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  • 1985-1989  (627)
  • 1955-1959
  • 1910-1914
  • Physical Chemistry  (627)
  • 101
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 51-61 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We have carried out a kinetic study of the 4-pyridinecarboxaldehyde plus n-hexylamine system, at 25°C, in water-dioxan mixtures (0-60% v/v) and in the pH range pKa + 1.5 〉 pH 〉 pKa - 1.5, where pKa is the pK value of the conjugate acid of the amine. The results obtained could be interpreted in terms of a rate constant for Schiff's base hydrolysis and a rate constant for the reaction between the nonprotonated n-hexylamine and the nonhydrated form of 4-pyridinecarboxaldehyde. Both constants decrease sharply as the dioxan content of the solvent increases, in a manner consistent with Marshall's model [J. Phys. Chem., 74, 346 (1970)]. It is suggested that the transition state of the rate-limiting step (carbinolamine dehydration) is highly solvated by water molecules and has a high separation of charges.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 102
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 31-50 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Kinetics of oxidation of thiosemicarbazide (TSC) and its hydrazone (Benzaldehyde thiosemicarbazone) by chloramine-T (CAT) and dichloramine-T (DCT) in aqueous methanol medium in the presence of perchloric acid has been studied. Oxidation of TSC by both the oxidants showed first order dependences in [oxidant], fractional order in [TSC] and nearly inverse first order in [H+]. The conversion of TSC into its benzaldehyde hydrazone changed the rate dependence in [CAT] from first to second order, while the dependence in [DCT] remained unchanged. The dependence in [TSC] changes from fractional order to zero order in both CAT and DCT oxidations. The rate followed inverse fractional order kinetics in [H+] in both the cases. Increase in ionic strength of the medium slightly decreased the rate, while the decrease in dielectric constant of the medium increased the rates of oxidations for both the oxidants. But the addition of reaction products, p-toluenesulphonamide and chloride had no effect on the rate. Oxidation of TSC with both the oxidants has been shown to follow Michaelis-Menten type mechanism. In hydrazone oxidations oxidants have been shown to disproportionate in slow steps to HOCl, which in turn attacks the substrate in fast steps to give the final products. [TSC] was varied at different temperatures and the constants of rate limiting steps were calculated at each temperature. Using the latter constants the activation parameters have been computed from the Arrhenius plots. The rate constants have been predicted from the rate law for the variation of [H+] at constant [TSC] and [oxidant]. The predicted values are in reasonable agreement with the experimental rate constants, providing additional support to the suggested mechanisms.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 103
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 83-99 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Using the elementary sensitivity densities, a reaction rate sensitivity gradient is obtained which is the derivative of the rate of species concentration change with respect to the rate coefficient. The dimensionless (log-normalized) form of the reaction rate sensitivity gradient is the ratio of the rate of concentration change of species i due to elementary reaction j and the net rate of concentration change of species i. This result provides a mathematical basis for the use of various forms of reaction rate analyses in the study of complex reaction mechanisms. The kinetic information inherent in the relative reaction rate matrix is extracted by principal component analysis. The method is used to analyze the mechanism of high-temperature formaldehyde oxidation and high-temperature propane pyrolysis. Ranking of the elementary reactions allowed us to reduce significantly the original mechanisms and a detailed study of the results revealed the reaction structures and the major reaction paths of the species.
    Zusätzliches Material: 6 Tab.
