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  • 101
    Electronic Resource
    Electronic Resource
    Photolysis of alkyl iodides at 147.0 nm. The reaction H + CnH2n + 1I → HI + CnH2n + 1Work supported in part by the U. S. Atomic Energy Commission. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 893-908 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 147 nm (8.4 eV) photolysis of gaseous C2H5I, n-C3H7I, and sec-C3H7I was investigated in the presence of and absence of HI. The main overall processes are: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{rcll} {{\rm C}_{\rm 2} {\rm H}_{\rm 5} {\rm I} + h\nu} &\to& {{\rm C}_{\rm 2} {\rm H}_{\rm 4} {\rm + H + I}} & {\phi = 0.75} \\{{\rm n{-} C}_{\rm 3} {\rm H}_{\rm 7} {\rm I} + h\nu }&\to& {{\rm C}_{\rm 3} {\rm H}_{\rm 6} {\rm + H + I}} & {\phi = 0.38} \\& \to&{ {\rm CH}_{\rm 3} +{\rm C}_{\rm 2} {\rm H}_{\rm 4} {\rm + I}} & {\phi = 0.47} \\ {\sec - \,{\rm C}_{\rm 3} {\rm H}_{\rm 7} {\rm I}\, + h\nu} &\to &{{\rm C}_{\rm 3} {\rm H}_{\rm 6} {\rm + H + I}} & {\phi = 0.80} \\ &\to&{ {\rm CH}_{\rm 3} +{\rm C}_{\rm 2} {\rm H}_{\rm 4} {\rm + I}} & {\phi = 0.07} \\\end{array} $$\end{document} These dissociative processes occur mainly as a result of initial cleavage of the weak C—I bond, followed by decomposition of the internally excited alkyl radicals. In all cases, approximately 5-10% of the alkyl radicals thus formed do not undergo dissociation at pressures around 3-7 torr. There is also evidence for the elimination of HI as well as C—C cleavage in the primary dissociation. The former is indicated by deuterium labeling experiments and the formation of cyclopropane (Φ = 0.04) as a product in the photolysis of n-C3H7I. Because the processes listed above provide a constant source of H atoms whose quantum yield can be exactly determined, it was feasible to obtain accurate values for ka/kb: For thermally equilibrated H atoms (300 K), ka/kb is 0.44 ± 0.04, 0.57 ± 0.06, 0.95 ± 0.1, and 0.024 ± 0.01 for C2H5I, n-C3H7I, sec-C3H7I, and C2H5Br, respectively.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050515
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  • 102
    Electronic Resource
    Electronic Resource
    Comparisons between experimental and calculated rate constants for dissociation and combination reactions involving small polyatomic molecules (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 947-963 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The experimental results on decomposition and combination reactions involving O3, HNO3, NH3, C2N2, and NO2Cl over extended temperature and pressure ranges are compared with the deductions from RRKM calculations. Quantitative fits of the data over the entire range are possible only if the external (overall) rotations are assumed to be involved in the reactions. Recommended rate constants for the reactions O + O2 + N2 → O3 + N2 and OH + NO2 + N2 → HNO3 + N2 are presented.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050605
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  • 103
    Electronic Resource
    Electronic Resource
    The very low-pressure dehydrogenation of cis-2-butene. The activation energy for 1,4-H2 elimination (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 991-1000 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrolysis of cis-butene-2 under conditions of very low pressure (VLPP) has been studied in the range of 1100-1300°K. The principal products are butadiene and H2, obtained in a unimolecular reaction. A competing reaction to form butene-l accounts for from 10% to 40% of the overall decomposition over the range. Using a «tight» model for the transition state and RRKM theory yields a high-pressure, unimolecular rate constant for the 1,4-H2 elimination of \documentclass{article}\pagestyle{empty}\begin{document}$$ \log \,k\left( {{\rm s}^{ - 1} } \right) = \left( {13.0 \pm 0.6} \right) - {{\left( {65 \pm 2} \right)} \mathord{\left/ {\vphantom {{\left( {65 \pm 2} \right)} \theta }} \right. \kern-\nulldelimiterspace} \theta } $$\end{document} where θ = 2.303RT in kcal/mol. There is some surface reaction of butadiene at these temperatures to yield H2 + nonvolatile residue. Butene-l proceeds to decompose irreversibly to allyl + methyl radicals which have been observed directly. Comparison with related reactions leads to the conclusion that orbital symmetry-forbidden, 1,2-H2 elimination from saturated organic compounds will have activation energies too high to observe.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050608
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  • 104
    Electronic Resource
    Electronic Resource
    Kinetics of the reactions of 2,4,6-tri-t-butylphenoxyl with cumene hydroperoxide, cumylperoxyl radicals, and molecular oxygen (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 869-877 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of 2,4,6-tri-t-butylphenoxyl (TBP) with cumene hydroperoxide (ROOH), cumylperoxyl radicals (RO2), and molecular oxygen in benzene solution have been investigated kinetically by the ESR method. The rate constant of the reaction TBP + ROOH has been estimated in the temperature range 27°-75°C: log10(k-7/M-1sec-1) = (7.1 ± 0.4) - (10.9 ± 0.6 kcal mole-1)/θThe ratio of the rate constants of reactions TBPH + RO2 products has been determined from the experimental dependence of the rate constant of reaction TBP with ROOH on [TBPH]0/[TBP]0. Putting k7 = 4.0 × 103M-1sec-1, we obtain k8 = (2.0 ± 0.2) × 108M-1sec-1 at 30°C. The reaction of TBP with O2 obeys the kinetic law -d[TBP]/dt = k′[O2][TBP]2. This is in accordance with scheme TBP + O2 ← TBP⃛O2 [I]; TBP⃛O2 + TBP · products, log10 (k′/M-2sec-1) = (-14.5 ± 0.9) + (27.2 ± 1.4)/θ at 66°-78°C, where ° = 2.303RT.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050513
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  • 105
    Electronic Resource
    Electronic Resource
    Kinetic solvent isotope effect for aromatic nucleophilic substitution in mixtures of EtOH and EtOD (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 911-917 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate coefficients for the ethoxydechlorination of 1-chloro-2,4-dinitrobenzene were measured in mixtures of EtOH and EtOD of different deuterium atom fraction n (n = 0., 0.259, 0.377, 0.581, 0.767, 0.958), at 25°C. The extreme solvent isotope effect, obtained by different extrapolation procedures, is (kD/kH) = 1.90 ± 0.02. The curved variation of kn/kH with n is interpreted by fractionation factor theory in terms of hydrogen-bonding solvation of ethoxide ion and transition state.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050602
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  • 106
    Electronic Resource
    Electronic Resource
    Pyrolysis of 2,4-dimethylhexene-l and the stability of isobutenyl radicals (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 929-946 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2,4-Dimethylhexene-l has been decomposed in single-pulse shock tube experiments. Rate expressions for the initial reactions are \documentclass{article}\pagestyle{empty}\begin{document}$$ k(C_4 H_7 - S - C_4 H_9 \to C_4 H_7 .(isobutenyl) + s - C_4 H_9 .) = 10^{15.6} \exp (- 33,200/T)\sec ^{ - 1} $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$ k(C_4 H_7 - S - C_4 H_8 \to _i C_4 H_8 + n - C_4 H_8 .) = 10^{12.5} \exp (- 26,900/T)\sec ^{ - 1} $$\end{document} sec-1 at 1.5-5 atm and 1050°K. This leads to ΔH°f300 (CH2 = C(CH3)CH2) = 124 kJ/mol, or an allylic resonance energy of 50 kJ/mol. Rate expressions for the decomposition of the appropriate olefins which yield isobutenyl radicals and methyl, ethyl, isopropyl, n-propyl, t-butyl, and t-amyl radicals, respectively, are presented. The rate expression for the decomposition of isobutenyl radical is \documentclass{article}\pagestyle{empty}\begin{document}$$ k{\rm (C}_{\rm 4} H_7 .(isobutenyl) \to C_3 H_4 (allene) + CH_3 .) = 10^{13.3} \exp (- 2,500/T)\sec ^{ - 1} $$\end{document} (at the beginning of the fall-off region). For the combination of isobutenyl and methyl radicals, the rate constant at 1020°K is \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm k(C}_{\rm 4} H_7 .(isobutenyl) + CH_3 . \to 2 - methylbutene - 1) = 10^{10.3} 1./mol\sec $$\end{document} Combination of this number and the calculated rate expression for 2-methylbutene-1 decomposition gives SC4H7. (1100) = 470 J/mol °K. This yields \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm k(C}H_3 + C_3 H_4 (allene) \to C_4 H_7 .(isobutenyl) = 10^{8.2} \exp (- 2,500/T)l./mol\sec $$\end{document} It is demonstrated that an upper limit for the rate of hydrogen abstraction by isobutenyl from toluene is \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm k(C}_{\rm 4} H_7 . + \emptyset CH_3 \to iC_4 H_8 + \emptyset CH_2 .)\underline \le 10^{8.3} \exp (- 6,000/T)l./mol\sec $$\end{document}
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050604
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  • 107
    Electronic Resource
    Electronic Resource
    Analysis of the kinetics of the thermal and chemically activated elimination of HF from 1,1,1-trifluoroethane: the C—C bond dissociation energy and the heat of formation of 1,1,1-trifluoroethane (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 965-975 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal, unimolecular elimination of HF from CH3CF3 was studied by three different groups over the temperature range 1000° to 1800°K. While the reported kinetic parameters varied greatly, it is shown here that these data may be satisfactorily correlated in terms of a four-center transition state. This correlation results in ΔE00 ++ = 69.2 kcal/mol, and log (k/s-1) = 14.6 - 72.6/θ. These results may then be combined with the kinetics of the chemically activated elimination of HF from CH3CF3 formed by the recombination of methyl and trifluoromethyl radicals. The data from three different laboratories are shown to be in excellent agreement. These data, combined with extant thermal data, yield as a best value DH00(CH3—CF3) = 99.6 ± 1.1 kcal/mol. This gives the unexpectedly high value of DH298°(CH3—CF3) = 101.2 ± 1.1 kcal/mol. It is suggested that dipoledipole interactions, primarily in CH3CF3, account for this surprisingly strong C—C bond dissociation energy. These results also yield δHf0(CH3CF3; g, 298) = -178.6 ± 1.5 kcal/mol.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050606
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  • 108
    Electronic Resource
    Electronic Resource
    The alpha effect. A review (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 1-26 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Instances of high reactivity (as signaled by a positive Brönsted deviation) by nucleophiles bearing one or more unshared pairs of electrons on an atom adjacent to the nucleophilic center (the alpha effect) are surveyed in the context of possible explanations for this phenomenon. No single cause appears to account satisfactorily for all the data. However, four factors (ground-state destabilization of the nucleophile, transition-state stabilization, solvent effect differences for alpha and nonalpha nucleophiles, and product stability) may be involved in contributory roles. The response to proton basicity of a substrate is probably not related to its susceptibility to the alpha effect. Carbon electrophiles seem to be receptive to the alpha effect in the order digonal 〉 trigonal 〉 tetrahedral. The inconsistent behavior of alpha nucleophiles makes the prediction of alpha effects rather risky and confirms the complicated nature of nucleophilic substitutions.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050102
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  • 109
    Electronic Resource
    Electronic Resource
    Very low-pressure pyrolysis. VIII. The decomposition of Di-t-amyl peroxideThis work was supported in part by Contract No. F44620-71-C-0103 with the Air Force Office of Scientific Research. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 55-65 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The very low-pressure pyrolysis (VLPP) technique has been applied to the pyrolysis of di-t-amyl peroxide (DTAP) over the temperature range 523-633°K. VLPP yields a low-pressure rate constant, kuni The conversion of kuni to k∞ which must be made to calculate the Arrhenius parameters, is accomplished via the RRKM theory. The transition state model used in the RRKM calculations was based on a transition state model which accurately reproduced the VLPP data for di-t-butyl peroxide for which the Arrhenius parameters are well known. For the decomposition of DTAP it was found that log k∞(300°K) = 15.8 - 36.4/θ, where θ = 2.303RT, in kcal/mole, and the units of k∞, are sec-1.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050106
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  • 110
    Electronic Resource
    Electronic Resource
    The homogeneous gas phase H2—D2 metathesis at room temperature: Reaction induced by specific vibrational excitation (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 93-106 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have demonstrated that reactions for which substantial activation energies are needed can be induced to occur at room temperature via specific vibrational excitation. Indeed, the indications are that the atom-switching reactions for which Ea 〉 25 kcal take place with high probability only when the activation energy is localized in the vibrational mode. In this preliminary report on the utilization of the stimulated Raman effect to generate substantial populations in the critical vibrational states required for the homogeneous atom exchange between H2 and D2, we first summarized the historical development of the concept. The experimental arrangement is then described and the analytical results tabulated; the observed dependence on relative concentrations is semiquantitatively rationalized on the basis of a model proposed in 1964. Independent shock tube and molecular beam investigations were similarly accounted for. Attention is called to the discrepancy between the generally concordant experimental results and the ab initio quantum mechanical calculations of the potential energy surface for 4H atoms.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550050109
