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  • 1985-1989  (114)
  • 1800-1809
  • 1986  (114)
  • 1808
  • Physical Chemistry  (114)
  • 101
    Electronic Resource
    Electronic Resource
    Drug-binding to biological macromolecules. A kinetic study of the system chlorodiazepoxide (librium) and bovine serum albumin (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1123-1132 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Kinetics of the binding of librium to bovine serum albumin were investigated at an ionic strength of 0.15 M, in the pH-range between 5.5 and 10.5, using the temperature-jump method. Two relaxation times were observed. The first, rapid one is assigned to the equilibrium between reactants and complex, whereas the second, slower relaxation time measures a conformational change of this complex. Both relaxation times are independent of pH up to about 8.0 when they increase sharply to a new plateau at a pH of about 9.3. A possible parallelism between this behavior and the N ⇌ B transition of albumin is discussed. The overall equilibrium constant K, as well as the equilibrium constant between the two conformers, K2, were estimated from our kinetic results. Whereas the change of K with changing pH was within the experimental error, the equilibrium between the two conformers of the complex is somewhat shifted by an increase of the pH. At all values of pH, however, they are present in comparable concentrations. The value of K was also measured spectrophotometrically. The results of the two methods showed reasonable agreement. The relaxation times were affected very little by a change in temperature between 12 and 25°C from which it is concluded that the isomerization has a high negative value of ΔS
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550181003
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  • 102
    Electronic Resource
    Electronic Resource
    Transient kinetic studies involving exciplex formation. Methods of analysis (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1163-1183 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this paper, rate parameters are extracted from fluorescene decay data in the framework of Feedback-Type Kinetics (k8 〈 k4). The exciplex dissociation (k4) and fluorescene decay rate constants (k8) have been obtained for the five following systems: For this task we have added to the straight line method of Ware which is valid in certain cases only at high perturber concentrations, a new but similar Taylor series method applicable at low concentrations. Thereafter, a safer and more general method of kinetic analysis based on a quasi-linear χ2 minimization procedure has been developed and applies to data in any range of concentration.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550181006
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  • 103
    Electronic Resource
    Electronic Resource
    Rate constants for one-electron oxidation by methylperoxyl radicals in aqueous solutions (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1185-1191 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for one-electron oxidation by the methylperoxyl radicals (CH3O2, HOCH2O2, -O2CCH2O2, and CCI3O2) in aqueous solutions have been measured by pulse radiolysis and found to be in the range of 3 × 105 to 6 × 108 M-1 s-1 for compounds with redox potentials between 0.6 and 0.1 V. Substitution on the methylperoxyl radical with OH or CO2- has only a minor effect on the rate of oxidation but substitution with three chlorines increases the rate constants by two orders of magnitude. The redox potential of the CH3O2 radical is estimated to be 0.6-0.7 V.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550181007
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  • 104
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of the explosive reaction of carbon monoxide and oxygen (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 181-202 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new technique is described for quantitative measurement of the conditions of reactant concentration at ignition in mixtures of carbon monoxide and oxygen. A thin film of carbon covering the surface of a quartz reaction vessel reacted with oxygen to form carbon monoxide and small quantities of water. Explosions were observed above 900 K over the pressure range 15-100 torr with ratios of CO/O2 far below those hitherto explored. The onset of explosion was favored by the addition of hydrogen, methane, and water and was inhibited by the addition of inert gases. A simple mechanism predicts the occurrence of an explosion over a wide range of product composition and total pressure.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180205
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  • 105
    Electronic Resource
    Electronic Resource