    Materialart: Digitale Medien
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  • 104
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 165-174 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The canonical formalism of the statistical adiabatic channel model is used to calculate limiting high pressure rate constants for the H + CH3 → CH4 recombination reaction on a recently reported analytic potential energy surface based on ab initio calculations. An effective adiabatic channel potential which incorporates the Gφφ matrix element of the twofold degenerate H3C—H transitional bending mode, quartic anharmonicity, and state selected mode coupling effects is implemented. The rate constants calculated over the temperature range 200-1000 K are in very good agreement with recent canonical variational transition state theory calculations performed on the same surface. The comparison with experimental results is also discussed.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 105
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 193-206 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The pyrolysis kinetics of the title compounds has been studied in a stirred-flow reactor over the temperature range 440-530°C and pressures between 5 and 14 torr. Benzyl t-butyl sulfide and phenyl t-butyl ether formed isobutene as product in over 98% yield, together with the corresponding benzyl thiol and phenol. The benzyl thiol decomposes to a large extent into hydrogen sulfide and bibenzyl. In the pyrolysis of phenyl t-butyl sulfide, the hydrocarbon products consisted of 80 ±5% isobutene plus 20% isobutane, while the sulfur containing products were thiophenol and diphenyl disulfide. Order one kinetics was observed for the consumption of the reactants. The first order rate coefficients, based on isobutene production, followed the Arrhenius equations: Benzyl t-butyl sulfide: \documentclass{article}\pagestyle{empty}\begin{document}$$k(s^{ - 1}) = 10^{13.82 \pm 0.41} \exp ( - 214 \pm 6{\rm kJ/mol }RT)$$\end{document} Phenyl t-butyl sulfide: \documentclass{article}\pagestyle{empty}\begin{document}$$k(s^{ - 1}) = 10^{12.03 \pm 0.39} \exp ( - 188 \pm 6{\rm kJ/mol }RT)$$\end{document} Phenyl t-butyl ether: \documentclass{article}\pagestyle{empty}\begin{document}$$k(s^{ - 1}) = 10^{14.30 \pm 0.21} \exp ( - 211 \pm 3{\rm kJ/mol }RT)$$\end{document}For benzyl t-butyl sulfide and phenyl t-butyl ether, the results suggest a unimolecular mechanism involving polar four center cyclic transition states. For phenyl t-butyl sulfide, the t-butyl-sulfur single bond fission mechanism is a parallel, less important process than the complex fission one.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 106
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989) 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 107
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 331-341 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The following reactions: were studied over the temperature ranges 533-687 K, 563-663 K, and 503-613 K for the forward reactions respectively and over 683-763 K, for the back reaction. Arrhenius parameters for chlorine atom transfer were determined relative to the combination of the attacking radicals. The ΔHr°(1) = -3.95 ± 0.45 kcal mol-1 was calculated and from this value the ΔH∮(C2F5Cl) = -2.66.3 ± 2.5 kcal mol-1 and D(C2F5-Cl) = 82.0 ± 1.2 kcal mol-1 were obtained. Besides, the ΔHr°(2) was estimated leading to D(CF2ClCF2Cl) = 79.2 ± 5 Kcal mol-1. The bond dissociation energies and the heat of formation are compared with those of the literature. The effect of the halogen substitutents as well as the importance of the polar effects for halogen transfer processes are discussed.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 108
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989) 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 109
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 375-386 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Kinetic studies of the transfer of hydrogen from 9,10-dihydrophenanthrene to anthracene were done at 350°C in the liquid phase. Principal products were phenanthrene and 9,10-dihydroanthracene. Autocatalysis occurred at low extents of reaction, where H-transfer from 9,10-dihydroanthracene to anthracene caused an increase in free radical concentrations. At higher extents of reaction, 9,10-dihydroanthracene inhibited rates by diverting intermediate 9-hydrophenanthryl radicals back to reactants. A quantitative kinetic model based on literature rate and thermodynamic data fits the observations well. A key net reaction is the transfer of an H-atom from a radical (9-hydrophenanthryl) to a molecule (anthracene). It is shown that this process does not involve a free H-atom intermediate. The derived rate constant for this exothermic process (7.5 × 103 M-1 s-1) is considerably greater than that for the related, but thermoneutral H-transfer between anthracene moieties (120 M-1 s-1).