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  • 111
    Electronic Resource
    Electronic Resource
    A flash photolysis resonance fluorescence kinetics study of ground-state sulfur atoms. III. Rate parameters for reaction of S(3P) with ethylene episulfide (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 149-153 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate constants for the reaction of S(3P) with ethylene episulfide were measured over a C2H4S concentration range of 5, a total pressure of 20-200 tort, and a flash intensity range of ˜4. Over this range of variables, the bimolecular rate constant was found to be invariant. Because of limitations imposed by the physical properties of the reactant C2H4S, temperature variations were necessarily held to the range 298-355°K. The bimolecular rate constant was found to be invariant over this limited temperature range, having a value of (4.47 ± 0.26) × 10-11 cm3 molec.-1 sec-1. The possible influence of this reaction in studies of the S(3P)-ethylene system are discussed.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550050113
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  • 112
    Electronic Resource
    Electronic Resource
    Masthead (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973) 
    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.550050201
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  • 113
    Electronic Resource
    Electronic Resource
    Chemical lasers produced from O(3P) atom reactions. I. Observation of CO and HF laser emissions from several O atom reactions (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 173-176 
    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.550050116
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  • 114
    Electronic Resource
    Electronic Resource
    A study of the bimolecular intersystem crossing reaction induced in the first excited singlet of SO2 by collisions with O2 and other atmospheric gases (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 107-117 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relative intensities of phosphorescence of SO2(3B1) molecules have been determined following the optical excitation of SO2(1B1) molecules by a 2662 Å laser pulse. From a kinetic treatment of these measurements, the intersystem crossing ratio, k2b/(k1b + k2b), was determined; SO2(1B1) + M → SO2(3B1) + M (2b); SO2(1B1) + M → SO2 + M (1b). With M = O2, N2, Ar, CO2, and CO, k2b/(k1b + k2b) = 0.030 ± 0.013, 0.034 ± 0.029, 0.025 ± 0.005, 0.052 ± 0.014, and 0.045 ± 0.028, respectively. These data allow a new, more quantitative evaluation of the extent of involvement of the “excess” triplet SO2 in the 3130 Å-irradiated mixtures of SO2 and CO at high pressures [5, 6]. The new data are also of direct interest in the determination of the theoretical maximum rates of photooxidation of SO2 in the sunlight-irratiated atmosphere of the earth.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550050110
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  • 115
    Electronic Resource
    Electronic Resource
    Kinetics of the reactions of cyclopropane derivatives. III. Gas-phase unimolecular isomerization of cyclopropyl cyanide to the cyanopropenes (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 137-147 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclopropyl cyanide isomerizes in the gas phase at 660°-760°K and 2-89 torr to give mainly cis- and trans-crotonitrile and allyl cyanide, with traces of methacrylonitrile. The reactions are first order, homogeneous, and unaffected by the presence of radical-chain inhibitors. The rate constants are given by Overall: \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} k/{\rm sec}^{ - 1} = (14.58 \pm 0.08) - (242.0 \pm 1.2){\rm kJ}\,{\rm mole}^{ - 1} /2.303RT$$\end{document} cis-Crotonitrile: \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} k/{\rm sec}^{ - 1} = (14.01 \pm 0.11) - (237.6 \pm 1.4){\rm kJ}\,{\rm mole}^{ - 1} /2.303RT$$\end{document} trans-Crotonitrile: \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} k/{\rm sec}^{ - 1} = (14.09 \pm 0.07) - (243.7 \pm 0.9){\rm kJ}\,{\rm mole}^{ - 1} /2.303RT$$\end{document} Allyl cyanide: \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} k/{\rm sec}^{ - 1} = (14.59 \pm 0.13) - (252.0 \pm 1.8){\rm kJ}\,{\rm mole}^{ - 1} /2.303RT$$\end{document} where the error limits are standard deviations. On the basis of a biradical mechanism, it is deduced that the —CH—CN radical center is resonance stabilized by ca. 30 kJ mole-1. Approximate equilibrium data are given for interconversion of the 1- and 3-cyanopropenes.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550050112
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  • 116
    Electronic Resource
    Electronic Resource
    Reaction of methyl radicals with atomic oxygen (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 47-53 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of hydrogen atoms with diazomethane was used as a source of methyl radicals to study the reaction of oxygen atoms with methyl radicals. This investigation verifies directly the earlier results that formaldehyde is a major product and that the rate constant is greater than 3×10-11cm3 molecule-1 sec-1.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050105
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  • 117
    Electronic Resource
    Electronic Resource
    Kinetics of chemically activated ethane (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 77-92 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chemically activated ethane, with an excitation energy of 114.9 ± 2 kcal/mole, was formed by reaction with methane of excited singlet methylene radicals produced by the 4358 Å photolysis of diazomethane. A decomposition rate constant of (4.6 ± 1.2) × 109 sec-1 was measured for the chemically activated ethane. This result agrees, via RRKM theory, with most other chemically activated ethane data, and the result predicts, via RRKM and absolute rate theory for E0 = 85.8 kcal/mole, E* = 114.9 kcal/mole, and kE = 4.6 × 101 sec-1, a thermal A-factor at 600°K of 1016.6±0.2 sec-1, in approximate agreement with the more recent experimental values. Combining 2 kcal/mole uncertainties in E0 and E* with the uncertainty in our rate constant yields an A-factor range of 1016.6±0.7 sec-1. It is emphasized that this large uncertainty in the A-factor results from an improbable combination of uncertainty limits for the various parameters. These decomposition results predict, via absolute rate theory (with E0(recombination) = 0) and statistical thermodynamic equilibrium constants, methyl radical recombination rates at 25°C of between 4.4 × 108 to 3.1 × 109 l.-mole-1-sec-1, which are 60 to 8 times lower, respectively, than the apparently quite reliable experimental value. A value of E0(recombination) greater than zero offers no improvement, and a value less than zero would be quite unusual. Activated complexes consistent with the experimental recombination rate and E0(recombination) = 0 greatly overestimate the experimental chemical activation and high pressure thermal decomposition rate data. Absolute rate theory as it is applied here in a straightforward way has failed in this case, or a significant amount of internally consistent data are in serious error. Some corrections to our previous calculations for higher alkanes are discussed in Appendix II.
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    URL: http://dx.doi.org/10.1002/kin.550050108
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  • 118
    Electronic Resource
    Electronic Resource
    The liquid-phase oxidation of 2,4-dimethylpentane (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 119-136 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The initiated oxidation of 2, 4-dimethylpentane in the neat liquid phase at 100°C with 760 torr O2 gives more than 90% of a mixture of 2,4-dihydroperoxy-2,4-dimethylpentane and 2-hydroperoxy-2, 4-dimethylpentane in a ratio of 7:1. The rate of oxidation depends closely on the [initiator]1/2, consistent with a mechanism in which chain termination occurs mostly by interactions of two 2-hydroperoxy-2, 4-dimethyl-4-pentylperoxy radicals. 2, 4-Dimethylpentane oxidizes only one sixth as fast as isobutane at the same rate of initiation at 100°C. In cooxidations of the same hydrocarbons, it is 0.71 as reactive as isobutane toward any of the peroxy radicals involved. 2, 4-Dimethylpentane oxidizes 7.5 times as fast at 1.25°C as at 50°C for the same rate of initiation, but the ratio of dihydroperoxide to monohydroperoxide increases only from 5 to 7, corresponding to a difference in activation energy between intramolecular and intermolecular abstraction of 1 kcal/mole. The overall activation energy (Ep - Et/2) is 10.7 kcal/mole, close to the value of 12 kcal/mole found for isobutane. Absolute values for Ep, Et, kp, kr, and kt were derived. Ring closure of 2-hydroperoxy-2, 4-methyl-4-pentyl radicals to oxetane, not detected during oxidation, was observed when this radical was generated at 100°C in the near-absence of oxygen. The ratio of rate constants for oxetane formation and addition of oxygen to the 2, 4dimethyl-2-hydroperoxy-4-pentyl radical is about 5.4 × 10-5 M at 100°C. Thus, ring closure to oxetane is too slow to compete with addition of oxygen above ˜200 torr. At 100°C, 2, 3-dimethylbutane gave no evidence of any intramolecular abstraction. However, 2, 3-dimethylpentane did give at least 12% 2, 4-glycol or hydroxyketone.
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    High-pressure photoionization mass spectrometry. Effect of internal energy and density on the ion-molecule reactions occurring in methyl, dimethyl, and trimethylamineSupported in part by the U.S. Atomic Energy Commission (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 177-186 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ion-molecule reactions of CH3NH2+, (CH3)2NH+, and (CH3)3N+ with the respective amines have been investigated at thermal kinetic energies in a high-pressure photoionization mass spectrometer at several wavelengths (energies) in the vacuum ultraviolet. The absolute rate coefficient for proton transfer from (CH3)3N+ to (CH3)3N decreases from 8.2 × 10-10 cm3/molecule · sec at 147.0 nm (8.4 eV) to 4.9 × 10-10 cm3/molecule. sec at 106.7-104.8 nm (11.7 eV). In dimethylamine, the rate coefficient decreases from 11.6 × 10-10 cm3/molecular. sec at 8 4 eV to 10.2 × 10-10 cm3/molecule osec at 11.7 eV, while no significant effect of energy was detected in methylamine. The reactions of several fragment ions are also reported. Experiments were also carried out at pressures up to 0.5 torr in order to investigate the further solvation of CH3NH2+, (CH3)2NH2+, and (CH3)3NH+. It was found that the maximum proton solvation numbers in methyl-, dimethyl-, and trimethyl-amine are 4, 3, and 2, respectively, under these conditions.
    Additional Material: 4 Ill.
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    Kinetics of the reactions of singlet molecular oxygen (O21Δg) with organic compounds in the gas phaseSupported in part by the Measures of Air Quality Program of the National Bureau of Standards. Presented at Symposium on Oxidation by Singlet Oxygen, American Chemical Society, Washington, D.C., September 1971. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 197-211 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of singlet molecular oxygen (O21Δg) with a series of organic compounds have been studied in the gas phase at 298°K. The concentration of singlet molecular oxygen was determined by titration with 2,5-dimethylfuran. The titration technique was checked using a photoionization technique. Absolute rate constants were measured on the basis of the loss of organic reactant and, in some cases, of singlet molecular oxygen. It was found that the usual method of producing singlet molecular oxygen in the gas phase can also, under some conditions, allow reactive species other than singlet molecular oxygen to enter the reactor, leading to serious errors in the determination of rate constants. This problem was eliminated by carrying out the rate measurements in the presence of a small amount of nitrogen dioxide a radical scavenger.
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    URL: http://dx.doi.org/10.1002/kin.550050204
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  • 121
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    The thermal decomposition of biacetyl (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 271-283 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of biacetyl has been studied at small percentage conversion over the temperature range 375-417°C. For these conditions, an almost quantitative mass balance was obtained by gas-chromatographic analysis. The following equation was obtained for the overall reaction Between 240° and 277°C, the decomposition of biacetyl initiated by methyl radicals has also been studied. As source of radicals, the thermolysis of azomethane was used. Moreover, the Arrhenius parameters of the following reactions were determined: where A is in sec-1 for reaction (1) and in cm3mole-1 sec-1 for reactions (3) and (4); E is in kcal/mole. Evidence is provided that the displacement reaction (4) proceeds by a two step mechanism.