    Effects of alkenes on the thermal decomposition of propane part II. Influence of ethylene (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 241-254 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Experiments with propane-ethylene mixtures in the temperature range 760-830 K resulted in refinement of the role of ethylene inhibition in the decomposition of propane. The source of the rate-reducing effect of ethylene is the reaction This replaces the decomposition chains more slowly by means of the reactions than H-atoms do by direct H-abstraction from propane. Analysis of the ratios of the product formation rates showed that the selectivity of the ethyl radical for the abstraction of hydrogen of different bond strengths from propane was practically the same as that of the H-atom. The ratio of the rate constants of hydrogen addition to ethylene and methyl-hydrogen abstraction from propane by the H-atom (3) was determined \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{k_3 }}{{k_8 }} = 10^{5.89 \pm 0.05} \exp ( - 30.8 \pm 1.1{\rm kJ mol}^{{\rm - 1}} /RT) $$\end{document} as was that of the decomposition and the similar H-abstraction of the ethyl radical \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{k_3 }}{{k_8 }} = 10^{5.11 \pm 0.61} \exp ( - 129 \pm 10{\rm kJ mol}^{{\rm - 1}} /RT){\rm mol}^{{\rm - 1}} {\rm dm}^{\rm 3}. $$\end{document}Interpretation of the influence of ethylene required the completion of the mechanism with further initiation of the reaction besides termination via ethyl radicals.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180209
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  • 106
    Electronic Resource
    Electronic Resource
    Gas phase kinetic study of the thermal reactions of t-butoxy radicals with germane, phosphine, and trimethylsilane (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 267-279 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hydrogen abstraction reactions of tert-butoxyl with germane, phosphine, and trimethylsilane were studied by pyrolyzing di-t-butyl peroxide in the temperature range of 403 to 458 K. From the reported rate constant for the tert-butoxy radical decomposition in the literature, the absolute rate constants were determined from the study of competitive reaction between t-butoxy radical decomposition \documentclass{article}\pagestyle{empty}\begin{document}$$ (t - {\rm BuO }\;{\hbox to 45pt{\rightarrowfill}} {\hskip-42pt ^{{\rm decompose}}}{\hskip1em} {\rm CH}_{\rm 3} {\rm COCH}_{\rm 3} + {\rm CH}_{\rm 3}) $$\end{document} and hydrogen abstraction reaction. (t-BuO + RH → t-BuOH + R, where RH = GeH4, PH3, and HSiMe3)The Arrhenius parameters are found to be as follows: TextEa(kcal mol-1)Log A(1.mol-1s-1)t-BuO + SiHMe32.18.5t-BuO + GeH41.99.1t-BuO + PH31.49.0
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180211
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  • 107
    Electronic Resource
    Electronic Resource
    Rate constants for the reactions of conjugated olefins with NO2 in the gas phase (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1-11 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Gas-phase rate constants for the reaction of NO2 with 16 conjugated olefins were determined at room temperature by either conventional methods for bimolecular processes or by competitive reactions. It was found that the rate constants for conjugated olefins were larger than those for simple mono-olefins by factors of 103-104. Temperature dependence studies reveal that the difference in the rate constants for the two types of reactions can primarily be attributed to differences in their activation energies: k1,3-cyclohexadiene = 5.8 × 10-14 exp[-(6.1 ± 1.6)/RT] cm3 molecule-1 s-1; kcis-2-butene = 4.68 × 10-14 exp(-11.2/RT) cm3 molecule-1 s-1 [2]. A linear free energy relationship between the reactions of OH and NO2 with conjugated diolefins was observed.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180102
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  • 108
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of oxidation of aliphatic aldehydes by peroxomonosulphate (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 49-58 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the oxidation of aliphatic aldehydes, formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, and trichloroacetaldehyde by Peroxomonosulphate (PMS) was carried out in aqueous perchloric acid medium (0.1-1 M H+) at constant ionic strength of 1.2 M in the temperature range 10°-60°C. The reactions of all the aldehydes were found to obey a total second-order kinetics, first order each with respect to [Peroxomonosulphate] and [aldehyde]. Acetaldehyde, propionaldehyde, and n-butyraldehyde exhibited acid catalysis with the concurrent occurrence of acid-independent reaction path conforming to the rate law \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d[{\rm PMS]}}}{{dt}} = k_a [{\rm PMS] [aldehyde] [H}^ +] + k_b [{\rm PMS] [aldehyde]} $$\end{document} Formaldehyde was found to undergo oxidation only by acid-dependent path (kb = 0) and trichloroacetaldehyde exhibited only the acid-independent reaction path (ka = 0). The products of oxidation were found to be the respective carboxylic acids in each case. The stoichiometry of the reaction, [Peroxomonosulphate]:[Aldehyde] = 1:1, indicated the absence of carbonyl-assisted decomposition and self-decomposition of peroxomonosulphate. The kinetic and thermodynamic parameters evaluated pointed to the mechanism of a fast nucleophilic attack of the oxidant on the aldehyde followed by slow acid catalyzed and/or uncatalyzed decomposition of the intermediate to product. A sharp comparison is made with the corresponding reactions of the similar peroxides, S2O82- and H2PO5-.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180106
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  • 109
    Electronic Resource
    Electronic Resource
    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    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.550180201
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  • 110
    Electronic Resource
    Electronic Resource
