)-1,2,3,3-tetrafluorocyclopropane as well as their decomposition to trans- and cis-perfluoro-2-butene, respectively, and CF2, was studied in the temperature range of 473-533°K, with an initial pressure of reactant of 1.5 to 7.0 Torr. Some runs were also made with the addition of SF6 as an inert gas up to a total pressure of 100 Torr. The reactions are first order and homogeneous. The rate constants for the geometrical isomerization fit the following Arrhenius relations: \documentclass{article}\pagestyle{empty}\begin{document}$$ {{\log {k}_{{trans}\to {cis}}}\mathord{\left/{\vphantom {{\log {k}_{{trans}\to {cis}}}{(\sec ^{ - 1})}}}\right.\kern-\nulldelimiterspace}{(\sec ^{ - 1})}}{ = }{{{(15}{.15}\pm{0}{.16)-(44,487}\pm{ 374)}}\mathord{\left/ {\vphantom {{{(15}{.15} \pm{0}{.16) - (44,487 }\pm { 374)}}{4.576{ }T}}} \right.\kern-\nulldelimiterspace} {4.576{ }T}} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {{\log {k}_{{trans}\to {cis}}}\mathord{\left/{\vphantom {{\log {k}_{{trans}\to {cis}}}{(\sec ^{ - 1})}}}\right.\kern-\nulldelimiterspace} {(\sec ^{ - 1})}}{ = }{{{(15}{.35} \pm {0}{.19) - (43,419 } \pm { 428)}} \mathord{\left/ {\vphantom {{{(15}{.35} \pm {0}{.19) - (43,419 } \pm { 428)}} {4.576{ }T}}} \right. \kern-\nulldelimiterspace} {4.576{ }T}} $$\end{document} and the corresponding equations for the decomposition of the trans and cis-cyclopropane are \documentclass{article}\pagestyle{empty}\begin{document}$$ {{\log {k}_{{trans}}} \mathord{\left/ {\vphantom {{\log {k}_{{trans}}} {(\sec ^{ - 1})}}} \right. \kern-\nulldelimiterspace} {(\sec ^{ - 1})}}{ = }{{{(15}{.14} \pm {0}{.28) - (46,700} \pm { 652)}} \mathord{\left/ {\vphantom {{{(15}{.14} \pm {0}{.28) - (46,700 } \pm { 652)}} {4.576{ }T}}} \right. \kern-\nulldelimiterspace} {4.576{ }T}} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {{\log {k}_{{cis}}} \mathord{\left/ {\vphantom {{\log {k}_{{cis}} } {(\sec ^{ - 1})}}} \right. \kern-\nulldelimiterspace} {(\sec ^{ - 1})}}{ = }{{{(15}{.39} \pm {0}{.26) - (46,639} \pm { 598)}} \mathord{\left/ {\vphantom {{{(15}{.39} \pm {0}{.26) -(46,639 } \pm { 598)}} {4.576{ }T}}} \right. \kern-\nulldelimiterspace} {4.576{ }T}} $$\end{document}.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550111208
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  • 110
    Electronic Resource
    Electronic Resource
    The detailed mechanism of the Dushman reaction explored by computer (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 693-703 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Since 1926 investigations of the Dushman reaction have relied mainly upon “constant-rate” measurements, usually by instrumental methods. Since about that time, the confusion surrounding this venerable reaction has been growing. In part, the confusion arises because the reaction involves reactive intermediate species that have not been studied directly - and may never be. Alternative detailed mechanisms have been assumed with little restraint. One of these, which is built around H2I2O3, has been explored by computer with promising results. The mechanism seems capable of reducing the confusion now attending the Dushman reaction and others related to it.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110703
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  • 111
    Electronic Resource
    Electronic Resource
    Homogeneous decomposition of vinyl ethers. The heat of formation of ethanal-2-yl (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 715-730 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal unimolecular decomposition of three vinylethers has been studied in a VLPP apparatus. The high-pressure rate constant for the retro-ene reaction of ethylvinylether was fit by log k (sec-1) = (11.47 + 0.25) - (43.4 ± 1.0)/2.303 RT at 〈T〉 = 900 K and that of t - butylvinylether by log k (sec-1) = (12.00 ± 0.27) - (38.4 ± 1.0)/2.303 RT at 〈T〉 = 800 K. No evidence for the competition of the higher energy homolytic bond-fission process could be obtained from the experimental data. The rate constant compatible with the C—O bond scission reaction in the case of benzylvinylether was log k (sec-1) = (16.63 ± 0.30) - (53.74 ± 1.0)/2.303 RT at 〈T〉 = 750 K. Together with ΔHf,3000(benzyl·) = 47.0 kcal/mol, the activation energy for this reaction results in ΔHf,3000(CH2CHO) = +3.0 ± 2.0 kcal/mol and a corresponding resonance stabilization energy of 3.2 ± 2.0 kcal/mol for 2-ethanalyl radical.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110705
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  • 112
    Electronic Resource
    Electronic Resource
    The thermal reactions of ethylene at 500°C in the presence and absence of small quantities of oxygen (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 757-774 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Initial rates of formation of primary products have been measured in the pyrolysis of ethylene at 500°C, and a mechanism for the reaction is proposed based on the isomerization of the n-hexyl radical. Additions of oxygen in amounts less than 0.1% markedly increased the rate of formation of all products, but oxygen was not completely consumed in the reaction. It is shown that secondary initiation processes are important at very low conversions, and butene-1 is the most reactive product. Bimolecular reactions between olefins and with oxygen are important steps in the mechanism.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110708
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  • 113
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of palladium (II) chloride catalyzed oxidation of allyl alcohol by potassium hexacyanoferrate (III) (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 813-819 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic study of the oxidation of allyl alcohol by potassium hexacyanoferrate (III) in the presence of palladium (II) chloride is reported. The reaction was observed by measuring the disappearance of the potassium hexacyanoferrate (III) spectrophotometrically. The reaction is first order with respect to allyl alcohol and palladium (II) chloride, inverse second order with respect to [Cl-], and zero order with respect to potassium hexacyanoferrate (III). The rate is found to increase linearly with hydroxyl ion concentration.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110802
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  • 114
    Electronic Resource
    Electronic Resource
    Estimating the positions of transition states from experimental data (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 853-865 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A procedure is suggested to estimate the positions of a transition state (TS) along the reaction coordinate in reaction series involving several radical reactions. It is based on the dependence between experimental activation energies U± and heat effects Q. Taking into account the shift of a TS position, the following relation between these quantities is obtained: U± -; U0± = A (Q - Q0)2 + B(Q - Q0). The subscript 0 indicates the standard reference reaction. For three series, namely, the hydrogen abstraction from hydrocarbon substrates by radicals CH3·, CF·3, and Br·, the bond lengths characterizing the TS reaction center are evaluated. The TS positions appear to vary significantly in the reaction series, which accounts for significant changes in the experimentally observed activation volumes. The derivation of the Hammond rule and the range of its validity for the series with polar and steric substituent effects are discussed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110805
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  • 115
    Electronic Resource
    Electronic Resource
    Abstraction of chlorine atoms from chloroalkanes. V. The liquid-phase reaction between Et3SiH radicals and CH2Cl2, CHCl3, CCl4, and CCl3CN (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 899-906 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of chlorine transfer from CH2Cl2, CHCl3, CCl4, and CCl3CN to the triethylsilyl radical was studied in the liquid phase by a competitive method. Br abstraction from 1-bromopentane was used as a reference. The following Arrhenius parameters were determined:where the error limits are two standard deviations (2σ). Based on these results, the observed reactivity trends in the chlorine transfer reactions of Et3Si radicals appear to primarily reflect the variation in entropy of activation rather than in activation energies.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110808
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  • 116
    Electronic Resource
    Electronic Resource
    Temperature dependence of the reactions of HO2 with NO and NO2 (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 67-87 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mixtures of N2O, H2, O2, and trace amounts of NO and NO2 were photolyzed at 213.9 nm, at 245°-328°K, and at about 1 atm total pressure (mostly H2). HO2 radicals are produced from the photolysis and they react as follows:Reaction (1b) is unimportant under all of our reaction conditions. Reaction (1a) was studied in competition with reaction (3) from which it was found that k1a/k31/2 = 6.4 × 10-6 exp { z-(1400 ± 500)/RT} cm3/2/sec1/2. If k3 is taken to be 3.3 × 10-12 cm3/sec independent of temperature, k1a = 1.2 × 10-11 exp {-(1400 ± 500)/RT} cm3/sec. Reaction (2a) is negligible compared to reaction (2b) under all of our reaction conditions. The ratio k2b/k1 = 0.61 ± 0.15 at 245°K. Using the Arrhenius expression for k1a given above leads to k2b = 4.2 × 10-13 cm3/sec, which is assumed to be independent of temperature. The intermediate HO2NO2 is unstable and induces the dark oxidation of NO through reaction (-2b), which was found to have a rate coefficient k-2b = 6 × 1017 exp {-26,000/RT} sec-1 based on the value of k1a given above. The intermediate can also decompose via Reaction (10b) is at least partially heterogeneous.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100106
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  • 117
    Electronic Resource
    Electronic Resource
    Kinetics of the thermal decomposition of bis-pentafluorine sulfur peroxide in the presence of carbon monoxide (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 111-116 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of F5SOOSF5, P, in the presence of CO has been investigated between 130.1° and 161.9°C at total pressures between 50 and 600 torr. The reaction is homogeneous, and the only final products formed are CO2 and S2F10. The rate of reaction is proportional to the pressure of P. The partial pressures of CO and O2 and the total pressure have no influence on the course of reaction: \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d\left[P \right]}}{{dt}} = k\left[P \right] $$\end{document}The results are explained by the following mechanism:
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550100109
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  • 118
    Electronic Resource
    Electronic Resource
    Masthead (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978) 
    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.550100401
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  • 119
    Electronic Resource
    Electronic Resource
    Fre-radical addition to olefins, Part 22L. L. T. Vertommen, J. M. Tedder, and J. C. Walton, J. Chem. Res. (S), 18 (1977).. Arrhenius parameters for the addition of trifluoromethyl radicals to vinyl monomers (CH2=CHX) (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 325-334 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative Arrhenius parameters have been determined for the addition of trifluoromethyl radicals to vinyl chloride (X=Cl), vinyl bromide (X=Br), acrylonitrile (X=CN), methyl vinyl ketone (X=COCH3), 2-methylbut-2-ene, and to iso-butene, taking the rate of addition to ethylene as standard. Addition occurred virtually exclusively at the unsubstituted end of all the olefins. The relative rates of addition at 164°C show very little variation. The preexponential terms for addition to the CH2 ends are constant within experimental error, and the small variations in rate are due principally to the activation energy term. The present results are put on an absolute scale using the previously determined Arrhenius parameters for addition to ethylene and are compared with data for other similar monomers determined previously.