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    URL: http://dx.doi.org/10.1002/kin.550050209
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  • 122
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    Heats of formation and kinetics of decomposition of nitroalkanesThis work supported by the U.S. Office of Naval Reseach under Contract N000-70-C-0190. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 261-269 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Heats of formation of solid, liquid, and gaseous nitroalkanes have been shown mostly to obey group additivity. Group values have been obtained for carbon atoms attached to one, two, and three nitro groups. The heat of formation of 1,1,1,3,5,5,5,-heptanitropentane, either solid or liquid, cannot be fitted to the scheme, even allowing for gauche effects. The differences between observed and estimated values for 1,1,1-fluorodinitroalkanes and 1,2-dinitroethane are larger than expected and should be further investigated. Activation energies have been calculated for decomposition by five-center elimination of HONO from mononitro- and dinitroalkanes using thermochemistry and estimated activation energies for the reverse reactions. The key data for these estimates were previously reported activation energies for the decomposition of nitroethane and 1,2-dinitropropane. The calculations also gave values for the heats of formation (in kcal/mole) of nitroethylene 12.4, and 1-nitropropylene 5.6, and 2-nitropropylene 1.6. Activation energies were calculated for the competing unimolecular reaction, C—N bond fission, from thermochemistry and previously reported activation energies for the decomposition of 1,1- and 2,2-dinitropropane. Comparison of Arrhenius parameters for the two competing processes, namely, HONO and C—N bond fission, shows that, for the geminate dinitroethanes and dinitropropanes, C—N bond fission is faster about 370°K and, for the mononitroalkanes and for all the mononitroalkanes and dinitroalkanes, C—N bond fission is faster above 770°K.
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  • 123
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    Flash photolysis of s-trinitrobenzene solutions (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 305-320 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Flash photolysis of s-trinitrobenzene (TNB) aerated solutions in alcohols generates a transient species with absorption maxima at 430 and 510 nm. The yield of the transient is a function of oxygen concentration, and its rate of formation is viscosity dependent. In deaerated solutions instead of the transient, a brown permanent product, identified as a charge transfer (CT) complex with absorption maxima at 470 and 550 nm, is produced. These species are formed only in polar solvents with relatively high proton affinity. The data suggest an intermolecular proton transfer, from electronically excited TNB to the solvent forming the anion The anion thereby produced interacts with oxygen in aerated alcohols to form the transient attributed to CT complex while in deaerated alcohols the anion reacts with the solvent to produce RO-, which leads to the CT complex RO…-TNB. This mechanism is supported by detailed kinetic and spectroscopic studies.
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  • 124
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    The photochlorination of perfluorocyclopentene (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 321-328 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase photochlorination of perfluorocyclopentene under continuous and intermittent illumination with 4360-Å radiation was studied between 10° and 60°C. The rate constants for the reactions. (3) \documentclass{article}\pagestyle{empty}\begin{document}$$ C_5 F_8 CL + Cl_2 \to C_5 F_8 Cl_2 + Cl $$\end{document} (4) \documentclass{article}\pagestyle{empty}\begin{document}$$ 2C_5 F_8 Cl \to \Pr oducts $$\end{document} were measured as k3 = (1.20 + 0.58) × 108 exp (-6.430 ± 177/RT) l·(mole sec) and k4 = (1.86 ± 0.76) × 107 l·(mole sec).
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  • 125
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    Kinetics of the thermal gas-phase isomerization of 1,2-epoxycyclohexane (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 353-361 
    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 decomposition of 1,2-epoxycyclohexane has been studied over the temperature range 680-740 K at pressures between 1.6 and 6 torr. Isomerization to cyclohexanone and 2-cyclohexen-1-ol accounts for ca. 97% of the primary reaction products and occurs by first-order, homogeneous, nonradical processes: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{cyclohexanone} /s^{ - 1} = 10^{14.58 \pm 0.35} \exp \left( { - 60,300 \pm 1,100/1.987T} \right) $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{cyclohexanone - 1 - o1} /s^{ - 1} = 10^{13.11 \pm .41} \exp \left( { - 55,800 \pm 1,300/1.987T} \right) $$\end{document}
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  • 126
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    A flash photolysis-resonance fluorescence kinetics study of ground-state sulfur atoms. IV. Rate parameters for reaction of S(3P) with propene and 1-butene (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 375-384 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the technique of flash photolysis-resonance fluorescence, absolute rate constants have been measured for the reaction of S(3P) with propene and 1-butene. Variations in experimental conditions included the following: temperature (215-500°K); total pressure a factor of 10; olefin concentration, a factor of 6; flash intensity (S atom concentration), a factor of 10. It was found that over these variations in the experimental conditions only the temperature had a measureable effect on the bimolecular rate constant. The derived Arrhenius rate expressions for the reactions (2) and (3) were as follows: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_2 = \left( {6.03 \pm 0.72} \right) \times 10^{ - 12} \exp \left( {\frac{{ - 0.38 \pm 0.09kcal/mol}}{{RT}}} \right) $$\end{document} temperature range 214-500°K \documentclass{article}\pagestyle{empty}\begin{document}$$ k_3 = \left( {7.41 \pm 1.15} \right) \times 10^{ - 12} \exp \left( {\frac{{ - 0.36 \pm 0.09kcal/mol}}{{RT}}} \right) $$\end{document} Units are cm3 molec-1 s-1.
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    Formation of association ions in the photoionization of alkyl halidesWork supported in part by the U. S. Atomic Energy Commission. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 445-454 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The methyl and ethyl chlorides and bromides, as well as methyl iodide, were photoionized in the vacuum ultraviolet at 300 K in a mass spectrometer over the pressure range 0.5 to approximately 100 millitorr. Under these conditions, stabilized parent ion dimers are found in CH3Br, CH3I, and C2H5Br, but not in the chlorides. Lower limits for the dissociative lifetimes of the ion-molecule collision complexes were estimated and are as follows: (CH3Br)2+, 1.6 μs; (CH3I)2+, 1.9 μs; and (C2H5Br)2+, 5.4 μs. An increase in photon energy (internal energy content of the reactant ion) decreases the dissociative lifetime of the collision complex in CH3I.
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  • 128
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    Kinetics of the thermal gas phase isomerization of bicyclo[4.1.0]heptane (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 469-475 
    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 decomposition of bicyclo[4.1.0]heptane has been studied over the temperature range of 708-769 K at pressures between 1 and 17 torr. Isomerization to 1-methylcyclohex-1-ene, methylenecyclohexane, and cycloheptene accounts for 96-98% of the primary reaction products and occurs by first-order, homogeneous, nonradical processes. \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{1 - methylcyclohex - 1 - ene3} /s^{ - 1} = 10^{14.98 \pm 0.50} \exp \left( { - 64600 \pm 1700/1.987T} \right) $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{1 - methylenecyclohexane} /s^{ - 1} = 10^{15.08 \pm 0.43} \exp \left( { - 65900 \pm 1400/1.987T} \right) $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{cyclohexane} /s^{ - 1} = 10^{14.82 \pm 0.28} \exp \left( { - 64900 \pm 1000/1.987T} \right) $$\end{document}
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    Masthead (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973) 
    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.550050401
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  • 130
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    Reactions of unsymmetrically substituted allyl radicals with methyl radicals (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 513-522 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Hg(63P1) photosensitized decompositions of 3-methyl-1-butene, 2-methyl-2-butene, 3,3-dimethyl-1-butene, and 2,3-dimethyl-1-butene have been used to generate 1-methylallyl, 1,2-dimethylallyl, 1,1-dimethylallyl, and 1,1,2-trimethylallyl radicals in the gas phase at 24 ± 1°C. From a study of the relative yields of the CH3 combination products, the relative reactivities of the reaction centers in each of these unsymmetrically substituted ambident radicals have been determined. The more substituted centers are found to be the less reactive, and this is ascribed primarily to greater steric interaction at these centers during reaction. Measurement of the ratio of trans- to cis-2-pentene formed from the 1-methylallyl radical, combined with published values for this ratio at higher temperatures, enabled the differences in entropy and heat of formation of the trans- and cis-forms of this radical to be calculated as 0.62 ± 0.85 J mol-1 K-1 and - 0.63 ± 0.25 kJ mol-1, respectively, at 298K. Approximate values of the disproportionation/combination ratios for reaction of CH3 with 1,1-dimethylallyl and 1-methylallyl have been estimated and used to compute rate constants for the recombinations of tert-butyl and isopropyl radicals that are in agreement with recently published data.
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  • 131
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    Deactivation of vibrationally excited hydrogen fluoride (v=2 and v=1) by atomic fluorine (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 553-558 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Measurements have been made which provide information concerning the rate of energy transfer between vibrationally excited HF and atomic fluorine. It was found that HF (v = 1) deactivates about seven times slower than was determined in previous experiments. The deactivation rate constant for HF (v = 2) is about six times larger than for HF (v = 1).
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    Thermolysis of dimethyl sulfoxideCommunication presented at the Fifth Symposium on Organic Sulfur Chemistry, Lund, Sweden, 1972. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 583-592 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of dimethyl sulfoxide at small extent of reaction has been studied at temperatures of 297-350°C and pressures of 10-400 Torr. The major products CH4, C2H4, and SO2 were shown to follow first-order kinetics. The activation energies for production of each was about 48 kcal·mole-1. A chain mechanism has been postulated in the light of the results of isotopic substitution experiments.
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  • 133
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    A differential technique which is independent of initial conditions for calculating the rate constant of a second-order reaction (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 621-627 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It has been shown that experimental errors of the initial conditions of a second-order reaction can cause erroneous results with the rate constant calculated directly from the differential or integrated rate expression. By means of a computer method, a differential technique has been developed so that precise initial reactant conditions are not necessary for calculating a second-order rate constant if continuous measurements of a single reaction variable are available. The technique has been successfully applied to the data of Kistiakowsky and Lacher on the condensation of acrolein and butadiene.
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  • 134
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    A measurement of the rate of the reaction N + H + M → NH + M (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 663-668 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The combination reaction between N and H atoms has been studied in a flow system by mixing H atoms produced by thermal dissociation of H2 with active nitrogen produced by a microwave discharge. Relative N atom concentrations were determined from the intensity of the yellow nitrogen afterglow. Absolute N and H atom concentrations were measured by EPR absorption spectroscopy. Absolute N atom concentrations were also determined by titration with NO. Upper and lower limits of 6.4 ± 1.5 × 10-32 and 3.1 ± 1.0 × 10-32 cm6 molecule-2 sec-1 were determined for the rate constant.
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    Masthead (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973) 
    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.550050501
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  • 136
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    Are HO radicals produced in the reaction of O(3P) with 1-C4H8? (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 715-717 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of O(3P) with 1-C4H8 was examined in the presence of CO which scavenges HO radicals to produce CO2. From the CO2 quantum yield, an upper limit to the efficiency of HO production in the reaction of O(3P) with 1-C4H8 was found to be 0.02 at both 298° and 473°K.
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    URL: http://dx.doi.org/10.1002/kin.550050419
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  • 137
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    Kinetics of diffusion-controlled reaction between chemically asymmetric molecules. II. Approximate steady-state solution (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 733-752 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The previously published equation for the rate of a diffusion-limited bimolecular reaction between chemically asymmetric molecules is studied numerically for the case that one of the reactant molecules is uniform. The results are reproduced quite well by a simple approximate chemical-kinetic steady-state scheme and, in principle, allow estimates of the size of the reactive region and of the activation-controlled rate to be made from the observed dependence of rate on solvent viscosity. The simple scheme is easily generalized to the case of two nonuniform reactants. In general, restriction of reactivity to some fraction of the molecular surface (i.e., a steric factor) must reduce the observable reaction rate, but to an extent which is moderated by the rotational diffusion of the reactant molecules.