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 110
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 431-437 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rates of reaction for the alkaline hydrolysis of various hydroxamic acids in the presence of cetyltrimethylammonium bromide have been determined. Empirical reaction orders of zero, one-half, and one were found for the hydroxamic acids depending upon reaction conditions and substrate structure. N-methylhydroxamic acids exhibited only first-order kinetics. The results are consistent with the Michaelis-Menten rate equation.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
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  • 111
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 465-476 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Pyrogallol (1,2.3-benzentriol, 1) reacts with dioxygen in weakly alkaline solutions to form purpurogallin (2,3,4,6-tetrahydroxy-5H-benzocycloheptene-5-one, 2) which then reacts to form purpurogalloquinone (3) which then decays to a product absorbing at 440 nm. The formation of 3 requires 1.5 mol O2 per mol 1, and 1.0 mol per mol 2. No O2 is consumed during the decay of 3, and this reaction, being insensitive to O2 concentrations and the presence of both superoxide dismutase (SOD) and catalase, does not appear to be an oxidation. The first-order rate of decay of 3 decreases with increasing pH. 1 and 3 react at pH 9.0 with a second-order rate constant of ca. 100 M-1 s-1. SOD inhibits the oxidation of 1 and 2. Slight and variable apparent inhibition of the oxidation of 2 and 3 by SOD may be due to trace impurities in 2, but not contamination by 1. The peak concentration of 3 is attained more rapidly during the oxidation of 1 than during the oxidation of 2. A kinetic scheme based on parallel oxidation of 1 by dioxygen and superoxide, and it which the semiquinone of 1 oxidizes 2, is partially successful in simulating the observed kinetic behavior.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 112
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 485-498 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Reactions of the hydroxyl radical, OH, with several reactants have been studied near 1200 K in shock tube experiments in which UV absorption was used to monitor the OH concentration. The values of the rate coefficients were found to be 2.7 × 1012, 2.6 × 1012, 2.8 × 1013, and 1.26 × 1013 cm3/mol-s for the reactions of OH with hydrogen, methane, cyclopentane, and isobutane, respectively. These measured values are compared with previous experimental results and transition-state theory calculations.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 113
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 535-546 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The near U-V photolysis of t-butyl nitrite has been studied over the temperature range 303-393 K. Under these conditions t-butyl nitrite was shown to be a very clean photochemical source of t-butoxy radicals. This allows a study of the decomposition of the t-butoxy radical to be made over this temperature range (3). Extrapolation of the rate constants k3 to high pressure and combination with our previous thermal data give the results: \documentclass{article}\pagestyle{empty}\begin{document}$$k_3 (\infty)/{\rm s}^{{\rm - 1}} = 10^{14.04 \pm 0.37} \exp (- 7519 \pm 70.5/T)$$\end{document}
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 114
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 575-591 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The title reaction has been studied in a static quartz reaction vessel between 587 and 658 K at pressures between 40 and 152 torr. The dehydrochlorination is the only significant reaction and is autoaccelerated by the produced HCl. Numerical modelling indicates that the Rice-Herzfeld mechanism, generally used for describing the pyrolysis of halogenated ethanes, has to be completed in the case of CC13CH3 with additional transfer reactions converting “dead” radicals into chain carriers and vice-versa. The numerical simulation fits the experimental results, in the absence as well as in the presence of different amounts of added HCl. The dehydrochlorination is also accelerated by the addition of CCl4, which can be explained in terms of additional elementary steps involving · CCl3 radicals.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 115
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 643-666 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Propyne (p-C3H4) or allene (a-C3H4) mixtures, highly diluted with Ar, were heated to the temperature range 1200-1570 K at pressures of 1.7-2.6 atm behind reflected shock waves. The thermal decompositions of propyne and allene were studied by both measuring the profiles of the IR emission at 3.48 μm or 5.18 μm and analyzing the concentrations of reacted gas mixtures. The mechanism and the rate constant expressions were discussed from both the profiles and the concentrations of reactant and products obtained. The rate constant expressions for reactions, (1) p-C3H4 → a-C3H4, (-1) a-C3H4 → p-C3H4, and (5) p-C3H4 + H → CH3 + C2H2 were evaluated.
    Zusätzliches Material: 14 Ill.
    Materialart: Digitale Medien
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  • 116