    Additional Material: 8 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100402
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    The mechanism of methanol formation and other reactions following formaldehyde adsorption on Ni(110) (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 871-882 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The adsorption/desorption and reactive behavior of formaldehyde was studied on clean single-crystal Ni(110) at adsorption temperatures down to 200 °K. For low exposures of the surface to formaldehyde, hydrogen and CO binding states were populated due to decomposition of the molecule upon adsorption. Higher exposures gave rise to a decomposition-limited hydrogen peak exhibiting an activation energy of 20 kcal/gmol and an apparent frequency factor of 1014 sec-1. At initial coverages of H2CO exceeding about 0.5, monolayer methanol was observed to form. The formation of methanol involved a hydrogen atom transfer between two adsorbed H2CO molecules and did not occur totally via surface hydrogen. Self-oxidation to form CO2 was also observed. The surface exhibited reaction heterogeneity, and the surface reactivity was observed to depend on the temperature of adsorption of reactants, suggesting strong adsorbate-induced surface “reconstruction.”
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100807
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  • 121
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    Kinetics of the gas-phase elimination of isopropyl α-substituted acetates (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 893-897 
    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 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550100809
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  • 122
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    Masthead (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978) 
    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.550100901
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  • 123
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    The participation of aromatic neighboring groups in gas-phase elimination reactions (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 923-929 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase pyrolysis of 2-chloroethylbenzene and p-methoxy-2-chloroethylbenzene was studied in a static system over the temperature range of 411°-471°C and a pressure range of 39-202 mm Hg. The reactions in seasoned vessels, with the propene inhibitor always present, were homogeneous, first-order, and unimolecular. The rate constants are given by the Arrhenius equation for 2-chloroethylbenzene: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k(\sec ^{- 1}) = (13.07 \pm 0.35) - (220.9 \pm 4.6){\rm kJ/mol/2}{\rm .303}RT $$\end{document} and for p-methoxy-2-chloroethylbenzene: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k(\sec ^{- 1}) = (13.81 \pm 0.34) - (228.4 \pm 4.6){\rm kJ/mol/2}{\rm .303}RT $$\end{document} The presence of phenyl substituents in the β position of ethyl chloride has been found to provide anchimeric assistance in these elimination reactions.
    Additional Material: 5 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550100903
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  • 124
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    The gas-phase pyrolysis of alkyl nitrites VI. t-Amyl nitritePart V, Int. J. Chem. Kinet., 9, 567 (1977). (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 931-943 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of decomposition of tert-amyl nitrite (t-AmONO) has been studied in the absence (120°-155°C) and presence (160°-190°C) of nitric oxide. In the absence of nitric oxide for low concentrations of tert-amyl nitrite (∼10-4M) and small extents of reaction (∼1%), the first-order homogeneous rates of acetone formation are a direct measure of reaction (1) since k3a ≫ k2(NO): The rate of acetone formation is unaffected by the addition of large amounts of carbon tetrafluoride or isobutane (∼1 atm) but is completely suppressed by large amounts of nitric oxide (1 atm 120°-155°C).The rate of reaction (1) is given by k1 = 1016.3±0.1 10-40.3±0.1/θ sec-1. Since (E1 + RT) and ΔH°1 are identical, both may be equated with D(t-AmO - NO) = 40.9 ± 0.1 kcal/mol and E2 = 0 ± 0.1 kcal/mol. The thermochemistry leads to the result that ΔH°f (t-AmO) = -26.6 ± 1 kcal/mol. From ΔS°1 and A1, k2 is calculated to be 1010.5±0.2 M-1·sec-1.Although the addition of nitric oxide completely suppresses acetone formation at lower temperatures, it reappears at higher temperatures. This is a result of reaction (3a) now competing with reaction (2), thus allowing k3a to be determined. The rate constant for reaction (3a) is given by k3a = 1014.7 ± 0.2 10-14.3 ± 1/θ sec-1. There are two possible routes for the decomposition of the tert-amyloxyl radical: The dominating process is (3a). From the result at 160°C that k3a/k3b = 80, we arrive at the result k3b = 1015.0-18.7/θ sec-1.In addition to the products accounted for by the radical split (1), methyl-2-but-1-ene and methyl-2-but-2-ene are produced as a result of the six-centre elimination of nitrous acid (5): The ratio k5a/k5b was 0.35. Unlike tert-butyl where the rates of the two paths were comparable [(l) and (5)], here the total rate of the elimination process was only 0.5% that of the radical split (1). The reason for this is not clear.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100904
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  • 125
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    Quasi-steady-state approximations in air pollution modeling: Comparison of two numerical schemes for oxidant prediction (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 971-994 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A numerical method to solve the set of differential equations which describes the chemical development in polluted air is presented. The photochemical lifetimes, continuously monitored for all compounds, determine how the integrations are performed at all times. Components with lifetimes less than 10% of the time step, which is taken as 30 sec, are assumed to be in photochemical equilibrium, while compounds with photochemical lifetimes greater than 100 times the time step are computed according to Euler's method. All other components are calculated from the exponential solution of the continuity equation. The computational accuracy may be improved by iteration on components assumed to be determined by the instant values of other components. The convergence of the iteration is speeded up by ordering the short-lived compounds in a hierarchical sequence. Since computational errors connected with QSSA methods are difficult to assess, comparison with an automatic scheme is necessary. Our method has been compared with Gear's method for a range of model mixtures of hydrocarbons, nitrogen oxides, and air, thought to cover most conceivable situations of atmospheric pollution. The agreement with Gear's method is within a few percent for all components all the time, in most cases even within 1%. No accumulation of deviations occur during long-term integrations (e.g., 48 hr with day and night shiftings), and differences which appear during periods with strong concentration gradients (e.g., after sunrise) vanish when the activity has culminated. The method presented here is considerably more efficient than Gear's method, with respect to both computer time and storage.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100907
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  • 126
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    Kinetics and mechanism of oxidation of diethyl ketone by N-bromosuccinimide (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 995-1002 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxidative kinetics of diethyl ketone in perchloric acid media in the presence of mercuric acetate have been studied by using N-bromosuccinimide (NBS) as oxidant in the temperature range of 25°-50°C. It has been found that the order with respect to NBS is zero while with respect to diethyl ketone and [H+], it is unity. Succinimide, sodium perchlorate, and mercuric acetate have an insignificant effect on the reaction rate, while the dielectric effect was negative. A solvent isotope effect (k0D2O/k0H2O = 1.6-1.8) at 35°C has been observed. On the basis of the available evidences a suitable mechanism consistent with the experimental results has been proposed in which it is suggested that the mechanistic route for NBS oxidation in an acidic medium is through the enol form of the ketone. The magnitude of the solvent effect also supports the mechanism. Various activation parameters have been calculated, and the 1,2-dicarbonyl compound has been identified as the end product of the reaction.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100908
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  • 127
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    The reaction of hydrogen atoms with 1-butanethiol and thiolane the role of chemically activated 1-butanethiol (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1043-1054 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of 1-butanethiol with hydrogen atoms has been studied at temperatures of 295° and 576° K under the pressure of 660 Pa, using a conventional discharge-flow apparatus. The reaction products (besides hydrogen sulfide and methane) under the low conversion range (∼10%) consisted mainly of n-butane, 1-butene, and propylene-propane, with the relative yields of 70, 25, and 5% at 295° K and 25, 50, and 10% at 576°K. Analysis of kinetic equations by numerical integration indicates that the following initial steps are consistent with the experimental results: where the following expressions have been derived for k1 and k2: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = 1.6 \times 10^9 \,\exp (- 9.3{\rm kJ/mol}/RT)\,\,1/{\rm mol} \cdot {\rm sec} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_2 = 1.3 \times 10^{10} \,\exp (- 13.3{\rm kJ/mol}/RT)\,\,1/{\rm mol}\cdot{\rm sec} $$\end{document}The subsequent reaction of the butylthio radical with hydrogen atoms leads to the chemically activated 1-butanethiol which either stabilizes to 1-butanethiol or decomposes to 1-butene and hydrogen sulfide, depending on the experimental conditions. A similar analysis of the data on the thiolane-H system has yielded the following rate parameters for the initial step to form the 4-mercapto-1-butyl radical: .
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550101004
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    The decomposition kinetics of chemically activated methyl-d1-methylsilane-d2 and ethylsilane-d3This paper was taken from the Ph.D. thesis, of T. H. Richardson, New Mexico State University, 1976. (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1055-1079 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition kinetics of chemically activated methyl-d1-methylsilane-d2 (DMS-d3*) and ethylsilane-d3 (ES-d3*) from the Si-D and C-H insertion reactions of CH2 (1A1) with methylsilane-d3 have been studied. The total rate constants for decomposition of chemically activated DMS-d3 and ES-d3 have been measured. The individual rate constants for molecular elimination of CH3D, CH2D2, and D2 from DMS-d3* and for molecular elimination of CH3CH2D and D2 from ES-d3* have been measured. All of the above rate constants exhibit the expected kinetic isotope effect when compared to those found previously in the undeuterated system. RRKM theory calculations of the rate constants for the expected C-Si and Si-D bond rupture processes, based on energetics and activated comple× models deduced previously for the undeuterated system, were carried out. In the case of DMS-d3* the RRKM theory calculations of rate constants for the bond rupture processes combined with experimental rate constants for the molecular elimination processes gave a total rate constant for decomposition in agreement with the measured value. The results of a high-pressure study of the CH3D/CH2D2 ratio from chemically activated DMS-d3 decomposition were consistent with complete randomization of internal energy up to a pressure of 4 atmospheres (lifetime of ∼1.7 × 10×11 sec). This is not an unexpected result in light of earlier work.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550101005
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  • 129
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    Ene reactions of olefins, part II. The addition of ethylene to propylene and to isobutene and the addition of propylene to propylene (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 389-405 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of ethylene-propylene and ethylene-isobutene mixtures has been studied in a static system over the temperature range of 682°-754° K and for initial pressures of each olefin of 33-300 torr. The following molecular ene reactions were observed and the rate constants measured: Using thermodynamic data, rate constants for the corresponding retro-ene decomposition reactions were calculated and compared to kinetic data reported for similar compounds. Other products were formed by radical chain processes, the main higher molecular weight ones being cyclopentene and 1-methylcyclopentene. A mechanism involving addition of allyl radicals is suggested for the formation of these products.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100405
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  • 130
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    The kinetics of ClO formation in the flash photolysis of chlorine-oxygen mixtures (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1233-1244 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The production of ClOO and ClO radicals following the flash photolysis of chlorine + oxygen mixtures has been studied. For the mechanism the following kinetic parameters were measured: k3K = 1.3 × 1010 l2/mol2·sec; k2/k3 = 17; and k3/∊(ClOO; 250 nm) = 9.7 × 105 cm/sec. Then k3 = 5.9 × 109 l/mol·sec, k2 = 1.0 × 1011 l/mol·sec, and ∊(ClOO; 250 nm) = 6.1 × 103 l/mol·cm. From limits established for the equilibrium constant K, ΔH°f (ClOO) = 94 ± 2 kJ/mol.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550101206
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  • 131
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    EPR kinetic study of the reactions of CF3Br with H atoms and OH radicals (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1205-1213 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of CF3Br with H atoms and OH radicals have been studied at room temperature at 1-2 torr pressures in a discharge flow reactor coupled to an EPR spectrometer. The rate constant of the reaction H + CF3Br → CF3 + HBr (1) was found to be k1 = (3.27 ± 0.34) × 10-14 cm3/molec·sec. For the reaction of OH with CF3Br (8) an upper limit of 1 × 10-15 cm3/molec·sec was determined for k8. When H atoms were in excess compared to NO2, used to produce OH radicals, a noticeable reactivity of OH was observed as a result of the reaction OH + HBr → H2O + Br, HBr being produced from reaction (1).