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    The mechanism of cooxidation of isobutyraldehyde and octene-2 (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 777-790 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of isobutyraldehyde-octene-2 cooxidation at 20°C has been investigated. The ratio of cis to trans epoxides in the reaction products shows that, at aldehyde concentrations lower than 1.0M, the epoxide is formed mainly by a radical route. The difference in the ΔH of formation of cis and trans epoxides is around 0.8 kcal/mole at 20°. The isobutyraldehyde involved in the radical epoxidation chain has been found almost quantitatively to be isopropylhydroperoxide, which is formed through the decarboxylation of i-PrCO2· radicals, addition of oxygen, and abstraction of hydrogen atoms from the aldehyde. A rate constant of about 14 M-1 sec-1 at 20° has been determined for the latter reaction. The chain length for the cooxdination reaction decreases from 75 to 20 as the isobutyraldehyde concentration goes from 1.0 to 0.3M. The termination step seems to involve mainly the interaction of two i-PrO2 · radicals. The cooxidation of octene-2 with pivalaldehyde follows a similar mechanism, but the chain length is about ten times higher under the same experimental conditions.
    Additional Material: 9 Ill.
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  • 139
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    The self-inhibited pyrolysis of isobutane (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 1007-1021 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of isobutane was investigated in the ranges of 770° to 855°K and 20 to 150 Torr at up to 4% decomposition. The reaction is homogeneous and strongly self-inhibited. A simple Rice-Herzfeld chain terminated by the recombination of methyl radicals is proposed for the initial, uninhibited reaction. Self-inhibition is due to abstraction of hydrogen atoms from product isobutene giving resonance-stabilized 2-methylallyl radicals which participate in termination reactions. The reaction chains are shown to be long. It is suggested that a previously published rate constant for the initiation reaction (1)\documentclass{article}\pagestyle{empty}\begin{document}$$ i - C_4 H_{10} \to CH_3 + i - C_3 H_7 $$\end{document} is incorrect and the value k1 = 1016.8 exp (-81700 cal mol-1/RT)s-1 is recommended. The values of the rate constants for the reactions (4i) \documentclass{article}\pagestyle{empty}\begin{document}$$ CH_3 + i - C_4 H_{10} \to CH_3 + i - C_4 H_9 $$\end{document} (4t) \documentclass{article}\pagestyle{empty}\begin{document}$$ CH_3 + i - C_4 H_{10} \to CH_4 + t - C_4 H_9 $$\end{document} (8) \documentclass{article}\pagestyle{empty}\begin{document}$$ CH_3 + i - C_4 H_8 \to CH_4 + 2 - methylallyl $$\end{document} are estimated to be \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{4i} = 10^{13.16} \exp (- 16300calmol^{ - 1} /RT)cm^3 mol^{ - 1} s^{ - 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{4t} = 10^{12.51} \exp (- 12900calmol^{ - 1} /RT)cm^3 mol^{ - 1} s^{ - 1} $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{8} = 10^{14.05} \exp (- 17600calmol^{ - 1} /RT)cm^3 mol^{ - 1} s^{ - 1} $$\end{document} From a recalculation of previously published data on the pyrolysis of isobutane at lower temperatures and higher pressures, the value k11c, = 109.6 cm3 mol-1 s-1 is obtained for the rate constant of recombination of t-butyl. A calculation which is independent of any assumed rate constants or thermochemistry shows that the predominant chain termination reaction is the recombination of two methyl radicals in the conditions of the present work and the recombination of two t-butyl radicals in those of our previous study at lower temperatures and higher pressures.
    Additional Material: 6 Ill.
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  • 140
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    Unexpectedly rapid vapor-phase reaction between bromine and methyl iodide (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 1047-1051 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The overall reaction (1) \documentclass{article}\pagestyle{empty}\begin{document}$$ Br_2 + CH_3 I \to IBr + CH_3 Br $$\end{document} occurs readily in the gas phase, even at room temperature in the dark. The reaction is much faster than the corresponding process \documentclass{article}\pagestyle{empty}\begin{document}$$ Br_2 + CF_3 I \to IBr + CF_3 Br $$\end{document} and does not involve the normal bromination mechanism for gas phase reactions. Reaction (1) is probably heterogeneous although other mechanisms cannot be excluded.The overall reactions (1) \documentclass{article}\pagestyle{empty}\begin{document}$$ Br_2 + CH_3 I \to IBr + CH_3 Br $$\end{document} (2) \documentclass{article}\pagestyle{empty}\begin{document}$$ Br_2 + 2CH_3 I \to I_2 + 2CH_3 Br $$\end{document} proceed, for all practical purposes, completely to the right-hand side in the vapor phase. The expected mechanism is (3) \documentclass{article}\pagestyle{empty}\begin{document}$$ Br_2 \to 2Br $$\end{document} (4) \documentclass{article}\pagestyle{empty}\begin{document}$$ Br + CH_3 I \to IBr + CH_3 $$\end{document} (5) \documentclass{article}\pagestyle{empty}\begin{document}$$ CH_3 + Br_2 \to CH_3 Br +Br $$\end{document} (6) \documentclass{article}\pagestyle{empty}\begin{document}$$ Br + IBr \to Br_2 +I $$\end{document} (7) \documentclass{article}\pagestyle{empty}\begin{document}$$ I + I + M \to I_2 + M $$\end{document} where reaction (3) is initiated thermally or photochemically. Reaction (4) is of interest because little kinetic data are available on reactions involving abstraction of halogen by halogen and also because an accurate determination of the activation energy E4 would prmit us to calculate an acccurate value of the bond dissociation energy D(CH3—I).
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  • 141
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    Low-pressure thermal decomposition of ONBr and ONCl in shock waves (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 1023-1037 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the low-pressure unimolecular decomposition of ONBr and ONCl in an argon bath have been determined at temperatures in the vicinity of 1000°K. Both molecules exhibit the usual depression of the observed activation energy below the bond dissociation energy. The Arrhenius expressions obtained are (units of cc mole-1 sec-1): \documentclass{article}\pagestyle{empty}\begin{document}$$ ONBr - Ar:\log k = (15.06 \pm 0.27) - (25.06 \pm 1.13)kcalmole^{ - 1} /\theta $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ ONCl - Ar:\log k = (15.95 \pm 0.52) - (43.79 \pm 2.04)kcalmole^{ - 1} /\theta $$\end{document} Treatment of the data by the classical RRK theory yields s ≅ 2.7 ± 1 for ONCl and 3.0 ± 0.6 for ONBr. Coupling the shock tube results for ONCl with lower-temperature data from Ashmore and Burnett [3], one obtains s ≅ 2.5 ± 0.5 and λ ≍ 1. If it is assumed that s is also 2.5 for ONBr, then one finds the surprising (but tentative) result that λONCl—Ar/λONBr—Ar ≍ 3 to 4.
    Additional Material: 7 Ill.
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  • 142
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    The CH3—NO bond dissociation energy (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 1067-1069 
    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.550050615
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  • 143
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    The methyl radical combination rate constant as determined by kinetic spectroscopy (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 1053-1065 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant for the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} + {\rm CH}_{\rm 3} + {\rm M}\mathop {\longrightarrow}\limits^{k_1 } {\rm C}_{\rm 2} {\rm H}_{\rm 6} + {\rm M} \,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\left( {{\rm M = He}} \right) $$\end{document} has been determined by means of vacuum ultraviolet flash photolysis and time-resolved kinetic spectroscopic observations of the 1504-Å absorption band of CH3. The measurements made using three different sources of methyl radicals (azomethane, dimethylmercury, and ketene-hydrogen) were in accord and yielded a value for the rate constant of k1 = (9.53 ± 1.17) × 10-11 cc molec-1 sec-1. A detailed error analysis is presented. The f-value for the 1504-Å band of CH3 is determined to be (2.5 ± 0.7) × 10-2.
    Additional Material: 2 Ill.
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  • 144
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    Masthead (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973) 
    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.550050101
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  • 145
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    Kinetics of the reactions of cyclopropane derivatives, part II. The gas-phase pyrolysis of cyclopropylamine (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 27-35 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: At temperatures of 356-425°C and pressures of 15-60 Torr, cyclopropylamine reacts to give an equimolar mixture of ammonia and N-propylidenecyclopropylamine as the initial product. The reaction is first order, homogeneous, and unaffected by the presence of radical inhibitors, and thus proceeds by an initial rate-determining unimolecular isomerization to give a reactive intermediate, which then reacts with a further molecule of cyclopropylamine to give the observed products. Reaction in the presence of added aliphatic amines gives other imines in addition, and the nature of these indicates that the intermediate is propenylamine or its tautomer propylideneamine:
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    URL: http://dx.doi.org/10.1002/kin.550050103
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  • 146
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    The deuterium isotope effect in disproportionation of CF2D radicals (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 169-171 
    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.550050115
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  • 147
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    Kinetics of the I2-catalyzed isomerization of allyl chloride to cis- and trans-1-chloro-1-propene. The stabilization energy of the chloroallyl radicalThis work was supported in part by Grant No. 00353-07 of the Environmental Protection Agency, Air Pollution Control Administration. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 155-167 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The I2-catalyzed isomerization of allyl chloride to cis- and trans- l-chloro-l-propene was measured in a static system in the temperature range 225-329°C. Propylene was found as a side product, mainly at the lower temperatures. The rate constant for an abstraction of a hydrogen atom from allyl chloride by an iodine atom was found to obey the equation log [k,/M-1 sec-1] = (10.5 ± 0.2) -; (18.3 ± 10.4)/θ, where θ is 2.303RT in kcal/mole. Using this activation energy together with 1 ± 1 kcal/mole for the activation energy for the reaction of HI with alkyl radicals gives DH0 (CH2CHCHCl—H) = 88.6 ± 1.1 kcal/mole, and 7.4 ± 1.5 kcal/mole as the stabilization energy (SE) of the chloroallyl radical. Using the results of Abell and Adolf on allyl fluoride and allyl bromide, we conclude DH0 (CH2CHCHF—H) = 88.6 ± 1.1 and DH0 (CH2CHCHBr—H) = 89.4 ± 1.1 kcal/ mole; the SE of the corresponding radicals are 7.4 ± 2.2 and 7.8 ± 1.5 kcal/mole. The bond dissociation energies of the C—H bonds in the allyl halides are similar to that of propene, while the SE values are about 2 kcal/mole less than in the allyl radical, resulting perhaps more from the stabilization of alkyl radicals by α-halogen atoms than from differences in the unsaturated systems.
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  • 148
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    The compilation and evaluation of chemical kinetics data; a descriptive survey of current efforts (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 213-230 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A description of the current range of activities being pursued in the compilation and evaluation of chemical kinetic data is given. The roles of individual scientists, professional groups, and national and international programs are detailed. The special problems attending on kinetic parameters are enumerated and discussed. An appendix is included which gives a comprehensive list of compilations and evaluations extant in the field of chemical kinetics.
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    URL: http://dx.doi.org/10.1002/kin.550050205
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  • 149
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    The kinetics of biacetyl phosphorescence sensitized in 2875 Å-irradiated SO2-biacetyl-added gas (CO2, CO, N2) mixtures. The nature of the SO2 excited states formed at high added gas pressures (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 243-260 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The quantum yields of sensitized biacetyl phosphorescence emission have been determined for SO2-biacetyl-CO2, SO2-biacetyl-N2, and SO2-biacetyl-CO mixtures irradiated at 2875 Å. Series of experiments were made at various SO2, biacetyl, and added-gas concentrations (up to 4 × 10-2 M). The kinetic data show an “excess” biacetyl emission which requires the participation of some undefined excited state or isomer of SO2 in addition to the emitting singlet (1SO2) and triplet (3SO2) states of SO2. These results confirm the experimental observations of Cehelnik et al. [12] and Wampler et al. [9] who reported that an “excess” quantum yield of CO2 occurred in 3130 Å-irradiated SO2-CO mixtures at high CO pressures. The kinetic analysis of the data is most consistent with the hypothesis of Wampler et al.; the nonreactive, undefined excited state or high-energy isomer of SO2, designated here as X, is formed in part as 1SO2 is quenched: 1SO2 + M → (SO2—M) (1); 1SO2 + M → 3SO2 + M (2); 1SO2 + M → X + M (3). X itself does not transfer energy to biacetyl. It decays largely by a nonradiative first-order process at low pressures, X → SO2 (5), but it generates 3SO2 by collisional perturbation at high pressures, X + M → 1SO2 + M (4). In terms of this mechanism, the following rate constant ratios are derived from the present study: k2/(k1 + k2 + k3) = 0.020 ± 0.010 (M = CO2), 0.021 ± 0.010 (N2), 0.019 ± 0.010 (CO); k3/(k1 + k2 + k3) = 0.14 ± 0.02 (M = CO2), 0.085 ± 0.012 (CO), 0.11 ± 0.02 (N2); and k5/k4 (mole/l) = 0.020 ± 0.004 (M = CO2), 0.016 ± 0.003 (CO), 0.021 ± 0.005 (N2).