    The use of transition-state theory to extrapolate rate coefficients for reactions of O atoms with alkanes (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 99-140 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conventional transition-state theory is used for extrapolating rate coefficients for reactions of O atoms with alkanes to temperatures above the range of experimental data. Expressions are developed for estimating structural properties of the activated complex necessary for calculating enthalpies and entropies of activation. Particular attention is given to the problem of the effect of the O atom adduct on the internal rotations in the activated complex. Differences between primary, secondary, and tertiary attack are discussed, and the validity of representing the activated complexes of all O + alkane reactions by a fixed set of vibrational frequencies and other internal modes is evaluated. Experimental data for reactions of O atoms with 15 different alkanes (CH4, C2H6, C3H8, C4H10, C5H12, C6H14, C7H16, C8H18, i-C4H10, (CH3)4C, (CH3)2CHCH(CH3)2, (CH3)3CC(CH3)3, c-C5H10, c-C6H12, c-C7H14) are reviewed.The following approximate expressions for ΔS
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180109
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  • 111
    Electronic Resource
    Electronic Resource
    Reaction rates for nucleophiles with cyanogen chloride: Comparison with two other digonal carbon compounds (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 165-180 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hydrolysis kinetics of CICN have been reinvestigated from pH 0.0-10.5 and from 18-40°C. In the pH range from 1-5, the hydrolysis rate is invariant and the activation parameters (ΔH
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180204
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  • 112
    Electronic Resource
    Electronic Resource
    The intimate ion pair mechanism in the maximally inhibited elimination kinetics of methyl 4-chlorobutyrate and methyl 5-chlorovalerate in the gas phase (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 203-213 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase elimination of methyl 4-chlorobutyrate and methyl 5-chlorovalerate has been reexamined, in a static system and seasoned vessel, over the temperature range of 419.6-472.1°C and pressure range of 45-108 torr. The reactions, under maximum inhibition with propene, are homogeneous, unimolecular, and obey a first-order rate law. The rate coefficients are given by the following Arrhenius equations: for methyl 4-chlorobutyrate, log (k1(s-1) = (13.41 ± 0.60) - (226.8 ± 8.2) kJ/mol/2.303RT; and for methyl 5-chlorovalerate, log k1(s-1) = (13.20 ± 0.02) - (227.6 ± 0.3) kJ / mol / 2.303RT. The pyrolysis rates are found to be about a half of the rates reported in a previous work. As already advanced, the carbomethoxy substituent appears to provide anchimeric assistance in the elimination process, where normal dehydrochlorination and lactone formation arise from an intimate ion pair type mechanism. The partial rates towards each of these products have been determined and reported.
    Additional Material: 10 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180206
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  • 113
    Electronic Resource
    Electronic Resource
    The high temperature pyrolysis of ethylbenzene (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1341-1353 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of ethylbenzene has been investigated behind reflected shock waves over the temperature and pressure ranges of 1350-2080 K and 0.25-0.5 atm using a 1.6% C8H10 — Ne mixture. Major products of the pyrolysis are C7H8, C7H7, C6H6, C4H2, C2H4, C2H2, and CH4; C8H8 appears throughout the temperature range as a minor product. Comparison of the product profiles obtained by time-of-flight mass spectrometry and the results of model calculations strongly supports the initiation step of β C—C bond homolysis for C8H10 dissociation. A 51 kinetic step reaction mechanism with 24 species was formulated to model the temperature and time dependence of the major products observed in our experiments.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550181206
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  • 114
    Electronic Resource
    Electronic Resource
    Room temperature rate constants for the reaction of OH with selected chlorinated and oxygenated hydrocarbons (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1355-1371 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study was conducted to measure the hydroxyl radical rate constants using a relative rate procedure in which the photolysis of methyl nitrite was the source of OH. During the course of this study, the OH rate constant was measured for a number of chlorinated solvents for which measurements have not previously been reported or for which there are few reliable measurements.Room temperature OH rate constants are presented for six chlorinated hydrocarbons (allyl chloride, benzyl chloride, chlorobenzene, epichlorohydrin, trichloroethylene, and vinylidene chloride) and four oxygenated hydrocarbons (acrolein, methacrolein, methyl ethyl ketone, and propylene oxide). Also included are OH rate constants for alkanes (ethane, propane, isobutane, and cyclohexane), alkenes (trans-2-butene and isoprene), and aromatic hydrocarbons (benzene, toluene, o-, m-, and p-xylene). Rate constants for compounds not previously reported include vinylidene chloride (1.49 ± 0.21 × 10-11 cm3 molecule-1 s-1) and benzyl chloride (2.96 ± 0.15 × 10-12 cm3 molecule-1 s-1). The analysis for chlorinated hydrocarbons included a correction for possible chlorine atom reactions.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550181207
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