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550101203
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  • 132
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    Quenching of biacetyl (3Au) molecules by near-resonant and off-resonant collisional partners (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1225-1232 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Laser-induced time-resolved phosphorescence has been used to evaluate the quenching of gaseous biacetyl (3Au) molecules by various molecules at 25°C. The quenching of biacetyl (3Au) molecules by biacetyl itself was not detectable under our experimental conditions, and a pressure-independent lifetime of 1.70 ± 0.08 msec was found. The bimolecular rate constants (units of l/mol·sec) for quenching of the 3Au molecules by cis-2-pentene, trans-2-pentene, cis-1,3-pentadiene, trans-1,3-pentadiene, and oxygen were found to be (3.3 ± 1.9) × 103, (4.0 ± 0.2) × 104, (3.9 ± 0.1) × 108, (1.3 ± 0.1) × 108, and (5.2 ± 0.4) × 108, respectively.
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    URL: http://dx.doi.org/10.1002/kin.550101205
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  • 133
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    The thermal reaction of 2-pentene around 500°C at low extent of reaction (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 529-544 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal reaction of 2-pentene (cis or trans) has been performed in a static system over the temperature range of 470°-535°C at low extent of reaction and for initial pressures of 20-100 torr. The main products of decomposition are methane and 1,3-butadiene. Other minor primary products have been monitored: trans-2-pentene, trans- and cis-2-butenes, ethane, 1,3-pentadienes, 3-methyl-1-butene, propylene, 1-butene, hydrogen, ethylene, and 1-pentene. The initial orders of formation, 0.8-1.1 for most of the products and 1.5-1.8 for 1-pentene, increase with temperature. The formation of the products and the influence of temperature on their orders can be essentially explained by a free radical chain mechanism. But cis-trans or trans-cis isomerization and hydrogen elimination from cis-2-pentene certainly involve both molecular and free radical processes. The formation of 1-pentene mainly occurs from the abstraction of the hydrogen atom of 2-pentene by resonance stabilized free radicals (C5H9.).
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    URL: http://dx.doi.org/10.1002/kin.550100602
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    The mechanism of the photochemical reactions of SO2 with isobutane excited at 3130 Å (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 557-580 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of the reactions of electronically excited SO2 with isobutane has been studied through the measurement of the initial quantum yields of product formation in 3130 Å irradiated gaseous binary mixtures of SO2 and isobutane and ternary mixtures of SO2, isobutane, C6H6 or CO2. Under low-pressure conditions (P 〈 10 torr) the kinetic treatment of the present data shows that only one singlet and one triplet state, presumably the 1B1 and 3B1 states, are involved in the photoreaction mechanism. The data give k2a = 8.4 × 109; SO2(1B1) + isobutane → products (2a); k5a ≃ k5 = 8.7 × 108 l./mol·sec; SO2(3B1) + isobutane → products (5a) SO2(3B1) + isobutane → (SO2) + isobutane (5b) k1a/k1 = 0.145 ± 0.037; SO2(1B1) + SO2 → SO2(3B1) + SO2 (1a) SO2(1B1) + SO2 → (2SO2) (1b) k2b/k2 = 0.273 ± 0.018; SO2(1B1) + isobutane → SO2(3B1) + isobutane (2b); SO2(1B1) + isobutane → (SO2) + isobutane (2c) error limits are ± 2 σ. The contribution from the excited SO2(1B1) molecules to the quantum yields of the photolyses of SO2-isobutane mixtures is not negligible. Under high-pressure conditions (P 〉 10 torr) the low-pressure mechanism coupled with the saturation effect on the phosphorescence lifetimes of SO2(3B1) molecules cannot alone rationalize the quantum yields. The evaluation suggests that some nonradiative intermediate state (X) is involved in the formation of “extra” triplet molecules. This ill-defined state decays largely nonradiatively to SO2 in experiments at low pressures, X → SO2 (12). In the presence of C6H6 the low-pressure data give k7 = (8.5 ± 1.8) × 1010, and the high-pressure data give k7 = (8.3 ± 0.6) × 1010 and (9.9 ± 0.9) × 1010l./mol·sec; SO2(3B1) + C6H6 → nonradiative products (7). These estimates are in good agreement with values directly measured from low-pressure lifetime studies, (8.1 ± 0.7) × 1010 and (8.8 ± 0.8) × 1010l./mol·sec.
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    URL: http://dx.doi.org/10.1002/kin.550100604
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    The Kinetics of alkyl radical reactions with aliphatic alcohol glasses as studied by electron spin resonance (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 637-648 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methyl radical reactions with matrix molecules in glasses C2H5OH, (CH2OH)2, n- and i-C3H7OH, n- and i-C4H9OH, n- and i-C5H11OH, C2D5OH, and i-C3D7OD, and the reactions of Ċ2H5, Ċ3H7, Ċ4H9, Ċ5H11 with methanol glasses have been studied. Alkyl radicals were produced by photolysis of diphenylamine-alkylhalide-alcohol mixtures using ultraviolet light. In all cases the alkyl radical decay follows the law c = c0 exp(-k √t). The √t law should not be associated with alkyl radical diffusion in a matrix. A method of processing the kinetics of those reactions in which one paramagnetic species changes into another with the total concentration being constant and the electron spin resonance spectra of both species overlapping, is described.
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    URL: http://dx.doi.org/10.1002/kin.550100609
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    Thermal decomposition of cyclopentane and related compounds (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 599-617 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclopentane has been decomposed in comparative-rate single-pulse shock-tube experiments. The pyrolytic mechanism involves isomerization to 1-pentene and also a minor pathway leading to cyclopropane and ethylene. This is followed by the decomposition of 1-pentene and cyclopropane. The rate expressions over the temperature range of 1000°-1200° K are \documentclass{article}\pagestyle{empty}\begin{document}$$ k(c-{\rm C}_{\rm 5} {\rm H}_{{\rm 10}} \to 1-{\rm C}_{\rm 5} {\rm H}_{{\rm 10}}) = 10^{16.1} \exp (- 42,700/T)\sec ^{- 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k(c-{\rm C}_{\rm 5} {\rm H}_{\rm 10} \to (c-{\rm C}_{\rm 3} {\rm H}_{\rm 6} + {\rm C}_{\rm 2} {\rm H}_{\rm 4}) = 10^{16.25} \exp (- 47,840/T)\sec ^{- 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k(1 - {\rm pentene} \to {\rm C}_{\rm 3} {\rm H}_{\rm 6} + {\rm C}_{\rm 2} {\rm H}_{\rm 5}) \sim 10^{16} \exp (- 35,900/T)\sec ^{- 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k(1 - {\rm pentene} \to {\rm C}_{\rm 3} {\rm H}_{\rm 6} + {\rm C}_{\rm 2} {\rm H}_{\rm 4}) \sim 10^{12.5} \exp (- 28,900/T)\sec ^{- 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k(c-{\rm C}_{\rm 3} {\rm H}_{\rm 6} \to {\rm C}_{\rm 3} {\rm H}_{\rm 6}) = 10^{14.3} \exp (- 31,100/T)\sec ^{- 1} {\rm at}\ {\rm 5}\ {\rm atm} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k(c-{\rm C}_{\rm 3} {\rm H}_{\rm 6} \to {\rm C}_{\rm 3} {\rm H}_{\rm 6}) = 10^{14.1} \exp (- 31,100/T)\sec ^{- 1} {\rm at}\ {\rm 1.7}\ {\rm atm} $$\end{document}Details of the cyclopentane decomposition processes are considered, and it appears that if the trimethylene radical is an intermediate, then ΔHf(trimethylene) ≤ 280 kJ/mol at 300°K.