    Additional Material: 4 Ill.
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  • 150
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    Masthead (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973) 
    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.550050301
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  • 151
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    The gas-phase thermal unimolecular elimination of 1,1-dimethylketene from 7,7-dimethylbicyclo[3.2.0]hept-2-en-6-one (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 285-293 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase thermal decomposition of 7,7-dimethylbicyclo[3.2.0]hept-2-en-6-one (DBH) to yield cyclopentadiene and 1,1-dimethylketene as primary products was studied in the temperature range of 470-550 °K using a static reaction system. First-order rate constants for the depletion of DBH based on the internal standard technique and gaschromatographic analyses were independent of the initial starting pressure (7-68 torr) and of the conversion, ranging between 5% and 89%. (Throughout this paper, 1 torr = (101.325/760) kNm-2, and 1 cal = 4.184J). The reaction is essentially homogeneous, as the nature of the reaction vessel surface (Teflon or glass) had no effect on the observed rate constants which fit the Arrhenius relationship \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k/s^{ - 1} = 12.90 \pm 0.22 - (37071 + 0.52{\rm kcal/mole})/\theta $$\end{document} where θ = 2.303 RT. These activation parameters, when compared with those for similar reactions involving the molecules bicyclo[3.2.0]hept-2-en-6-one, bicyclo[3.2.0]heptan6-one, and cyclobutanone, demonstrate a very small effect of the alkyl substituents bonded to the carbon atom adjacent to the carbonyl carbon. Accepting the previously discussed concerted and pronounced polar nature of the mechanism for these retro-ketene addition reactions, the present data suggest that considerable changes in charge densities between the ground and transition state are only occurring on the two opposite centers of the molecule, with the negative charge residing essentially on the oxygen atom and the positive charge on the opposing bridgehead carbon atom. It then appears that the charge separation in the transition state is more appropriately described as being pseudo-zwitterionic rather than quadrupolar in nature.
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  • 152
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    Kinetics of the reactions of cyclopropane derivatives. IV. Kinetic isotope effect in the isomerisation of cyclopropylamine (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 329-331 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The high-pressure isotopic rate ratio kH/kD for isomerisation of cyclopropylamine and cyclopropylamine-N-d2 is 1.06 at 649-678 K, supporting a mechanism which does not involve migration of hydrogen from the amine group in the rate-determining step.
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    URL: http://dx.doi.org/10.1002/kin.550050303
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  • 153
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    High temperature decomposition of ethane (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 345-352 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Measurements of the rate of formation of methane in the thermal decomposition of ethane in dilute mixtures with argon were made by the shock tube technique. Derived values of the rate constant of the dissociation reaction are compared with earlier data of the same type and with recent shock tube data on the combination of methyl radicals. An RRKM calculation correlating all the data is described, from which an Arrhenius equation for the range 1000-1500°K, log k∞ = 16.9 - 89,500/2.3RT, is obtained.
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    URL: http://dx.doi.org/10.1002/kin.550050305
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  • 154
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    The reactions of atomic hydrogen and active nitrogen with hydrogen azide (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 559-576 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Detection of atoms by mass spectrometry has been used to study the reactions of hydrogen azide, HN3, with H atoms and active nitrogen, in a fast flow reactor at pressures of about 1 torr. Stoichiometry and products of the H + HN3 reaction have been determined and the rate constant of the initial step, assumed to be H + HN3 → NH2 + N2, was found to be 2.54 × 10-11 exp (-4600/RT) cm3 molecule-1 s-1, in the temperature range of 300-460K. The formation of NH3 and H2 products has been discussed from the different secondary steps which may occur in the mechanism. For the reaction of active nitrogen with HN3, evidence has been found for the participation of excited nitrogen molecules produced by a microwave discharge through molecular nitrogen. The influence of excited nitrogen molecules has been reduced by lowering the gas flow velocity. It was then possible to study the N + HN3 reaction for which the rate constant of the initial step was found to be 4.9 × 10-15 cm3 molecule-1 s-1 at room temperature. Finally, the occurrence of these elementary reactions has been discussed in the mechanism of the decomposition flame of HN3.
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    URL: http://dx.doi.org/10.1002/kin.550050407
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  • 155
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    A new mechanism for gas phase ozone-olefin reactions (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 397-413 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new mechanism for gas phase ozone-olefin reactions is proposed. The mechanism involves biradical intermediates which can react in a variety of ways. One of the possible reaction modes corresponds to the Criegie mechanism originally proposed to explain solution ozonolysis reactions and generally also accepted in the past for gas phase reactions. However, an examination of the gas phase data on ozone-olefin reactions and of the thermochemical and kinetic requirements for these reactions indicates that the Criegie reaction mode may be the least important of various other reaction possibilities. Those other reaction possibilities involve intramolecular H abstractions and rearrangements in biradical intermediates. The proposed mechanism provides very reasonable explanations for a number of unusual observations on gas phase ozonolysis. These are the formation of peroxidic bound products, aldehyde and 1,2-dicarbonyl product fluorescences, and unexpected carbonyl product formations.
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    URL: http://dx.doi.org/10.1002/kin.550050310
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  • 156
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    Further studies on the dissociation of HBr behind shock wavesThis work was supported by the U.S. Air Force under Contract No. F04701-72-C-0073. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 425-444 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Previously reported shock tube studies of the dissociation of HBr in the temperature range of 2100-4200°K have been extended to lower temperatures (1450-2300°K) in pure HBr. The course of reaction was followed by monitoring the radiative recombination emission in the visible spectrum from Br atoms. The results imply that, in the lower range of temperatures, the activation energy of dissociation, E in the expression AT-2e-E/RT, can be approximated by the HBr bond energy (88 kcal/mole). It was also found that, in this temperature range, the rate of HBr dissociation is sensitive to the Br2 dissociation rate and the HBr + Br exchange rate. When these rates were adjusted to bring computed reaction profiles into agreement with experimental ones, it was found that the higher-temperature data could also be fitted reasonably well with an HBr dissociation activation energy of 88 kcal/mole, contrary to the conclusions of our previous work, which favored an activation energy of 50 kcal/mole. The “best value” for k1Ar, the rate coefficient for HBr dissociation in the presence of Ar as chaperone, appears to be 1021.78 ± 0.3 T-2 10-88/θ cc/mole sec, where θ = 2.3 RT/1000; that for k1HBr, is 1022.66T-210-88/θ. A detailed review is given of the rate coefficients for the other pertinent reactions in the H2-Br2 system, viz., Br2 dissociation and reactions of HBr with H and Br.
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    URL: http://dx.doi.org/10.1002/kin.550050312
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  • 157
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    Relative rate constants for the reactions of trichloropropenyl radical. Application of the two-parameter Taft equation (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 477-486 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relative rate constants for the hydrogen atom abstraction by CCl3CH=CH· radical from CH2Cl2, CHCl3, CH3COCH3, CH3CN, C6H5CH3, C6H5OCH3, CH3CHO, and CH3OH in the liquid phase at 20°C have been measured. It was shown that these reaction rate constants are correlated by the two-parameter Taft equation with ρ* = 0.726 ± 0.096, r* = 1.22 ± 0.16. A relationship between r* and bond dissociation energy D(R—H) has been found for the abstraction reactions of different free radicals.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550050316
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    Very low-pressure pyrolysis. IX. The decomposition of azoethane, azoisopropane, and 2,2′-azoisobutaneThis work was supported by Contract No. F44620-71-C-0103 with the United States Air Force Office of Scientific Research. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 495-512 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The very low-pressure (VLPP) technique was used to study the pyrolysis of azoethane (AE), azoisopropane (AIP), and 2,2′-azoisobutane (AIB). The low pressure rate constants were related to the high-pressure Arrhenius parameters by means of the RRKM theory. This procedure in itself does not yield an unambiguous set of parameters. However, thermochemical and kinetic arguments are given which support the following values of log k∞ for the pyrolysis of AE, AIP, and AIB, respectively: 16.4-49.7/θ 16.6-47.9/θ, and 16.4-42.8/θ, where θ = 2.303RT in kcal/mole. The flow dependence of kuni was used to estimate the collisional efficiencies of the azo compounds relative to the wall.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550050318
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  • 159
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    Liquid-phase hydrogen abstraction from chlorinated ethanes by chlorine atoms (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 539-543 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hydrogen abstraction from the chlorinated ethanes by chlorine atoms has been investigated in the liquid phase. Rate constants relative to that for hydrogen abstraction from chloroform have been measured between 267° and 333°K using a competition technique. The results are compared with gas-phase data.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550050404
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  • 160
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    The pyrolysis of trimethylene sulfide. A unimolecular decomposition (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 545-551 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of decomposition of trimethylene sulfide to ethylene and thioformaldehyde was investigated in a single-pulse shock tube using the «relative rate» technique. The extent of reaction was measured in the reflected shock regime from 860° to 1170°K, but experimental difficulties limited the useful data to the temperature range of 980°-1040°K. The first-order rate constant was found to be k = 1013.0 exp (-48,200/RT) sec-1. This result sets an upper limit of 50 kcal/mole for the standard enthalpy of formation of CH2S, with 35 kcal/mole as a more likely value. The isomerization of cyclopropane to propene was used for the reference reaction; in turn, this was checked, in a relative rate experiment, against the pyrolysis of cyclohexene.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550050405
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  • 161
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    Constant time interval method for analysis of reaction rate data (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 577-582 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the study of chemical kinetics, many integrated reaction rate equations have the form In [f(A) + a] = bt + c, where a, b, and c are constants and f(A) is some function of the concentration of a reactant (or product) which can be calculated from the data. The left-hand side of this equation cannot be graphed versus time if the constant a is unknown. However, it is shown that f(A2) varies linearly with f(A1) if A2 is the concentration of reactant measured at a constant time interval later than A1. The constants a and b can be determined from the linear graph. A number of specific examples are considered.
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    URL: http://dx.doi.org/10.1002/kin.550050408
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  • 162
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    Investigation of the rate coefficient for O(3p) + NO2 → O2 + NOThis work was supported by Contract DAHC04-70-c-0034 with the Army Research Office, Durham, North Carolina. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 615-620 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Measurements of the rate coefficient of the reaction (O3P) + NO2 → O2 + NO have been made at 296°K and 240°K, using the technique of NO2* chemiluminescent decay. Values of 9.3 × 10-12 cm3 molec-1 sec-1 at 296°K and 10.5 × 10-12 cm3 molec-1 sec-1 at 240°K were obtained, in excellent agreement with the recent results of Davis, Herron, and Huie [1]. The earlier lower values may have resulted from loss of NO2 on surfaces.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550050411
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  • 163
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    A classical trajectory study of the effect of reaction barrier height on the vibrational energy transfer efficiency in the Cl + HCl systemThis work was sponsored by the McDonnell Douglas Independent Research and Development Program (IRAD). (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 629-642 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of reaction barrier height and initial rotational excitation of the reactants on the overall rate of H atom exchange between atomic chlorine and HCl (v = 0) and on the 0 → 1 vibrational excitation of HCl via reactive and nonreactive collisions have been investigated using quasiclassical trajectory techniques. Two empirical LEPS potential energy surfaces were employed in the calculations having reaction barrier heights of 9.84 and 7.05 kcal mol-1. Trajectory studies of planar collisions were carried out on each surface over a range of relative translational energies with the ground-state HCI collision partner given initial rotational excitation corresponding J = 0, 3, and 7. Initial molecular rotation was found to be relatively inefficient in promoting the H atom exchange; the computed rate coefficient for H atom exchange between Cl + HCl (v = 0, J = 7) was only 4 times larger than that for CI + HCI (v = 0, J = 0). The vibrational excitation rate coefficient exhibited a stronger dependence on initial molecular rotational excitation. The observed increase in the vibrational excitation rate coefficient with increasing initial molecular rotational excitation was due primarily to nonreactive intermolecular R → V energy transfer. The vibrational excitation rate coefficients increase with decreasing reaction barrier height.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550050413
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  • 164
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    The thermal decomposition of azomethane. III. Kinetics of the noninhibited reaction (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 691-714 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of azomethane (A) has been studied in a static system at temperatures between 250° and 320°C and at pressures between 5 and 402 torr, with particular attention to identification of products. Major products, in decreasing order of importance, were nitrogen, methane, ethane, methylethyldiimide, dimethylhydrazone, propane, tetramethylhydrazine, ethylene, methylpropyldiimide, and methylethylhydrazone. Carbon balance at the lowest pressure and highest temperature was 92%, but decreased with increasing pressure and decreasing temperature owing to the formation of a polymer. A fairly simple mechanism accounts reasonably well for a short chain in the decomposition, propagated by the radical CH3N2CH2 (B), and for the five most abundant products, except ethane. It turns out that there is a second source of ethane, arising by C2H5 + A → C2H6 + B; this explains an anomalously high apparent activation energy for the reaction CH3 + A → CH4 + B. Ethyl radicals are also shown to be responsible for the formation of propane, ethylene, methylethylhydrazone, and methylpropyldiimide. The radical B decomposes to CH3 + CH2 + N2, and the methylene radical (probably both singlet and triplet) is shown to yield C2H5 at low pressure and high temperature, and mostly polymer at high pressure and low temperature.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550050418
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  • 165
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    The temperature dependence and the mechanism of the SO2 (3B1) quenching reactions (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 669-690 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Arrhenius parameters have been determined for the SO2(3B1) quenching reaction (9), SO2(3B1) + M → (SO2 — M), for 21 different molecules as quenching partner M. The rate constants were calculated from phosphorescence lifetime measurements made over a range of reactant pressures and temperatures. Excitation of the SO2 (3B1) molecules was accomplished by two very different methods: (1) a 3829 Å laser pulse generated the triplet directly through absorption within the “forbidden” SO2 (3B1) → SO2 (1A1) band; (2) a broadband Xe-flash system generated SO2(3B1) molecules and triplets were formed subsequently by intersystem crossing, SO2(1B1) + M → SO2(3B1) + M. The measured rate constants were independent of the method of triplet formation employed. For the atmospheric gases, the activation energies (kcal/mole) were identical within the experimental error: N2, 2.9 ± 0.4; 02, 3.2 ± 0.5; Ar, 2.8 ± 0.6; CO2, 2.8 ± 0.4; CO, 2.7 ± 0.4; CH4, 2.5 ± 0.6. This energy corresponds to the first region of the SO2(3B1) → SO2(1A1) absorption spectra in which Brand and coworkers observe strong perturbations. It is suggested that the quenching in these cases results largely from the physical process involving potential energy surface crossing to another electronic state. Activation energies for SO2(3B1) quenching by the paraffinic hydrocarbons show a regular decrease in the series ethane, neopentane, propane, n-butane, cyclohexane, and isobutane, which parallels closely the decrease in C—H bond energies in these compounds. These and other data are most consistent with the dominance of chemical quenching in these cases. The rate constants for the olefinic and aromatic hydrocarbons and nitric oxide show only very small variations with temperature change, and they are near the kinetic collision number. These data support the hypothesis that quenching in these cases is associated with the formation of a charge-transfer complex and subsequent chemical interactions between the SO2(3B1) molecule and the π-system of these compounds.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550050417
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  • 166
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    Reactions in the gas and liquid phases: Comparison of kinetic and thermodynamic data (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 769-776 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An analysis is made of relationships to be expected between the enthalpies and entropies of reactions carried out in the gas and liquid phases, assuming ideal thermodynamic behavior of the components. The results of the analysis are compared with experimental results reported in the literature. Some discrepancies are noted. These may be the consequence of experimental error or may be due to substantial deviations from thermodynamic ideality. If the latter is commonplace, there will be difficulties in making useful predictions and correlations of thermodynamic and kinetic parameters in the liquid phase.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050505
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  • 167
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    Addition of ethyl radicals to carbon monoxide. Kinetic and thermochemical properties of the propionyl radicalAbstracted in part from the M.S. Thesis of William W. Thompson, Colorado State University, 1973. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 791-803 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Azoethane was irradiated in the presence of carbon monoxide in the temperature range of 238 to 378 K. Kinetic parameters for the addition of ethyl radicals to carbon monoxide and for the decomposition of propionyl radicals were determined. The rate constants were found to be log k(cm3 mol-1 sec-1) = 11.19 - 4.8/θ and log k(sec-1) = 12.77 - 14.4/θ, respectively. Estimated thermochemical properties of the propionyl radical are ΔHf0 = -10.6 ± 1.0 kcal mol-1, S0 = 77.3 ± 1.0 cal K-1 mol-1, and D(C2H5CO—H) = 87.4 kcal mol-1.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550050507
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  • 168
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    Time-resolved fluorescence studies on the formation and decomposition of the aromatic hydrocarbon-aliphatic amine exciplex in solution (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 833-839 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fluorescence rise and decay processes were measured and rate parameters were determined for the pyrene-tri-n-butylamine and pyrene-N,N-diethylaniline exciplex system in various solvents. An additional activation energy over that for the diffusional motion appears necessary for both exciplex formation and the deactivating quenching processes in the case of the pyrene-tri-n-butylamine system. The rate-determining step for these processes is electron transfer in the encounter collision leading to the nonrelaxed electron transfer state.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550050510
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  • 169
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    Kinetics and mechanism of the substitution of olefinic ligands by triphenylantimony in (π-monoolefin) tetracarbonyliron complexes (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 805-817 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Fe}\left( {{\rm CO}} \right)_4 \left( {{\rm CH}_2{{=\!=}} {\rm CHX}} \right) + {\rm SbPh}_3 \to {\rm Fe}\left( {{\rm CO}} \right)_4 {\rm SbPh}_3 + {\rm CH}_2{{=\!=}}{\rm CHX}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \left( {{\rm X} = {\rm OEt},{\rm Ph},{\rm Bu}^n ,{\rm Cl},{\rm Br},{\rm CO}_2 {\rm Me},{\rm CN}} \right) $$\end{document} have been studied in toluene solution. The reaction occurs by a dissociative mechanism and the observation of an appreciable mass law retardation effect shows that Fe(CO)4 is produced as an intermediate. Analysis of the effect of the substituent X on the stability of the complexes leads to the conclusion that π-backbonding between the metal and the olefinic ligand is the major cause of the M-olefin bond strength.
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    URL: http://dx.doi.org/10.1002/kin.550050508
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  • 170
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    A comparison of the thermal and photochemical oxidation of 2-propanol by two peroxoanions (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 859-868 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chain length (i.e., relative quantum yield) for the oxidation of 2-propanol by peroxodisulfate ion at 25°C has been studied. A number of initial experiments were carried out in order to clarify the influence of dissolved oxygen, light intensity, cupric ion, and acetone absorption. After these problems were understood, conditions satisfactory for evaluation of chain length were chosen. The chain length was found to be 500 (to within ±100). The difference between this value and the thermal oxidation chain length of 1800 at 60° is, in both direction and magnitude, as expected for a common mechanism and a low activation energy for the propagation steps. A remarkable difference is seen for comparable reactions of peroxodisulfate and peroxodiphosphate anions.
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    URL: http://dx.doi.org/10.1002/kin.550050512
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  • 171
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    Masthead (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973) 
    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.550050601
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  • 172
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    A simple empirical method for the estimation of activation energies in radical molecule metathesis reactions (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 879-892 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several new empirical methods are presented for the prediction of activation energies E of the metathetical transfer reaction of single bonded atoms in radical-molecule reactions of the type A· + BC → AB + C· The methods assign additive contributions to E for the endgroups A· and C·, neglecting the effect of the transferred atom B. Most of the predicted values agree to within l kcal mol-1 with the experimental activation energies (average error = 0.82 and standard deviation = 1.02 kcal mol-1). This is comparable to the best of the more complex schemes available for such estimation.
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    URL: http://dx.doi.org/10.1002/kin.550050514
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  • 173
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    The kinetics reaction of 1-chloro-2,3-epoxypropane with n-butyl and iso-butyl alcohols (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 919-927 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of 1-chloro-2,3-epoxypropane with n-butyl and isobutyl alcohols and their 3-chloro-2-hydroxypropyl ethers, respectively, in the presence of boron fluoride diethyl etherate catalyst are of the first order with regard to 1-chloro-2,3-epoxypropane as well as to the catalyst. In the catalyst concentration range of 1.4 to 47.3 mmol/l., the participation of the catalyst in the reaction is incomplete. The mechanism of the reactions resembles SN2 in regard to changes of activation entropy and influence of dielectric constant of the reaction medium upon the reaction rate. The established values of K (the ratio of propagation to initiation rates) are suitable for calculating the compositions of the adducts obtained. The experimentally obtained yields of 3-chloro-2-hydroxypropyl ethers of lower alcohols are compared with those calculated from the kinetically determined values of K.
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    URL: http://dx.doi.org/10.1002/kin.550050603
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    A method for computer analysis of kinetics of competing first- and second-order reactions (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 977-989 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Competing first- and second-order reactions of transient molecular species (e.g., triplet states and free radicals) are a common occurrence in kinetic studies such as flash photolysis and pulse radiolysis. We have developed a method for analyzing the decay kinetics of any species (Y) whose disappearance is described by -dY/dt = k1Y + k2Y2. The computer program (written in time-sharing BASIC) employs an iterative technique to obtain the least-squares estimates of the three parameters in the integrated rate equation.
    Additional Material: 5 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550050607
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  • 175
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    The gas-phase kinetics of the reaction of 1,1,1-trifluoroethyl iodine with HI: The C—I bond dissocation energy in 2,2,2-trifluoroethyl iodide (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 1001-1006 
    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 reaction of 2,2,2-trifluoroethyl iodide with hydrogen iodide has been studied over the temperature range of 525°K to 602°K and a tenfold variation in the ratio of CF3CH2I/HI. The experimental results are in good agreement with the expected free radical-mechanism: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm I}_2 + {\rm M} \rightleftharpoons 2{\rm I} + {\rm M} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm RI} + {\rm I}\mathop{\rightleftharpoons}\limits_2^1 {\rm R} + {\rm I}_2 $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm R} + {\rm HI} \mathop{\rightleftharpoons} \limits_{4}^{3} {\rm RH} + {\rm I} $$\end{document}An analysis of the kinetic data yield:\documentclass{article}\pagestyle{empty}\begin{document}$$ \log (k_1/ \rm I. \rm mol^{ - 1} s^{ - 1}) = (11.5 \pm 0.1) - (1.99 \pm 0.2)/\theta $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_2 /k_3 = (0.65 \pm 0.4) + 1.0/\theta $$\end{document} where θ =2.303RT in kcal/mol. If these results are combined with the assumption that E2 = 0 ± 1 kcal/mol, then one obtains DH0298 (CF3CH2—I) = 56.3 kcal/mol. This result may be compared with DH0298(CH3CH2—I) = 52.9 kcal/mol and suggests that substitution of three fluorines for hydrogen in the beta position strengthens the C—I bond slightly.
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    URL: http://dx.doi.org/10.1002/kin.550050609
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  • 176
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    Absolute rate constants for reactions of free radicals in the high-temperature photolysis of formamide vapor. II. Amino radicals (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 1039-1046 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rotating-sector method has been applied to the photoinitiated radical-chain decomposition of formamide at 300°C to measure the rate constant for the bimolecular disappearance of NH2 radicals. The decomposition is propagated by the reactions (1) \documentclass{article}\pagestyle{empty}\begin{document}$$ NH_2 + NH_2 CHO \to NH_3 + NH_2 CO $$\end{document} (2) \documentclass{article}\pagestyle{empty}\begin{document}$$ NH_2 CHO \to N_2 + CO $$\end{document} Conditions were chosen so that reaction (1) was rate controlling and NH2 the terminating radical. A flow system was employed with C2F6 as a carrier gas at a pressure of 300 Tort, and the chain reaction was initiated by the photolysis of either formamide or NH3. A value of 4.7(±2.0) × 1010 (M ·sec)-1 was estimated for the termination reaction (3) \documentclass{article}\pagestyle{empty}\begin{document}$$ 2NH_2 \to N_2 H_4 $$\end{document} and a value of 8.4 × 106 (M ·sec)-1 for reaction (1) in the same system, both at 300°C.