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    URL: http://dx.doi.org/10.1002/kin.550100607
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  • 137
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    The recombination of iodine atoms in the presence of nitric oxide (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 733-743 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The recombination of iodine atoms following the flash photolysis of iodine in the presence of nitric oxide is interpreted through the mechanism with k1 = 3.5 × 109 l.2/mol2·sec; k2 ≈ 1 × 1011 l./mol·sec; k3 = 2.1 × 107 l./mol·sec at 298°K; E3 = 11 kJ/ mol; and ΔH°1 = 76 ± 6 kJ/mol. Lower and upper limits for the equilibrium constant are also established. The absorption spectrum of INO has been extended down to 223 nm and extinction coefficients for the region of 223-310 nm and 360-460 nm have been measured.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100707
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  • 138
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    The quantum efficiency of the primary processes in formaldehyde photolysis at 3130 Å and 25°C (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 713-732 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of the photolysis of formaldehyde was studied in experiments at 3130 Å and in the pressure range of 1-12 torr at 25°C. The experiments were designed to establish the quantum yields of the primary decomposition steps (1) and (2), CH2O + hν → H + HCO (1): CH2O + hν → H2 + CO (2), through the effects of added isobutene, trimethylsilane, and nitric oxide on ΦCO and ΦH2. The ratio ΦCO/ΦH2 was found to be 1.01 ± 0.09(2σ) and (ΦH2 + ΦCO)/2 = 1.10 ± 0.08 over the range of pressures and a 12-fold change in incident light intensity. Isobutene and nitric oxide additions reduced ΦH2 to about the same limiting value, 0.32 ± 0.03 and 0.34 ± 0.04, respectively, but these added gases differed in their effects on ΦCO. With isobutene addition ΦCO/ΦH2 reached a limiting value of 2.3; with NO addition ΦCO exceeded unity. The addition of small amounts of Me3SiH reduced ΦH2 to 1.02 ± 0.08 and lowered ΦCO to 0.7. These findings were rationalized in terms of a mechanism in which the “nonscavengeable,” molecular hydrogen is formed in reaction (2) with φ2 = 0.32 ± 0.03, while the “free radical” hydrogen is formed in reaction (1) with φ1 = 0.68 ± 0.03. In the pure formaldehyde system these reactions are followed by (3)-(5): H + CH2O → H2 + HCO (3); 2HCO → CH2O + CO (4); 2HCO → H2 + 2CO (5). The data suggest k4/k5 ≅ 5.8. Isobutene reduced ΦH2 by the reaction H + iso-C4H8 → C4H9 (20), and the results give k20/k3 ≅ 43 ± 4, in good agreement with the ratio of the reported values of the individual constants k3 and k20.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100706
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  • 139
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    Kinetics and mechanism of hydrogen-oxygen difluoride reaction in magnesium (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 773-781 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the H2-OF2 reaction was studied in the temperature range of 160°-310°C at 1 atm total pressure in a magnesium stirred-flow reactor. Initial concentration ranges were 1/2-1/2 mol·% OF2, 3/16-5 mol·% H2, and 1/4-5.0 mol·% O2; helium was used as the diluent. When the reactants were in a mole ratio of 3/2 (H2/OF2), the rate of disappearance of H2 was 1.5 times that of OF2, consistent with the previously reported stoichiometry. The rate of disappearance of OF2 was strongly influenced by OF2 concentration, weakly influenced by H2 concentration, and inhibited by the oxygen formed in the reaction. An increase in the surface area did not produce a significant change in the rate of reaction. These concentration dependencies led to a proposed ten-step mechanism from which was derived the following rate equation: \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{- d(\rm {OF}_2)}}{{dt}} = \frac{{k_0 (\rm {OF}_2)^2}}{{(\rm {O}_2)^{1/2}}}\left(1 + \frac{{\alpha (\rm {OF}_2)}}{{\alpha (\rm {OF}_2) + \beta (\rm {H}_2)}}\right) $$\end{document} where k0 is a complex combination of elementary rate constants and α and β are elementary rate constants. An Arrhenius treatment of k0 gave \documentclass{article}\pagestyle{empty}\begin{document}$$ k_0 = 10^{8.41 \pm 0.24} \exp (- 17,300 \pm 500/RT)(\rm {l}./\rm {mol})^{1/2} /\sec $$\end{document}These experimental Arrhenius parameters are lower than those predicted from reported and estimated elementary rate constants. The possibility of heterogeneous contributions is discussed.
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    URL: http://dx.doi.org/10.1002/kin.550100710
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  • 140
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    Wavelength dependence of the quantum efficiencies of the primary processes in formaldehyde photolysis at 25°C (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 805-819 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The quantum efficiencies of the primary processes in formaldehyde photolysis (φ1 and φ2) were determined as a function of wavelength in the range from 2890 to 3380 Å and at 25°C: CH2O + hν → H + HCO (1); CH2O + hν → H2 + CO (2). The estimates of φ2 were derived from ΦH2 values obtained in photolyses of CH2O-isobutene mixtures at high isobutene concentrations where H-atom scavenging was essentially complete. Values of φ1 + φ2, obtained from the ΦH2 values from the pure CH2O photolyses, were very near unity at all but the longest wavelengths employed: ΦH2 = φ1 + φ2 = 1.02 (2930 Å); 1.12 (3130 Å); 1.06 (3150 Å); 1.01 (3250 Å); 1.0 (3335 Å); 0.75 (3380 Å). Our results showed that the onset of photodissociation of CH2O by process (1) was at 3370 ± 10 Å; this corresponds to D(H-CHO) = 84.8 plusmn; 0.3 kcal/mol. The values of φ1 increased regularly with decreasing wavelength from 0 at 3370 Å to ∼0.7 at 3175 Å. Little further variation in φ1 occurred from 3175 to 2890 Å. For experiments at λ = 3300 Å, the addition of CO2 (∼300 torr) reduced φ2, while the effect on φ1 appeared to be small. The present results coupled with the solar irradiance estimates of Peterson [24] and the extinction data for CH2O from McQuigg and Calvert [7] were used to make new estimates of the apparent first-order rate constants (min-;1 × 103) of process (1) in the lower atmosphere at various solar zenith angles (in parentheses): 2.31 (0°); 2.17 (20°); 1.71 (40°); 0.92 (60°); and 0.17 (78°). The corresponding first-order rate constants (min-1 × 103) for solar light absorption by CH2O in the lower atmosphere are 7.74 (0°); 7.38 (20°); 6.18 (40°); 3.80 (60°); and 0.96 (78°).
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100803
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  • 141
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    A comparison of two single-pulse shock-tube techniques: The thermal decomposition of ethyl chloride and n-propyl chloride (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 855-869 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This investigation presents a detailed examination of the relative reliability of the comparative and absolute rate methods as they are applied to kinetic studies in the single-pulse shock tube. For this purpose two previously studied reactions, the thermal elimination of HCl from ethyl chloride and n-propyl chloride, were selected and mixtures of these compounds were shock heated to temperatures in the range of 960°-1100°K. The experimental results were analyzed by both methods and the rate constants obtained from these analyses are compared with those of previous studies. The advantages and shortcomings of both methods are noted and it is concluded that reliable kinetic data can be obtained by the absolute rate (isolation technique) method with careful examination of the gas-dynamic flow conditions and taking cognizance of the incident shock deceleration. The limitations of the comparative rate technique encountered in the present study were similar to those detailed in previous investigations.
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    URL: http://dx.doi.org/10.1002/kin.550100806
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  • 142
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    Radiation-induced dechlorination of carbon tetrachloride in cyclohexane and n-hexane mixtures. III. The kinetics of liquid-phase reactions of trichloromethyl radicals (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 905-909 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of gamma-radiation-induced free-radical chain reactions in solutions of carbon tetrachloride in mixtures of varying composition of cyclohexane and n-hexane was investigated in the temperature range of 296°-413°K. Trichloromethyl radicals were produced by the reaction of radiolytically generated alkyl radicals with the solute. The kinetics of the following reactions were studied: The following rate expression was obtained: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_4 /k_5 = 0.32 \pm 0.04 - (0.14 \pm 0.07)/\theta $$\end{document} The error limits are the standard deviation from the least mean-square Arrhenius plots. The present results, combined with previously measured activation parameters for hydrogen-atom abstraction from c-C6H12 and n-C6H14 by CCl3 radicals relative to CCl3 combination, afford experimental evidence that the decay of trichloromethyl species in alkane solutions is a diffusion-limited process. The thesis that activation energies of reactions (4) and (5) in the liquid phase are equal to their respective values in the gas phase is confirmed.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550100811
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  • 143
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    Competition between multiphoton fluorescence and multiphoton ionization in NO (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 945-954 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A nitrogen laser pumped tunable dye laser has been used to observe the three-photon ionization of NO through a two-photon resonance with the C2II state. Fluorescence is also observed from this state. The wavelength dependence of both signals have been measured. A reaction mechanism is postulated, which includes the initial two-photon excitation of the C2II state as the rate-limiting step. This mechanism predicts the observed second-order intensity dependence of the ionization signal and shows that the simple rate equation treatment is valid in this system.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100905
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  • 144
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    Masthead (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978) 
    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.550101001
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  • 145
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    Decay kinetics of aryloxy and semiquinone radicals in the presence of copper ions (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1005-1018 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decay kinetics of aryloxy and semiquinone radicals in the presence of copper ions in aqueous solutions has been studied by means of the flash photolysis technique. The radicals are involved in electron transfer reactions and those leading to the formation of intermediate complexes with copper ions. The complexes of p-benzosemiquinone anion radicals and 2-hydroxyphenoxy radicals with cupric ions decay in bimolecular self-reactions at a much slower rate than the original radicals. The increased stability of the complexes compared with the initial radicals is attributed to partial delocalization of the unpaired electron over the electron shell of copper and to steric hindrances in the self-reactions of complexes.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550101002
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  • 146
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    Thermal stability of cyclohexane and 1-hexene (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1119-1138 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism and initial rates of decomposition of cyclohexane and 1-hexene have been determined from single-pulse shock-tube experiments. The main initial processes involve isomerization of cyclohexane to 1-hexene, followed by decomposition of 1-hexene. From comparative rate experiments the following rate expressions have been derived: \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm cyclohexane} \to 1 - {\rm hexene}) = 10^{16.7} \exp (- 44,400/T)\,\,\sec ^{- 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_B (1 - {\rm hexene} \to {\rm C}_{\rm 3} {\rm H}_{{\rm 5}} \cdot {\rm + nC}_{\rm 3} {\rm H}_{{\rm 7}} \cdot) = 10^{15.9} \exp (- 35,600/T)\,\,\sec ^{- 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{\rm M} (1 - {\rm hexene} \to 2{\rm C}_{\rm 3} {\rm H}_6) = 10^{12.6} \exp (- 28,900/T)\,\,\sec ^{- 1} $$\end{document} The 1-hexene bond-braking reaction leads to an allylic resonance energy of 42.7 kJ and a heat of formation of allyl radicals of 176.6 kJ (300°K). There appear to be general relations relating the rate expressions for the decomposition of alkynes, alkanes, and alkenes. Studies on the induced decomposition of cyclohexane have also been carried out.
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    URL: http://dx.doi.org/10.1002/kin.550101103
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  • 147
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    Evidence for a diradical intermediate in the Diels-Alder reaction of 2-butene with cyclohexa-1,3-diene (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1183-1187 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550101108
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  • 148
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    The accuracy of the pseudo-steady-state approximation for radicals in thermal cracking (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1189-1193 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550101109
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  • 149
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    Masthead (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978) 
    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.550101201
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  • 150
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    Studies by the electron cyclotron resonance (ECR) technique. XII. Interactions of thermal-energy electrons with the molecules CHF3, CHClF2, and CHCl2F (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1215-1223 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the ECR technique the electron scavenging properties of the halomethanes CHF3, CHClF2, and CHCl2F were investigated. A brief discussion is given on the evaluation of experimental data for inefficient polar scavengers. Absolute attachment rate constants were obtained from the decrease of the cyclotron resonance signal upon addition of the above scavengers. For the molecules CHF3 and CHCl2F the activation energies for the capture processes are given. Possible capture mechanisms are discussed.