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    Masthead (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972) 
    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.550040101
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    The decomposition of chemically activated n-butane, isopentane, neohexane, and n-pentane and the correlation of their decomposition rates with radical recombination rates.Abstracted in part from the Ph.D. Thesis of W. L. Hase, New Mexico State University, 1970.The National Science Foundation is gratefully acknowledged for financial support (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 1-35 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The total decomposition rates of the chemically activated alkanes n-butane, n-pentane, isopentane, and neohexane were measured using an internal comparison technique. Chemical activation was by the C—H insertion reaction of excited singlet-state methylene radicals. A total of ten rate constants ranging from 4.6 × 105 to 2.3 × 107 sec-1 were measured for these alkanes at different excitation energies. These rates correlate via RRKM theory calculations with thermal A-factors in the range of 1016.1 to 1017.1 sec-1 for free rotoractivated complex models and in the range of 1016.4 to 1017.8 sec-1 for vibrator-activated complex models. It was found that high critical energies for decomposition, “tight” radical models, and activated complex models with free internal rotations were required to correlate the decomposition rates of these alkanes with estimated alkyl radical recombination rates. The correlation is just barely possible even for these favorable extremes, indicating that there may be a basic discrepancy between the recombination rate and decomposition rate data for alkanes.
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  • 179
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    The rate of dissociation of allyl iodide in shock wavesWork supported in part by the Army Research Office, Durham, N. C. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 87-102 
    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 allyl iodide has been measured from 742plusmn;K to 1068±K and from 169 to 1429 torr using a shock tube method in which the disappearance of allyl iodide and the appearance of iodine are followed simultaneously. The kinetics are first order in allyl iodide and probably are slightly dependent upon total pressure. Mathematical modeling shows that they are compatible with a mechanism consisting of three reactions: The experiments yield the rate constant k1, the high-pressure limiting value of which is found to be \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} k_\infty (\sec ^{ - 1}) = (14.45 \pm 0.4) - (42.8 \pm 2.4{\rm kcal})/2.3RT$$\end{document} in reasonable agreement with that predicted using the methods of Benson and O'Neal [1].
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    URL: http://dx.doi.org/10.1002/kin.550040108
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  • 180
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    Iron (II) and iron (III) isotope exchange in water-dimethyl sulfoxide mixturesAbstracted in part from the Ph.D. Thesis of Marian S. Henry, University of Minnesota, December 1970. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 37-48 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of the isotope exchange reaction between iron(II) and iron(III) perchlorates has been measured in a solvent mixture containing a 3:2 mole ratio of water to dimethyl sulfoxide over the temperature range from 25° to -98°C. In this temperature range, the reactants can diffuse together faster than they can undergo isotope exchange. The activation enthalpy and entropy for the acid-independent reaction were 6.0 ± 1.2 kcal/mole and -38 ± 17 cal/deg mole, respectively. Below -22°C, the acid-dependent exchange reaction did not contribute significantly to the exchange. In liquid media at -112° and -117°C and in a solid glass at -136°C, no isotope exchange was observed over the period of a calculated half-life for the reaction. At these temperatures, the rate at which the reactants diffuse together is slower than the calculated rate of isotope exchange. In a solid glass at -196°C, no isotope exchange was observed over the period of one week.
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  • 181
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    The reactions of C2F5 radicals with benzene in the vapor phase (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 79-86 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: C2F5 radicals were generated in the presence of benzene vapor by the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$({\rm C}_{\rm 2} {\rm F}_{\rm 5} {\rm CO})_2 {\rm O} + hv \to {\rm CO} + {\rm CO}_2 + 2{\rm C}_{\rm 2} {\rm F}_5 $$\end{document} The radicals react with the benzene by addition and pseudo H abstraction The rate constant kadd for the addition reaction (7) is given by \documentclass{article}\pagestyle{empty}\begin{document}$$\log k_{add} /k_{c^{1/2} } {\rm cm}^{{\rm 3/2}} {\rm mole}^{ - 1/2} \sec ^{ - 1/2} = (4.49 \pm 0.10) - (4210 \pm 150)/\theta $$\end{document} where θ = 2.303RT cal/mole and kc is the rate constant for combination of C2F5 radicals. The addition becomes reversible above 110°C. The reactions of CF3 and C2F5 radicals with benzene vapor are compared.
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  • 182
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    The kinetics of the reactions of O(3P) atoms with dimethyl ether and methanol (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 103-116 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction of O + CH3OCH3 were investigated using fast-flow apparatus equipped with ESR and mass-spectrometric detection. The concentration of O(3P) atoms to CH3OCH3 was varied over an unusually large range. The rate constant for reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm O} + {\rm CH}_{\rm 3} {\rm OCH}_3 \to {\rm OH} + {\rm CH}_{\rm 2} {\rm OCH}_{\rm 3} $$\end{document} was found to be k = (5.0 ± 1.0) × 1012 exp [(-2850 ± 200/RT)] cm3 mole-1 sec-1. The reaction O + CH3OH was studied using ESR detection. Based on an assumed stoichiometry of two oxygen atoms consumed per molecule of CH3OH which reacts, we obtain a value of k = (1.70 ± 0.66) × 1012 exp [(-2,280 ± 200/RT)] cm3 mole-1 sec-1 for the reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm O} + {\rm CH}_{\rm 3} {\rm OH} \to {\rm OH} + {\rm CH}_{\rm 2} {\rm OH}$$\end{document} The results obtained in this study are compared with the results from other workers on these reactions. The observation of essentially equal activation energies in these two reactions is indicative of approximately equal C—H bond strengths in CH3OCH3 and CH3OH. This is in agreement with recent measurements of these bond energies.
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  • 183
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    A quantitative study of alkyl radical reactions by kinetic spectroscopy. II. Combination of the methyl radical with the oxygen molecule (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 129-149 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CH}_{\rm 3} + {\rm O}_{\rm 2} (+ {\rm M}) \to {\rm CH}_{\rm 3} {\rm O}_{\rm 2} {\rm (+ M)}$$\end{document} have been studied, using the technique of flash photolysis and kinetic spectroscopy to follow the methyl radical concentration. The order of the reaction lies between 2 and 3 throughout the range of pressure from 25 to 380 torr at 22°C, and the results are consistent with a single reaction sequence: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} {\rm CH}_{\rm 3} + {\rm O}_{\rm 2} \mathop {{\rm \rightleftharpoons}}\limits_{\rm b}^{\rm a} {\rm CH}_{\rm 3} {\rm O}_{\rm 2} ^* \\ {\rm CH}_{\rm 3} {\rm O}_{\rm 2} ^* {\rm } + {\rm M}\mathop {{\rm \rightarrow}}\limits^{\rm c} {\rm CH}_{\rm 3} {\rm O}_{\rm 2} {\rm + M} \\ \\\end{array}$$\end{document} The limiting values of the third-order rate coefficients at low pressures are (3.6±0.3) × 1011 1.2 mole-2 sec-1 when M is neopentane, and (0.94 ± 0.03) × 1011 1.2 mole-2 sec-1 when M is nitrogen. The limiting value of the second-order rate coefficient at high pressures is (3.1 ± 0.3) × 108 1. mole-1 sec-1. The rate constant for the independent second-order reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CH}_{\rm 3} + {\rm O}_{\rm 2} \to {\rm CH}_{\rm 2} {\rm O} \to {\rm OH}$$\end{document} is shown to be not much greater than 2 × 105 1. mole-1 sec-1, so that this reaction does not complete significantly with the combination reaction.This new interpretation is contrary to currently accepted views.
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    The reaction of CH3N3 with C2H4. A homogenous, bimolecular processAbstracted from a Dissertation submitted by M. S. O'Dell, Jr. to the Graduate school of Arts and Sciences in partial fulfillment of the requirement for the Ph.D. degree of the Catholic University of America. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 363-365 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550040313
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  • 185
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    The reaction of C2F5 radicals with H2S (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 395-403 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of C2F5 radicals with H2S \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {(2)} & {{\rm C}_{\rm 2} {\rm H}_{\rm 5} + {\rm H}_{\rm 2} {\rm S} \to {\rm C}_{\rm 2} {\rm F}_{\rm 5} {\rm H} + {\rm HS}} & {k_H } \\ \end{array}$$\end{document} was studied over the range 1°-123°C using C2F5 radicals generated by photolysis of perfluoropropionic anhydride. The rate constant kH for reaction (2) is given by \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k_H ({\rm cm}^{\rm 3} {\rm mole}^{ - 1} \sec ^{ - 1}) = (11.70 \pm 0.19) - (4260 \pm 290)/\theta$$\end{document} where θ = 2.303RT/cal mole-1. The relevance of this result to conflicting published data on the analogous reaction between CF3 radicals and H2S is discussed. It is concluded that there is little difference in the Arrhenius parameters for reaction of CF3 and C2F5 radicals with H2S.
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  • 186
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    Bromination of dichloromethane, chlorofluoromethane, and dichlorofluoromethaneThis paper is part XXIV of the series “Free Radical Substitution in Aliphatic Compounds.” For part XXIII, see ref [1]. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 69-77 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dichloromethane, chlorofluoromethane, and dichlorofluoromethane have been brominated competitively with each other and with chloroform and methyl chloride. Using the literature values for the rates of bromination of these latter two compounds, the rate constants for the three former compounds have been determined: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} k_2 ({\rm CH}_{\rm 2} {\rm Cl}_{\rm 2} {\rm)} = (9.77 \pm 1.44) \times 10^9 \exp (- 10,860 \pm 480{\rm cal}/RT) \\ k_2 ({\rm CH}_{\rm 2} {\rm F Cl)} = (7.76 \pm 1.59) \times 10^{10} \exp (- 14,800 \pm 800{\rm cal}/RT) \\ k_2 ({\rm CHF Cl}_{\rm 2} {\rm)} = (1.05 \pm 1.48) \times 10^{10} \exp (- 13,300 \pm 570{\rm cal}/RT) \\ \end{array}$$\end{document} where R is taken to be 1.987 cal deg-1 mol-1 (1 cal = 4.186 J).
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  • 187
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    Very low-pressure pyrolysis. VII. The decomposition of methylhydrazine, 1,1-dimethylhydrazine, 1,2-dimethylhydrazine, and tetramethylhydrazine. Concerted deamination and dehydrogenation of methylhydrazineThis work was supported in part by Air Force Rocket Propulsion Laboratory, Contract No. FO-4611-69-C-0096, and in part by the National Aeronautics and Space Administration Contract No. NAS7-472. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 433-448 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constants (kuni) for the first-order disappearance of the title molecules have been determined under VLPP conditions. The kuni are not the rate constants of ultimate interest since they reflect the fact that energy transfer competes with the chemical decomposition. Use of the Rice-Ramsperger-Kassel-(Marcus) [RRK(M)] theory allows the determination of the high-pressure rate constants (kα), if the mode of decomposition is known. The heats of formation of the radicals NH2, CH3NH, and (CH3)2N are known. These values should be usable for prediction of the activation energy for N—N bond homolysis in the hydrazines. Measured rate constants for UDMH and TMH bear this out, but the rate constant for MMH does not. This and other evidence lead to the conclusion that MMH decomposes via molecular concerted elimination of NH3 and H2 not and by N—N bond scission. The following values are preferred from this work (θ = 2.303RT in kcal/mole). Mode of decomposition is N - N bond scission unless noted otherwise in parenthesis: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{ll} \underline{{{{\rm Molecule}}}}& \underline{{{{\rm log }k_\infty /\sec ^{ - 1} (298^\circ {\rm K})}}}\\ {{{{\rm MMH}}}}&{{{13.2{\rm - }54/\theta (- {\rm NH}_{\rm 3});}}}\\ {} & {13.5{\rm - }57/\theta (- {\rm H}_{\rm 2})} \\ {{\rm UDMH}} & {17.0{\rm - }63/\theta } \\ {{\rm SDMH}} & {{\rm 13}{\rm .5 - 57/}\theta {\rm (} - {\rm H}_{\rm 2} {\rm)}} \\ {{\rm TMH}} & {{\rm 17}{\rm .4 - 54/}\theta } \\\end{array}$$\end{document}.
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    The rate of the gas phase iodination of cyclobutane. The heat of formation of the cyclobutyl radicalThis work was supported, in part, by Grant No. AP 00353-07 of the Environmental Protection Agency, Air Pollution Control Administration. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 487-495 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase iodination of cyclobutane was studied spectrophotometrically in a static system over the temperature range 589° to 662°K. The early stage of the reaction was found to correspond to the general mechanism \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} {\rm RH} + {\rm I} \cdot \mathop {{\rm \rightleftharpoons}}\limits^1 {\rm R} \cdot + {\rm HI} \\ {\rm R} \cdot + {\rm I}_{\rm 2} \mathop {{\rm \rightleftharpoons}}\limits^2 {\rm R} - {\rm I} + {\rm I} \cdot \\ \end{array}$$\end{document} where the Arrenius parameters describing k1 are given by log k1/M-1 sec-1 = 11.66 ± 0.11 - 26.83 ± .31/θ, θ = 2.303RT in kcal/mole. The measured value of E1, together with the fact that E-1 = 1 ± 1 kcal/mole, provides ΔHf,2980(c-C4H7.) = 51.14 ± 1.0 kcal/mole, and the corresponding bond dissociation energy, D(c-C4H7—H) = 96.8 ± 1.0 kcal/mole. A bond dissociation energy of 1.8 kcal/mole higher than that for a normal secondary C—H bond corresponds to one half of the extra strain energy in cyclobutene compared to cyclobutane and is in excellent agreement with the recent value of Whittle, determined in a completely different system. Estimates of ΔHf0 and entropy of cyclobutyl iodide are in very good agreement with the equilibrium constant K12 deduced from the kinetic data. Also in good agreement with estimates of Arrhenius parameters is the rate of HI elimination from cyclobutyl iodide.
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  • 189
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    The photolysis of N2O at 2139 Å and 1849 Å (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 497-512 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The method of chemical difference was utilized to accurately determine the relative importance of all the reaction steps in the direct photolysis of N2O at 2139 Å (25° and 250°C) and 1849 Å (25° C), as well as in the Hg6(1P1)-sensitized photolysis of N2O at 1849 Å (25°C). In all cases, the primary process is predominantly, if not exclusively, \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm (1)}} & {{\rm N}_{\rm 2} {\rm O} + hv{\rm or H}_{\rm g} 6(^1 P_1) \to {\rm N}_{\rm 2} + {\rm O(}^{\rm 1} D{\rm)}} \\\end{array}$$\end{document} Experiments with trace amounts of C3H6 added showed a slight, but not significant, difference in product ratios (N2 and O2). From these experiments the quantum yield of O(3P) from all possible sources was estimated as 0.02 ± 0.02. Experiments with excess N2 at 1849 Å indicated that O(1S) was not produced in the direct photolysis. The O(1S) yield is probably zero, and certainly 〈0.05. The O(1D) atom can react with N2O via \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} \begin{array}{*{20}c} {{\rm (2)}} & {{\rm O(}^{\rm 1} D{\rm)} + {\rm N}_{\rm 2} {\rm O} \to {\rm N}_{\rm 2} + {\rm O}_2 } \\\end{array} \\ \begin{array}{*{20}c} {{\rm (3)}} & {{\rm O(}^{\rm 1} D{\rm)} + {\rm N}_{\rm 2} {\rm O} \to 2{\rm NO}} \\\end{array} \\ \end{array}$$\end{document} The ratio k2/k3 was found to be 0.69 ± 0.05 in all cases. When combined with other data from our laboratory, the average value is 0.65 ± 0.07. This represents the value for translationally energetic O(1D) atoms. When excess He was added to remove the excess translational energy, k2/k3 rose to 0.83 ± 0.06, which is in reasonable agreement with the value of 1.01 ± 0.06 found in another laboratory. We conclude that for O(1D) atoms with no excess thermal energy, k2/k3 = 0.90 ± 0.10.
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    Rates of reaction of atomic oxygen with C2H3F, C2H3Cl, C2H3Br, 1,1-C2H2F2, and 1,2-C2H2F2 (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 521-527 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the reactions of atomic oxygen (O3P) with C2H3F, C2H3Cl, C2H3Br, 1,1-C2H2F2, and 1,2-C2H2F2 have been measured at 307°K using a discharge-flow system coupled to a mass spectrometer. The rate constants for these reactions are (in units of 1011 cm3 mole-1 s-1) 2.63 ± 0.38, 5.22 ± 0.24, 4.90 ± 0.34, 2.19 ± 0.18, and 2.70 ± 0.34, respectively. For some of these reactions, the product carbonyl halides were identified.
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    Masthead (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972) 
    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.550040601
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  • 192
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    Radical reactions of highly polar molecules. Chlorination of halopropanes (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 331-338 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In polychloro-2,2-difluoropropanes, where a large inductive effect results in relatively low reactivity to chlorination, the presence of additional chlorine causes an increased reactivity of the hydrogens geminal to the chlorine and a reduced reactivity of the remote (third carbon) hydrogens. The ways in which resonance, inductive effect, and steric crowding interact in the rates of chlorination of polar molecules are discussed.
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  • 193
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    Computational modeling of the mechanisms of the free radical-chain reaction of alkanes with oxygen. The oxidation of isobutane, n-butane, and isopentane (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 345-362 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general computational method for obtaining complete solutions of time-dependent kinetic equations has been developed and applied to free radical-initiated reactions of alkanes with oxygen. The method has been applied to the low-temperature, peroxide-initiated oxidations of isobutane and isopentane. Using available independently measured and estimated values for the rate constants and activation parameters for each of the 20 proposed reaction steps for the oxidation of isobutane, the rates and products have been calculated for both the liquid phase and gas phase in the range of 100°-155°C. The calculated rates and products of oxidation agree with published experimental values. The oxidation of isopentane was examined by a 32-reaction model. The rate constants were estimated using values for the appropriate rate steps in the oxidation of n-butane and isobutane. The calculation of the oxidation rate and products agree with our experiments.
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  • 194
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    A flash photolysis-resonance fluorescence kinetics study of ground-state sulfur atoms. II. Rate parameters for reaction of S(3P) with C2H4 (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 383-394 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate constants for the reaction of S(3P) with ethylene were measured over an ethylene concentration range of 7, a total pressure of 50 to 400 torr, and a flash intensity range of 10. At 298°K, the bimolecular rate constant was found to be invariant over this range of variables and had a measured value of 4.96 × 10-13 cm3 molec-1 s-1. Over the temperature range of 218° to 442°K, the rate data could be fit to a simple Arrhenius equation of the form \documentclass{article}\pagestyle{empty}\begin{document}$$k_1 = (7.13 \pm 0.74) \times 10^{ - 12} {\rm exp}\left({\frac{{{\rm - 1}{\rm .58} \pm {\rm 0}{\rm .08 kcal/mole}}}{{RT}}} \right)$$\end{document} Units are cm3 molec-1 s-1. The dependence of the measured value of k1 on the concentration of the reaction product ethylene episulfide is discussed.
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  • 195
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    Masthead (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972) 
    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.550040201
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    Rate constants for alkyl radical recombination. II. The isopropyl radical This work has been supported in part by Grant No. AP 00353-06 of the Environmental Protection Agency, Air Pollution Control Administration, and in part by an A.C.S.-P.R.F., Type D, grant. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 151-157 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Products of radical combination from the free-radical buffer system \documentclass{article}\usepackage{amssymb}\pagestyle{empty}\begin{document}$${{\rm R}^{\rm .} + {\rm R}^{\rm '} {\rm I}\mathop {\leftrightharpoons}\limits^{{\rm K}_{{\rm RR}}}{\rm RI} + {\rm R}^{'}}$$\end{document}. have been analyzed for the two cases, R = Me, R′ = iPr and R = Et, R′ = iPr. Results are consistent with the previously examined system where R = Me, R′ = Et, and give a value of kP for iPr· combination of 108.6±1.1 M-1 sec-1.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550040203
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  • 197
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    The Gas-phase thermal unimolecular isomerization of n-propylidenecyclopropylamine to 5-ethyl-1-pyrroline (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 169-174 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase thermal isomerization of N-propylidenecyclopropylamine has been studied in the temerature range of 573° to 635°K. The reaction is homogeneous and kinetically first order and yields 5-ethyl-1-pyrroline as the sole product. The rate constants are independent of pressure in the range of 2.5 to 55 torr and fit the Arrhenius relationship log k(sec-1) = (14.05 ± 0.06) - (47.77 ± 0.16)/θ where θ = 2.303 RT in units of kcal/mole, or log k(sec-1) = (14.05 ± 0.06) - (199.9 ± 0.7)/θ, where θ = 2.303RT in kJ/mole. From considerations of a biradical pathway it is concluded that the resonance stabilization energy of the substituted 2-aza-allyl radical is very similar to that of the methallyl radical.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550040205
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  • 198
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    Thermal decomposition of 3-chloro-3-trichloromethyldiazirine in solution (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 229-233 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of 3-chloro-3-trichloromethyldizairine in carbon tetrachloride and iso-octane has been investigated over the temperature range 75-115°C. The products, tetrachloroethylene and nitrogen, are formed quantitatively by a first-order reaction which is probably unimolecular: The results yielded the following Arrhenius equations: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} k({\rm CCl}_{\rm 4} {\rm)} = {\rm 10}^{{\rm 13}{\rm .8} \pm {\rm 0}{\rm .2}} \exp (- 29,200 \pm 200/RT)\sec ^{ - 1} \\ k(iso - {\rm octane)} = {\rm 10}^{{\rm 13}{\rm .8} \pm {\rm 0}{\rm .2}} \exp (- 29,000 \pm 150/RT)\sec ^{ - 1} \\ \end{array}$$\end{document}.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550040209
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  • 199
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    The SO2-sensitized phosphorescence of biacetyl vapor in photolyses at 2650 and 2875 Å. The intersystem crossing ratio in sulfur dioxide (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 175-189 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Quantum yields of the triplet sulfur dioxide (3SO2)-sensitized phosphoresence (Φsens) in biacetyl (Ac2) have been determined in experiments over a wide range of pressures of SO2 and Ac2. Excited singlet sulfur dioxide (1SO2) was generated using 2650-Å and 28757hyphen;Å light. The values of Φsens were dependent on the [SO2]/[Ac2] ratio, as anticpated theoretically. However, in runs at a fixed [SO2]/[Ac2] ratio, the measured Φsens values were dependent on the total pressure. This theoretically unexpected effect is probably largely the result of biacetyl triplet diffusion with deactivation at the cell wall. Treatment of the quantum yield data in terms of the complete mechanism gave new estimates of the following rate functions: 1SO2 + SO2 → (2SO2) (1), 1SO2 + SO2 → 3SO2 + SO2 (2), k2/(k1 + k2) = 0.082 ± 0.003 (2650 Å), 0.095 ± 0.005 (2875 Å) 3SO2 + Ac2 → SO2 + 3Ac2 (9a), 3SO2 + Ac2 → SO2 + Ac2 (9b), k9a + k9b = (8.4 ± 2.1) × 1010 (2650 Å), (8.1 ± 3.0) × 1010 l./mole-sec (2875 Å) 3SO2 → SO2 + hvp (6), k6 = (7.3 ± 1.3) × 101 sec-1.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550040206
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  • 200
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    Vibrational excitation of deuterium fluoride and hydrogen fluoride by atomic and diatomic species (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 293-306 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The vibrational excitation of HF and DF and the energy transfer efficiencies for various collision partners were investigated over the temperature and pressure ranges of 1400°K to 4100°K and 0.1 to 0.3 atm, respectively. The extent of excitation was determined as a function of time by continuously monitoring the infrared emission intensity at the center of the 1-0 vibration-rotation band of the molecule. Collisional efficiencies of HF, N2, O2, F, Cl, and DF in relaxing HF and of DF, HF, and N2 in relaxing DF are reported. A comparison with relaxation data for pure HF taken at lower temperature suggests that long-range attractive forces are mechanistically of major importance in the relaxation process. The relatively high efficiency of atomic chlorine in relaxing HF, i.e., (τP)HF-HF/(τP)HF-C1 ≥ 5 at 3000°K is discussed in terms of our previous result for atomic fluorine, i.e., (τP)HF-HF/(τP)HF-F = 18.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550040306
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