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    URL: http://dx.doi.org/10.1002/kin.550101204
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  • 151
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    Thermal stability of primary amines (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 41-66 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tertiary-amyl amine has been decomposed in single-pulse shock-tube experiments. Rate expressions for several of the important primary steps are \documentclass{article}\pagestyle{empty}\begin{document}$$ k(t{\rm C}_5 {\rm H}_{11 - {\rm NH}_2} \to t{\rm C}_5 {\rm H}_{11}\!\!\cdot + {\rm NH}_2\cdot) = 10^{15.9} \exp (-39,700/T)\sec ^{- 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm C}_2 {\rm H}_5- {\rm C}({\rm CH}_3)_2{\rm NH}_2 \to {\rm C}_2 {\rm H}_5 \cdot + \cdot{\rm C}({\rm CH}_3)_2{\rm NH}_2) = 10^{16.5} \exp (- 38,500/T)\sec ^{- 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k(t{\rm C}_5 {\rm H}_{11} {\rm NH}_2 \to {\rm C}_5 {\rm H}_{10} + {\rm NH}_3) 〈10^{14.5} \exp (- 37,200/T)\sec ^{- 1} $$\end{document}This leads to D(CH3—H) - D(NH2—H) = -10.5 kJ and D[(CH3)3C—H] - D[(CH3)2NH2C—H] = + 6 kJ.The present and earlier comparative rate single-pulse shock-tube data when combined with high-pressure hydrazine decomposition results-(after correcting for fall off effects through RRKM calculations) gives \documentclass{article}\pagestyle{empty}\begin{document}$$ [k_r^2 (t{\rm C}_5 {\rm H}_{11} \cdot,{\rm NH}_2 \cdot)/k_r (t{\rm C}_5 {\rm H}_{11} \cdot,t{\rm C}_5 {\rm H}_{11} \cdot)k_r ({\rm NH}_2 \cdot,{\rm NH}_2 \cdot)]^{1/2} \sim 2\,{\rm at}\,1100^o {\rm K} $$\end{document} where kr(…) is the recombination rate involving the appropriate radicals. This suggests that in this context amino radical behavior is analogous to that of alkyl radicals. If this agreement is exact, then \documentclass{article}\pagestyle{empty}\begin{document}$$ k_\infty ({\rm N}_2 {\rm H}_4 \to 2{\rm NH}_2 \cdot) = 10^{16.25} \exp (- 32,300/T)\sec ^{- 1} $$\end{document} Rate expressions for the primary step in the decomposition of a variety of primary amines have been computed. In the case of benzyl amine where data exist the agreement is satisfactory. The following differences in bond energies have been estimated: \documentclass{article}\pagestyle{empty}\begin{document}$$ D(i{\rm C}_3 {\rm H}_7 {-\!-} {\rm H}) {-\!-} D[{\rm CH}_3 ({\rm NH}_2){\rm CH} {-\!-} {\rm H}] = 14.3\,{\rm kJ} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ D({\rm C}_2 {\rm H}_5 {-\!-} {\rm H}) - D({\rm NH}_2 {\rm CH}_2 {-\!-} {\rm H}) = 15.9\,{\rm kJ} $$\end{document}
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    URL: http://dx.doi.org/10.1002/kin.550100105
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  • 152
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    Kinetics of the gas-phase reaction between iodine and trifluorosilane and the bond dissociation energy D(F3Si—H) (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 101-110 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reaction has been investigated in the temperature range 667-715K. The only reaction products were trifluorosilyl iodide and hydrogen iodide. The rate law \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d\left[{{\rm I}_2} \right]}}{{dt}} = \frac{{k\left[{{\rm I}_2} \right]^{1/2} \left[{{\rm F}_3 {\rm SiH}} \right]}}{{1 + k\prime \left[{{\rm HI}} \right]/\left[{{\rm I}_2} \right]}} $$\end{document} was obeyed over a wide range of iodine and trifluorosilane pressures. This expression is consistent with an iodine atom abstraction mechanism and for the step \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm I}^ \cdot + {\rm F}_3 {\rm SiH}\mathop {\longrightarrow}\limits^1 {\rm F}_3 {\rm Si}^\cdot + {\rm HI} $$\end{document} log k1(dm3/mol·sec) = (11.54 ± 0.17) - (130.5 ± 2.2 kJ/mol)/RT In 10 has been deduced. From this the bond dissociation energy D(F3Si—H) = (419 ± 5) kJ/mol (100.1 kcal/mol) is obtained. The kinetic andthermochemical implications of this value are discussed.
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    URL: http://dx.doi.org/10.1002/kin.550100108
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  • 153
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    Very low-pressure pyrolysis (VLPP) of cyclopentene (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 117-123 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The unimolecularity of the thermal dehydrogenation of cyclopentene has been confirmed using the technique of very low-pressure pyrolysis (VLPP). Application of RRKM theory shows that the experimental unimolecular rate constants obtained over the temperature range of 942°-1152°K are consistent with the high-pressure Arrhenius parameters given by\documentclass{article}\pagestyle{empty}\begin{document}$$ \log (k/\sec ^{-1}) = 13.35 - 61/\theta $$\end{document} where θ = 2.303 RT kcal/mol. These parameters are in good agreement with static and shock tube studies. No firm evidence could be found for any side reactions or reversibility under the experimental conditions used.
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    URL: http://dx.doi.org/10.1002/kin.550100110
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  • 154
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    Kinetics of fluorescence decay of SO2 excited in the 2662-3273 Å region (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 125-154 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of fluorescence decay of SO2 excited in the 2975-3273 Å region was studied using a powerful, frequency doubled, tunable dye laser system. The existence of two emitting species, first observed by Brus and McDonald, was confirmed. The collision-free lifetimes of the long-lived (L) species ranged from 100 to 300 μsec and the short-lived (S) species from 17 to 43 μsec over the wavelength range employed. The magnitude of the bimolecular quenching rate constant for the L state was a function of the excitation energy; the data show that about 1 kcal/mol of internal energy is lost per collision of the SO2(L) species excited in the range of 2998-3107 Å. Studies of the relative initial fluorescence intensity of the S to that of the L state (IS°/IL°) were made in experiments which extended to 0.11 mtorr. The pressure dependence of the IS°/IL° ratio for experiments at 3107, 3211, and 3225 Åproved that the S and L states do not decay independently. Either efficient bimolecular S → L conversion occurs or bimolecular S ⇄ L interconversion of both states is important. These data coupled with spectroscopic studies of Hamada and Merer and Shaw and coworkers favor the designation of the S and L states as SO2(1A2) and SO2(1B1), respectively. However, if the assignment is correct, then the band origin of the 1B1 state must be at a somewhat longer wavelength, λ〉 3273 Å than tentative spectroscopic assignments suggest. Bimolecular quenching rate constants for the L and S components with various atmospheric gases were determined in 3130- and 2662-Å studies.
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    URL: http://dx.doi.org/10.1002/kin.550100202
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  • 155
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    Computer study of the hydrogen atom recombination reaction under high pressure conditions (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 197-212 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hydrogen-atom recombination reaction has been simulated using a molecular dynamics technique recently formulated by the authors [1]. The rate of recombination has been calculated over a range of temperatures and inert gas concentrations (He and Ar) and agrees well with available experimental data. The calculations reproduce the negative activation energy characteristic of an atom recombination process. Over the range of conditions studied recombination was found to proceed via the energy transfer mechanism only, no evidence of bound HAr or HHe species was observed. Recombination was found to occur through an intermediate metastable diatomic molecule which is in equilibrium with its environment and from which there is a bottleneck to the formation of a stable molecule. The initial formation of a metastable species is sensitive to the hydrogen-inert gas potential, but relaxation of the total energy is primary determined by the mass of the third-body and the collision frequency.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100206
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  • 156
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    Diffusion of hydrogen atoms in spherical vessels (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 233-248 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A previously developed model for active species concentration profiles in infinite cylindrical systems has been extended to include the spherical system. The model couples the processes of diffusion to and reaction at the wall. Predictions of time buildup under conditions of homogeneous production by light, and time decay after extinguishing the light source, are made for H atoms. Such predictions require a knowledge of the wall recombination coefficient and the binary diffusion coefficient for H in heat bath gas. The model is experimentally tested by measuring the first-order decay constants of H at room temperature in various pressures (10-1500 torr) of six heat bath gases. The atomic concentration is monitored by Lyman-α absorption photometry. The results show good agreement with model predictions in the various heat bath gases up to ∼400 torr and depend only on one parameter,γ, the recombi-nation coefficient. This should be contrasted with the earlier work where slight variation in γ was invoked. The rate constants at pressures higher than 400 torr are consistently higher than model predictions.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100303
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  • 157
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    The heat of formation of the acetonyl radical VLPP studies of acetonyl bromide, isopropenylmethylether, and hexanedione-2,5 in a search for acetonyl stabilization energy (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 295-306 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of acetonyl bromide, isopropenylmethylether, and hexanedione-2,5 was studied using the very-low-pressure pyrolysis (VLPP) technique. The acetonyl radical is a product of each reaction. Arrhenius parameters determined are or acetonyl bromide ← acetonyl + Br: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k\left({\sec ^{- 1}} \right) = 16.0 - 62.5/\theta\,{\rm at}\,300^{\rm o} {\rm K} $$\end{document} and for isopropenylmethylether ← acetonyl + CH3: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k\left({\sec ^{- 1}} \right) = 15.8 - 66.3/\theta\,{\rm at}\,300^{\rm o} {\rm K} $$\end{document} These lead to values of acetonyl stabilization energy (SE) of 0.8 and -4.0 kcal/mol, respectively. Comparison of the pyrolyses of hexanedione-2,5 and 2,5-dimethylhexane indicate a value of SE ∼ 2 kcal/mol. The total of these results is taken, along with previous work, to indicate that 0 ≲ SE ≲ 2 kcal/mol.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100306
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  • 158
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    Reactions of (CO2)2+ and (CO)2+ association ions (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 335-366 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactons of (CO2)2+ and (CO)2+ with various additives have been investigated using the NBS high-pressure photoionization mass spectrometer at total pressures of 0.4-1.0 torr of either CO2 or CO. The additives include CH4, CD4, C2H2, O2, H2O, 15,14N2O, and CO in both CO2 and 13CO2. Second- and third-order rate coefficients based on an ambipolar diffusion model are reported for 25 separate reaction pairs at 295°K, as well as sequential cationic reaction mechanisms. An approximate value of 225 ± 3 kcal/mol (941 ± 13 kJ/mol) was derived for ΔHf (CO)2+ based on the kinetics observed in various CO-additive mixtures. Some projections regarding the utility of the data under other conditions are also included.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100403
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  • 159
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    Erratum (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 423-423 
    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.550100408
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  • 160
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    The evaluation of rate constants in rate laws containing two terms (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 417-422 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simple computerized method using APL is described which gives the rate constants for systems obeying the rate law -d[A]/dt = k1[A][B] + k2[A] m [B]l from sets of concentrations and times. Applications are discussed.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100407
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  • 161
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    Masthead (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978) 
    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.550100501
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  • 162
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    A program system for computer integration of multistep reaction rate equations using the gear integration method (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 461-469 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A program system is described for the integration of the rate equations resulting from large systems of elementary reactions. The Gear integration method is used for this problem, which frequently may exhibit stiffness instability when other integration methds are employed. No usage of the quasi-steady-state approximation is necessary. Ease in varying the reaction mechanism and simplicity of input structure are coupled with efficient execution and minimal demands for program storage as key features. The input-output structure, method of operation, and implementation are summarized, along with core storage requirements and execution times for trials using an IBM 360/44 computer.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550100505
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  • 163
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    Rate constant and activation energy for the gaseous reaction between hydroxyl and formaldehyde (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 519-527 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant k4 has been measured at 268°, 298°, and 334° K for the reaction CH2O + 2OH → CO + 2H2O relative to that for OH + OH (k2) by competition experiments in a discharge flow tube using mass-spectrometric analysis. Based on k2 = 2.24 × 10-12cm3/molec·sec at 298°K and E2 = 4 kJ/mol, k4 = (6.5 ± 1.5) × 10-12cm3/molec·sec at 298°K and E4 = (6 ± 2)kJ/mol.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100509
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  • 164
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    Masthead (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978) 
    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.550100601
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  • 165
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    Thallation of fluorenes: A kinetic and mechanistic study (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 581-589 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of thallation of fluorene with thallium triacetate (TTA) in HOAc-H2SO4 solutions led to the rate expression \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm rate = [TTA]}^{\rm 2} [{\rm fluorene}] $$\end{document}The rate of thallation is found to increase with increasing acid concentration, and a sixth-order dependence on [H2SO4] is observed. Decrease in solvent polarity increases the rate of thallation. The effect of substituents is in accord with the electrophilic substitution at an aromatic system. Thallation occurs at 4-position. A mechanism similar to aromatic bromination is proposed for the thallation of fluorene.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100605
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  • 166
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    The kinetics of the thermal gas-phase reaction Br2 + C6F5I → BrI + C6F5Br. An attempt to determine the bond dissociation energy D(C6F5-I) (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 591-598 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the thermal bromination reaction have been studied in the range of 261°-391°C. The observed rate law is compatible with initiation by the step for which we obtain \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_6 (cm^3 /mol - \sec) = (13.41 \pm 0.26) - (11700 \pm 700)/\theta $$\end{document} where Θ = 2.303RT cal/mol. Using the above value of E6, we have \documentclass{article}\pagestyle{empty}\begin{document}$$ {D(C}_{\rm 6} {\rm F}_{{\rm 5}^{\rm -}} {\rm I)} \to {\rm 53.5}\ {\rm kcal/mol} $$\end{document}This result disagrees with values of D(C6F5-I) obtained in other ways and we conclude that reaction (3) probably does not involve initiation by reaction (6). Instead, initiation may involve an addition of Br to the ring in C6F5I followed by decomposition of the adduct to give C6F5Br. If correct, this implies that the Arrhenius parameters above refer to the addition reaction rather than to reaction (6).
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100606
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  • 167
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    On the oxidation of malonic acid by ceric ions (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 619-636 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of malonic acid by ceric ions has been investigated in sulfuric acid solution under a variety of conditions. The initial rate at low ceric ion concentrations is first order in each of the two reactants and has an activation energy of 11.6 kcal/mol; the instantaneous rate constant increases somewhat with time during a single run. At higher concentrations of ceric ion, semilogarithmic plots are sigmoid with a reduced rate constant at long times. The rate decreases slightly with increasing sulfuric acid concentration. Rates of carbon dioxide evolution may be much less than rates of ceric ion reduction because of supersaturation effects. The observations can be explained if dissolved oxygen reacts with organic radicals to catalyze the rate of initial attack on malonic acid, but oxygen must also be consumed irreversibly during these reactions. Computations with plausible rate constants have simulated the experimental observations. These oxygen effects can rationalize peculiar almost discontinuous changes in rate when bromomalonic acid is oxidized by ceric ion. These effects may also explain the previously puzzling observation that some Belousov-Zhabotinsky solutions are oscillatory in bulk but become quiescent but excitable when spread in a thin film in contact with air.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100608
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  • 168
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    Masthead (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978) 
    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.550100701
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  • 169
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    On the reactivity of diethyl hydroxyl amine toward free radicals (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 677-686 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diethyl hydroxyl amine is an efficient trap for alkyl, alkoxy, and peroxy radicals. The specific rate constant for the reaction of ethyl radicals (gas phase, 25°C), tert-butoxy radicals (benzene solution, 115°C), and poly (peroxystyryl) peroxy radicals (styrene solution, 50°C) were evaluated as 7.2 × 105, 7.7 × 107, and 2.9 × 105 M-1·sec-1, respectively. Several possible secondary reactions of the nitroxide radicals are discussed.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100704
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  • 170
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    The kinetics of the reactions of methyl radicals with Br2, Cl2, and BrCl (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 745-757 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general competitive method is described for the study of the kinetics of the reactions of radicals with halogens and interhalogen compounds in the gas phase. The method is applied to the reactions over the temperature range of 48°-199°C. It is found that \documentclass{article}\pagestyle{empty}\begin{document}$$ \log (k_6 /k_5) = \log (k_\varepsilon /k_7) = (- 0.042 \pm 0.060) - (8700 \pm 1300)/\theta $$\end{document} where Θ=2.303RT J/mol. Also \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} A_7 = 1/2A_{5,} \,\,\,\,\,\,\,\,\,\,\,\,E_7 = E_5 \\ A_8 = 1/2A_{6,} \,\,\,\,\,\,\,\,\,\,\,\,E_8 = E_6 \\ \end{array} $$\end{document}There is no correlation between differences in activation energies and differences in enthalpy changes for these reactions, but polar effects may be important in reactions (7) and (8).
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100708
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  • 171
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    Masthead (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978) 
    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.550100801
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  • 172
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    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
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 15 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550100802
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  • 173
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    Chemical lasers produced from O(3P) atom reactions. V. CO laser emissions and vibrational population distribution in the flash-initiated SO2-CFBr3 systemThe preliminary results of this work were first reported at the 166th Annual Meeting of the American Chemical Society, Chicago, Illinois, August 1973. (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 839-853 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: CO laser emission at 5 μm was detected when SO2 and CFBr3 were flash photolyzed in the vacuum ultraviolet above 165 nm. Over 40 vibrational-rotational transitions ranging from Δv = 2 → 1 to 14 → 13, with the exception of those between 8 → 7 and 11 → 10, were identified. The CO emission is believed to result from the O + CF reaction:The vibrational population of the CO has been measured by means of a CO laser resonance absorption method. The CO was found to be vibrationally excited to v = 24 with a vibrational temperature of about 1.4 × 104°K. The “surprisal analysis” of the observed CO distribution showed the possible occurrence of a minor process (presumably O + CFBr) that generated vibrationally colder CO. The effects of various additives on the CO emission were also examined. The addition of CO2 to a D2-SO2-CFBr3-He mixture resulted in a simultaneous osciallation at 3.6, 5, and 10.6 μm due to DF, CO, and CO2, respectively. Additionally, the utilization of the O + CFn (n = 1, 2, 3) reactions as F-atom sources for HF-laser operation in flash-initiated systems were demonstrated.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100805
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  • 174
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    Kinetics and mechanism of oxidation of aliphatic ketoximes by thallium(III) acetate - part I (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 883-891 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidative cleavage of some aliphatic ketoximes by thallium(III) acetate was studied in the temperature range of 20-40°C. The reactions were followed by determination of the rates of disappearance of thallium(III) acetate for variations in [substrate], [Tl(III)], [H+], ionic strength, temperature, etc. The reactions were found to be totally second order-first order with respect to each reactant. The second-order rate constants and thermodynamic parameters were evaluated and discussed. The mechanism proposed involves one-electron oxidation to the iminoxy radical followed by an another one-electron oxidation to the hydroxynitroso compound which dimerizes and decomposes to give the carbonyl compounds and hyponitrous acid.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100808
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  • 175
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    Reaction of H with C2N2 at pressures near 1 torr (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 899-904 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of disappearance of C2N2 in the presence of a large excess of H atoms has been measured in a discharge-flow system at pressures near 1 torr and temperatures in the range of 282-338 K. Under these conditions the reaction has a small negative temperature coefficient. A transition from second-order to third-order kinetics with decreasing pressure occurs at pressures near 1 torr. The results are discussed in terms of the mechanism where k7 = (1.5 ± 0.2) × 10-15 cm3/molec1·sec is found for the forward rate of reaction (7). The results also give k7k8/k-7 = 3.7 × 10-31 cm6/molec2·sec and k7k9/k-7 = 3.0 × 10-32 cm6/molec2·sec, the first being probably an upper limit and the second probably a lower limit; hence k8/k9 = 12 is found as an upper limit.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100810
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  • 176
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    Permanganate ion oxidations X. Kinetics and mechanisms of the initial stage in the oxidation of 4-hydroxy-2-pyrimidinethiolsThis paper was presented in part at the 4th Annual Xavier-MBS Biomedical Symposium, New Orleans, Louisiana, April 6, 1976, at the 1977 Pacific Conference on Chemistry and Spectroscopy, Anaheim, California, October 12, 1977, and at the Eighth International Symposium on Organic Sulfur Chemistry, Portorož, Yugoslavia, June 19, 1978. (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 911-922 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Permanganate ion rapidly oxidizes the thiol group in 2-thiouracils (2,3-dihydro-2-thioxo-4(1H)-pyrimidinones, 4-hydroxy-2-pyrimidinethiols) to the corresponding uracil-2-sulfonates in phosphate-buffered solutions. The oxidations, which are first order in oxidant and first order in reductants, are characterized by relatively small energies of activation (Ea ≅ 4.3-6.7kcal/mol) and relatively large negative entropies of activation (ΔS
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100902
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  • 177
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    Correlation of activation energies of radical-molecule metathesis reactions with enthalpic, polar, and steric parameters (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 955-970 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that the activation energies E oF chlorine atom abstraction by cyclohexyl radicals and hydrogen atom abstraction by Cl atoms from polychloroalkanes can be correlated with the bond dissociation energies D and the Taft polar and steric substituent constants σ* and Es by the expression: \documentclass{article}\pagestyle{empty}\begin{document}$$ \Delta E = \alpha \Delta D + \rho \sigma ^* + \delta E_{\rm s} $$\end{document} where ΔE and ΔD represent the differences between the E and D values of a given substrate and those of a reference compound (CH3 substituted substrate) and α, ρ, and δ are the corresponding correlation coefficients. The use of this expression allows quantitative evaluation of the relative contribution of the various factors affecting the activation energies of these reactions and estimation of related thermochemical data.
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    URL: http://dx.doi.org/10.1002/kin.550100906
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  • 178
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    Stopped-flow studies of the mechanisms of ozone-alkene reactions in the gas phase propene and isobutene (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1019-1041 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of ozone with propene and isobutene have been studied in the gas phase at 298°K and 530 Pa (4 torr) using a stopped-flow reactor coupled to a photoionization mass spectrometer. Reactant and product concentrations were followed as a function of reaction time. The major reaction products monitored were CH2O, CH3CHO, CO2, and H2O from the propene reaction, and CH2O, (CH3)2CO, CO2, and H2O from the isobutene reaction. The observations were interpreted on the basis of the Criegee mechanism for ozonolysis in solution: for which we find kA≈kB.In the gas phase the carbene peroxy radical is postulated to isomerize and decompose into molecular and free-radical products.
    Additional Material: 14 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550101003
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  • 179
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    Masthead (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978) 
    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.550101101
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  • 180
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    Unusual H2-forming chain reaction in the 3130-Å photolysis of formaldehyde-oxygen mixtures at 25°C (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1099-1117 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic study has been made of the 3130-Å photolysis of CH2O (8 torr) in O2-containing mixtures (0.02-8 torr) and in the presence of added CO2 (0-300 torr) at 25°C. Quantum yields of formation of H2, CO, and CO2 and the loss of O2 were measured. ΦH2 and ΦCO were much above unity. In an explanation of these unexpected results, a new H-atom-forming chain mechanism was postulated involving HO2 and HO addition to CH2O: CH2O + hν → H + HCO (1) H + CH2O → H2 + HCO (3) H + O2 + M → HO2 + M (6) HCO + O2 → HO2 + CO (8) HO2 + CH2O → (HO2CH2O) → HO + HCO2H (15) HO + CH2O → H2O + HCO† (16); HCO† → H + CO (19) HO + CH2O → H2O + HCO (17) and HO + CH2O → HCO2H + H (18). When the results are rationalized in terms of this mechanism, the data suggest k16 ≫ k17 and k16/k18 ≅ 0.5. The data require that a reassessment of the relative rates of reactions (7) and (8) be made, since in the previous work HCO2H formation was used as a monitor of the rate of reaction (7) HCO + O2 + M → HCOO2 + M (7). The present data from experiments at PCH2O = 8 torr and PO2 = 1-4 torr give k7[M]/(k7[M] + k8) ≥ 0.049 ± 0.017. These data coupled with the k8 estimates of Washida and coworkers give k7 ≥ (4.4 ± 1.6) × 1011 l2/mol2·sec for M = CH2O. The reaction sequence proposed here is consistent with the observed deterimental effect of O2 addition on the laser-induced isotope enrichment in HDCO. In additional studies of CH2O-O2-isobutene mixtures it was found that ΦH2 was equal to φ2 as estimated in O2-free CH2O-isobutene mixtures. These results suggest that the increase in CO (ν = 1) product observed with O2 addition in CH2O photolysis does not result from perturbations in the fragmentation pattern of the excited CH2O, but it is likely that it originates in the occurrence of the exothermic reaction HCO + O2 → HO2 + CO (ν = 1).
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  • 181
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    Chemical actinometry at 147.0 nm (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1161-1166 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hexafluoroacetone (HFA) and O2 were photolyzed at 147.0 nm to investigate their use in chemical actinometry. The products, CO for the former and O3 in the latter case, were monitored. For accurate comparison, both of these substances were irradiated by a single light source with two identical reaction cells at 180° to each other. The light intensities I were measured under the same integrated as well as instantaneous photon flux based on φO3 and φCO (quantum yield) as 2 and 1, respectively. Optimum conditions for maximum product yield were 5.0 torr HFA pressure and an O2 flow rate of 200 ml/min at 1 atm pressure for a 20-minute photolysis period. For light intensity variations between 1.09 × 1014 and 2.10 × 1015 photons absorbed/sec, the ratio IO2/IHFA was found to be unity. Calibration with the commonly used N2O actinometer for a φN2 value of 1.41 showed that IN2O/IHFA and IN2/IO2 are unity. Both HFA and O2 are suitable chemical actinometers at 147.0 nm with φCO and φO3 of 1 and 2, respectively. The light intensity determination in the first case involves the measurement of only one product which is noncondensible at 77°K, whereas wet analysis for O3, the only product, in the second actinometer is necessary. Both of these determinations are quite simple and are preferable over product analysis in N2O actiometry, wherein N2 separation from other noncondensibles at 77°K is required.
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  • 182
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    The gas-phase pyrolysis of alkyl nitrites. VII. Primary and secondary nitrites in the presence of nitric oxide (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1195-1203 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Although our pyrolytic studies of five alkyl nitrites (RONO) have shown that it is possible to determine precise, acceptable values for k1: we have been uncertain about the mechanism for the first order production of nitroxyl from primary and secondary nitrites. Nitroxyl could arise either from the direct elimination process (5) or from the disproportionation of the alkoxyl radical concerned and nitric oxide: Thus kexp = k5 or k1k6/[k2 + k6]. If the route is reaction (6), Eexp should be identical to E1, since the ratio k6/k2 is temperature independent. We preferred the elimination process because Eexp 〈 E1 and Aexp was in agreement with transition-state calculations for such elimination processes. This study was concerned with the pyrolyses of ethyl and i-propyl nitrites in the presence of nitric oxide. The results show that nitroxyl is produced via the disproportionation of the alkoxyl radical and nitric oxide, as originally suggested by Levy. This is supported by the wealth of particularly photochemical data in the literature. Our and other previous spuriously low Arrhenius parameters are attributed to heterogeneous effects.
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  • 183
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    Comprehensive chemical kinetics, Volume 8, Proton Transfer, edited by C. H. Bamford and C. F. H. Tipper, Elsevier, Amsterdam, The Netherlands; New York, 1977. 261 pp. Price: $39.95. (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 425-425 
    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.550100409
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  • 184
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    Kinetics of the thermal decomposition of trans-1,2-dicyanocyclobutane (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 453-459 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the thermal decomposition of trans-1,2-dicyanocyclobutane, which yields only vinyl cyanide, have been studied in the temperature range of 570°-660°K using a stirred-flow reactor. The reaction was found to be first order and homogeneous with rate constants represented by the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}k{\rm (sec}^{- 1} {\rm) =}{{{\rm (16}{\rm .0} \pm {\rm 0}{\rm .3)} - {\rm (52}{\rm .9} \pm {\rm 0}{\rm .8)}} \mathord{\left/ {\vphantom {{{\rm (16}{\rm .0} \pm {\rm 0}{\rm .3)} - {\rm (52}{\rm .9} \pm {\rm 0}{\rm .8)}} \theta}} \right. \kern-\nulldelimiterspace} \theta} $$\end{document} where θ = 2.303 RT kcal/mol. The Arrhenius parameters are considerably higher than previously reported. On the assumption of a biradical mechanism the results are consistent with a cyano stabilization energy of ∼5 kcal/mol, in good agreement with the results of recent studies of related systems.
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  • 185
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    Dynamics of a conformational change in aqueous 18-crown-6 by an ultrasonic absorption method (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 471-487 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A temperature dependence study of the ultrasonic amplitudes, velocities, and relaxation times for a presumed conformational transition of noncomplexed aqueous 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) is discussed. At all temperatures a single relaxation was observed within a 15-255-MHz frequency range. The equilibrium constant for the presumed conformational transition \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CR}_1 \mathop \rightleftarrows\limits^{K_{12} } {\rm CR}_2 $\end{document} was determined to be K21 = (2 ± 2) × 10-2. The activation parameters are ΔH21≠ = 10.2 ± 1.0 kcal/mol, ΔS21≠ = 7.7 ± 0.2 cal/(mol·deg), ΔH12≠ = 7.4 ± 1.0 kcal/mol, and ΔS12≠ = 7.7 ± 0.2 cal/(mol·deg), while the thermodynamic enthalpy and entropy were found to be -2.6 ± 1.0 kcal/mol and 0 ± 0.2 cal/(mol·deg), respectively. The rate constants at 25.0°C for the presumed conformational transition are k21 = (1.0 ± 0.3) × 107 sec-1 and k12 = (6.2 ± 0.2) × 108 sec-1.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550100506
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  • 186
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    Gas-phase pyrolysis of 2,2,3,3-tetramethylbutane using a wall-less reactor (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1245-1257 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of 2,2,3,3-tetramethylbutane (TMB) has been studied using the wall-less reactor. Under homogeneous conditions up to 670°C, the activation energy is 43.2 kcal/mol and log A is 10.70. The products are 2-methylpropene, hydrogen, propene, 2-methyl-2-butene, ethane, ethene, methane, neopentane, and 2,3-dimethyl-2-butene in order of abundance. Addition of toluene, cyclopentadiene, or nitrous oxide to the system increases both the activation energy and the A factor; whereas oxygen decreases both the activation energy and the A factor. Incorporation of stainless-steel rods to provide surface has only a modest effect upon the rate. In view of this evidence, it appears that the homogeneous pyrolysis of TMB at higher pressures is a chain reaction under the described conditions.
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    URL: http://dx.doi.org/10.1002/kin.550101207
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  • 187
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    Molecular beam sampling (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1091-1097 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Beam attenuation and mass discrimination in effusive and quasieffusive molecular beams of gaseous mixtures have been studied experimentally in an instrument of conventional design, and have been rationalized in terms of transition flow effects and elastic scattering. Their implication in the quantitative monitoring of reacting chemical systems is examined, with particular emphasis in the case of the very-low-pressure pyrolysis technique.
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  • 188
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    Very-low-pressure pyrolysis of N-methyl aniline and N,N-dimethyl aniline. Enthalpy of formation of the anilino and N-methyl anilino radicals (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1139-1149 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the thermal unimolecular decompositions of N-methyl aniline and N,N-dimethyl aniline into anilino and N-methyl anilino radicals, respectively, have been studied under very low-pressure conditions. The enthalpies of formation of both radicals, ΔH°f,298°K(PhṄH,g) = 55.1 and ΔH°f,298°K(PhṄMe,g) = 53.2 kcal/mol, which have been derived from the experimental data, lead to BDE(PhNH-H) = 86.4 ± 2, BDE[PhN(Me)-H] = 84.9 ± 2 kcal/mol and to a value of 16.4 kcal/mol for the stabilization energy of the PhNH radical (relative to MeNH). These results are discussed in connection with earlier work. At high temperatures, the anilino radical loses HNC and forms the very stable cyclopentadienyl radical, a decomposition comparable to that of the phenoxy radical.
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  • 189
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    Electrocyclic versus homolytic decompositions of peroxides: Solvent and phase effectsTaken in part from the M.Sc. Thesis of P. M. Rahimi, Brock University, 1975. (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 185-195 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of isopropyl peroxide in solvents is shownto be a competition between unimolecular homolysis (kr) and an electrocyclic reaction yielding H2 plus acetone (kH). The value of kH increases markedly with increasing solvent polarity: PhCH3 〈 i-PrOH 〈 MeOH 〈 H2O. Log kH correlates linearly with Et (or Z). The effect on kr is similar but less pronounced. Log kr's for both i-Pr2O2 and t-Bu2O2 are shown to correlate with the molar solubility parameter δ. The negligible contribution of the electrocyclic reaction to thermal decompositions of peroxides in the vapor phase is thus not due to peculiar behavior of that reaction, which clearly has a polartransition state. It is argued that the transition state for unimolecular homolysis has no polar character despite the apparent sensitivity of homolysis rates to solvent polarity.
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  • 190
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    Radiationless transitions between excited singlet states of biacetyl (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 213-226 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Emission processes from lower excited states S1 (fluorescence) and T1 (phosphorescence) have been studied in the gas and liquid phases when biacetyl is excited into the second singlet state S2. (In agreement with Kasha's rule no fluorescence is observed from the S2 state.)In the liquid phase, when biacetyl is excited into the singlet states S1 and S2, no difference is observed between these emission processes. This phenomenon certainly results from an efficient nonradiative transition between the second excited singlet state S2 and the first excited state S1 with practically no excess vibrational energy. The quantum yield of this transition is almost unity and does not depend on the nature of the solvent.In the gas phase no emission processes are observed when biacetyl is excited into the S2 state at low pressure (less than 10 mm Hg). High pressure of inert gas is necessary in order to observe these processes. As for excitation into the S1 state with vibrational energy, loss of vibrational energy through collisions occurs from the S2 state. The quantum yield of the S2 → S1 transition by excitation at 290 nm is estimated around 0.5-0.6 at 6 atm of inert gas (ethane, ethylene, or carbon dioxide).
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  • 191
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    The mechanism of the vapor-phase chlorination of benzene derivatives (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 249-275 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reaction, displaying peculiar characteristics as to relative rates and isomer distributions, has been studied in detail. Prior to this study, different mechanisms had been advanced by several groups. Kinetic features (isomer patterns, relative and absolute rates, reaction orders, influences of additives, H/D isotope effects) strongly point to a free-radical (chain) process, in which (1) is a crucial step. This abstraction reaction, endothermal by about 6 kcal/mol, apparently proceeds via a transition state closely resembling the free aryl radical. Relative rates and isomer distributions therefore reflect differences in stabilization energies, or in DH°(Ar - H). With high arene-Cl2 intake ratios or, more pronounced, with CCl4 as the reagent, aryl radicals also lead to biaryl, where arene successfully competes with the halogenating agent. This interpretation is quantitatively supported by our observation that “added,˝” recognizable aryl radicals yield the same chlorination-arylation product ratio, and by the results of competitive chlorination of benzene and chloroform over a temperature range of 200°C, where the latter study substantiates the value DH0(C6H5 - H) ≈ 109 kcal/mol.
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    URL: http://dx.doi.org/10.1002/kin.550100304
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  • 192
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    Activation parameters and kinetic isotope effect in the system tropaeolin O-OH- (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 407-415 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the deprotonation of tropaeolin O by OH- ions was investigated between 9° and 30°C, and by OD- ions at 24.7°C. The pH range was 10.7-12.5, and the ionic strength 0.1M throughout. All results were obtained by the temperature jump method. On the basis of a mechanism suggested earlier, rate constants k31 for the reaction between OL- and the internally bonded weak acid and k32 for the opening of the internal hydrogen bond were evaluated. The activation energies in ordinary water were found to be ΔH≠31 = 3.6 kcal/mol, ΔS≠31 = -19 eu, and ΔH≠32 = 27 kcal/mol, ΔS≠32 = 46 eu. The kinetic isotope effect was k31H2O/k31D2O ∼ 1.5 and k32H2O/k32D2O ∼ 0.9. The unusual results for reaction path are discussed in terms of solvent participation.
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    URL: http://dx.doi.org/10.1002/kin.550100406
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  • 193
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    Stopped-flow study of the gas-phase reaction of ozone with organic sulfides: Dimethyl sulfide (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 433-452 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The autoinhibiting reaction of ozone with dimethyl sulfide (DMS), has been studied at 296°K and 1.1 kPa (8 torr) as a function of the concentrations of both reactants. The major products of the reaction are H2CO, H2O, CO, and SO2. The specific rate of primary attack of O3 on DMS is immeasurably slow. It is suggested that the rapid overall rate observed for this reaction is due to a chain reaction initiated by the very slow primary reaction. It is concluded that reaction (1) cannot be important under atmospheric conditions and that the major loss process for DMS in the atmosphere is probably reaction with photochemically generated free radicals.
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  • 194
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    HCO radical kinetics: Conjunction of laser photolysis and intracavity dye laser spectroscopy (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 427-431 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: HCO radical at a concentration of about 1014 cm-3 is produced by monochromatic laser photolysis of H2CO with a 0.6 mJ frequency-doubled, flashlamp-pumped dye laser pulse. Intracavity dye laser spectroscopy quantitatively monitors HCO absorbance near 614 nm as a function of delay time between photolysis and probing pulses. Rate constants for HCO + O2 and HCO + NO are found to be 4.0 ± 0.8 × 10-12 and 1.45 ± 0.2 × 10-11 cm3 molecule-1 sec-1.
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  • 195
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    Application of RRKM theory to the reactions OH + NO2 + N2 → HONO2 + N2 (1) and ClO + NO2 + N2 → ClONO2 + N2 (2); a modified gorin model transition state (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 489-501 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants as a function of both temperature and pressure were calculated for the title reactions using RRKM theory in conjunction with a modified Gorin transition state. The modification introduces a hindrance parameter which accounts for repulsive interactions between the rotating fragments. At the highest stratospheric pressures (∼50 torr) and at stratospheric temperature (∼220°K), the extent of “falloff” from first-order [N2] dependence is ∼70% for reaction (1) and ∼35% for reaction (2).
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    URL: http://dx.doi.org/10.1002/kin.550100507
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  • 196
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    Recombination of carbon monoxide and oxygen atoms (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 503-517 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The recombination of carbon monoxide and oxygen atoms was studied in reflected shock waves in H2:O2:CO:Ar = 0.1:1:24:75 with 1300 〈 T5 2200 K and 2 〈 P5 〈 4 atm. Reaction progress was monitored by observations of the carbon monoxide flame spectrum near 435 nm and carbon dioxide thermal emission near 4.2 μm. Data analysis was accomplished with the aid of computer modeling using a 27-reaction mechanism. Computer modeling experiments also showed that these measurements were sensitive primarily to the rate of the reaction CO + O + M = CO2 + M and only slightly sensitive to the rates of other reactions. The best fit to the data was achieved with a rate constant for this reaction of 7.7 × 10-35 exp[19 kJ/RT] cm6 s for the temperature range of these experiments. Correlation of this result and previous data covering the temperature range 250 〈 T 〈 11,000 K confirms that this recombination reaction is governed by a nonadiabatic curve crossing with an activation barrier of about 20 kJ and subsequent deactivation of a singlet CO2 molecule.
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    URL: http://dx.doi.org/10.1002/kin.550100508
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  • 197
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    Very low-pressure pyrolysis (VLPP) of but-1-yne the heat of formation and stabilization energy of the propargyl radicalPresented in part at the Fifth International Symposium on Gas Kinetics, Manchester, U.K., July 1977 (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 545-555 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The unimolecular decomposition of but-1-yne has been investigated over the temperature range of 1052° - 1152°K using the technique of very low-pressure pyrolysis (VLPP). The primary process is C—C bond fission yielding methyl and propargyl radicals. Application of RRKM theory shows that the experimental rate constants are consistent with the highpressure Arrhenius parameters given by \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k(\sec ^{- 1}) = (1.55 \pm 0.3) - (74.2 \pm 2.0)/\theta $$\end{document} where θ = 2.303 RT kcal/mol. The parameters are in good agreement with estimates based on shock-tube studies. The activation energy, combined with thermochemical data, leads to DH°[HCCCH2—CH3] = 76.0, ΔHf°(HCCĊCH2,g) = 81.4, and DH° [HCCCH2—H] = 89.2, all in kcal/mol at 300°K. The stabilization energy of the propargyl radical SE° (HCCĊCH2) has been found to be 8.8 kcal/mol. Recent result for the shock-tube pyrolysis of some alkynes have been analyzed and shown to yield values for the heat of formation and stabilization energy of the propargyl radical in excellent agreement with the present work. From a consideration of all results it is recommended that ΔHf,300°(HCCĊCH2,g) = 81.5±1.0, DH300°[HCCCH2—H] = 89.3 ± 1.0, and SE° (HCCĊCH2) = 8.7±1.0 kcal/mol.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100603
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  • 198
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    Anchimeric assistance in the gas-phase pyrolysis of β-thiomethylethyl chloride (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 649-652 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100610
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  • 199
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    On the reactivity of amines toward tert-butoxy radicals (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 653-656 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100611
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  • 200
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    Reactions of NO2+ and solvated NO2+ ions with aromatic compounds and alkanes (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 657-667 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constants and modes of reaction of NO2+ and C2H5ONO2NO2+ with aromatic compounds and alkanes have been determined in a pulsed ion cyclotron resonance mass spectrometer. Both ions undergo competing charge transfer and substitution reactions (NO2+ + M → MO+ + NO; C2H5ONO2NO2+ + M → MNO2+ + C2H5ONO2) with aromatic molecules. In both cases, the probability that a collision results in charge transfer increases with increasing exothermicity of that process. The C2H5ONO2NO2+ ion does not undergo charge transfer with molecules having an ionization potential greater than about 212 kcal/mol (9.2 eV); this observation leads to an estimate of 13 kcal/mol for the binding energy between NO2+ and C2H5ONO2. The importance of the substitution reaction depends on the number of substituents on the aromatic ring and the molecular structure, and, in the case of C2H5ONO2NO2+ ions, on the energetics of the competing charge transfer process. Both NO2+ and C2H5ONO2NO2+ undergo hydride transfer reactions with alkanes. For both these ions, k(hydride transfer)/k (collision) increases with increasing exothermicity of reaction, but in both cases the rate constants of reaction are unusually low when compared with other hydride transfer reactions of comparable exothermicity which have been reported in the literature. This is interpreted as evidence that the attack on the alkane preferentially involves the nitrogen atom (where the charge is localized) rather than one of the oxygen atoms of NO2+.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100702
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