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 621-633 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Kinetics of oxidation of thiocyanate ion (NCS-) by iodine monochloride and iodine has been studied in aqueous perchloric acid medium. The rates of oxidations followed the rate laws: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {- \frac{{d[{\rm ICl]}}}{{dt}} = \frac{{k[{\rm ICl][NCS}^ -][{\rm H}^ +]}}{{l + {\rm K[NCS}^ -][{\rm H}^ +]}}} \\ {- \frac{{d[{\rm I}_{\rm 2}]}}{{dt}} = \frac{{k'[{\rm I}_{\rm 3} ^ -][{\rm NCS}^ -][{\rm H}^ +]}}{{[{\rm I}^ -][1 + {\rm K'[H}^ +]]}}{\rm at low [H}^ +]} \\ {{\rm and} - \frac{{d[{\rm I}_{\rm 2}]}}{{dt}} = \frac{{k''[{\rm I}_{\rm 2}]}}{{k'' + [{\rm H}^ +][{\rm I}^ -]}}{\rm at high [H}^ +]} \\ \end{array} $$\end{document} Variations in ionic strength and dielectric constant of the medium had little effects on the rates of reactions with both the oxidants. Mechanisms consistent with the observed rate laws have been suggested. Rate limiting steps have been identified and the constants of some of these steps have been evaluated by varying [NCS-] at each temperature. Activation parameters were computed from the Arrhenius plots. The rate constants predicted from the rate law as [NCS-], and [H+], varied in iodine monochloride oxidation, are in good agreement with the experimental values providing support to the proposed mechanism.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 117
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 689-701 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The thermal decomposition of propane was studied behind reflected shock waves over the temperature range 1100-1450 K and the pressure range 1.5-2.6 atm, by both monitoring the time variations of absorption at 3.39 μm and analyzing the concentrations of the reacted gas mixtures. The rate constants of the elementary reactions were discussed from the results. The rate constant expressions, k1 = 1.1 × 1016 exp (-84 kcal/RT) s-1 and k4 = 9.3 × 1013 exp(-8 kcal/RT) cm3 mol-1 s-1, of reactions C3H8 → CH3 + C2H5 and C3H8 + H → n-C3H7 + H2 were evaluated, respectively.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 118
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 715-727 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The UV absorption spectrum and the kinetics of the self combination reaction of the CCl3 radical were studied by flash photolysis in the temperature range 253-623 K. Experiments were performed at the atmospheric pressure, except for a few runs at the highest temperatures, which were performed between 30 and 760 torr. CCl3 radicals were generated by flash photolysis of molecular chlorine in the presence of chloroform. The UV spectrum exhibits a strong unstructured band between 195 and 260 nm with a maximum at 211 ± 2 nm. The absorption cross section, measured relative to σ(HO2), is σ(CCl3) = (1.45 ± 0.35) × 10-17 cm2 molecule-1 at the maximum. This value takes into account the uncertainty in σ(HO2) which was taken equal to (4.9 ± 0.7) × 10-18 cm2 molecule-1. The absolute rate constant for the CCl3 mutual combination was determined by computer simulation of the transient decays. The rate constant, which exhibits a slight negative temperature coefficient, can be expressed as: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_6 = (3.3 \pm 0.8) \times 10^{- 12} (T/298)^{- 1.0 \pm 0.2} {\rm cm}^{\rm 3} {\rm molecule}^{- 1} {\rm s}^{- 1} {\rm at 760 torr}{\rm.} $$\end{document}The study of the pressure dependence showed that only a slight fall-off behavior could be observed at the highest temperature (623 K). This result was corroborated by RRKM calculations which showed that the rate constant is at the high pressure limit under most experimental conditions below 600 K.
    Zusätzliches Material: 4 Ill.
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  • 119
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of the solvolytic aquation of cis-(Bromo) (imidazole) bis(ethylenediamine) cobalt (III) and cis-(Bromo) (N-methylimidazole) bis(ethylenediamine) cobalt(III) have been investigated in aqueous methanol media with methanol content 0-80% by weight and at temperatures 40-55°C. The pseudo-first order rate constant decreases with increasing methanol content. Plots of log kaqs vs. Ds-1 (where Ds is the bulk-dielectric constant of the solvent mixture) and log kaqs vs. the Grunwald-Winstein Y-solvent parameter are nonlinear, the curvature of the plots is relatively more significant for the imidazole complex. The plots of log kaqs vs. molfraction of methanol (XMeOH) for both the substrates also deviate from linearity, the deviation being less and less marked, particularly for the N-methyl imidazole complex, as the temperature is increased. Hence preferential solvation phenomenon appears to be less significant when the N-H proton of imidazole is replaced by -CH3 group. The plots of calculated values of the transfer free energy of the dissociative transition state, cis-{[(en)2Co(B)]3+}* (B = imidazole, N-methylimidazole), relative to that of the initial state, cis-[Co(en)2(B)Br]2+, for the transfer of the ions from water to the mixed solvent, against XMeOH exhibit maxima at XMeOH = 0.06, 0.27, and 0.12, 0.36 and minima at XMeOH = 0.12 and 0.19 for cis-[(en)2Co(imH)Br]2+ and its N-methylimidazole analogue respectively which are in keeping with the solvent structural changes around the initial state and transition state of these substrates as the solvent composition is varied.Plots of activation enthalpy and entropy against molfraction of the solvent mixtures exhibit maxima and minima. This type of variations of the activation parameters, ΔH≠ and ΔS≠, with XMeOH speaks of the enthalpy and entropy changes associated with the solvent-shell reorganization of the complex ions both in the initial and in the transition states which contribute appreciably to the overall activation enthalpy and entropy of the aquation reaction.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 120
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 355-365 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Using a relative rate method, rate constants have been determined at 296 ± 2 K for the gas-phase reactions of the OH radical with toluene, the xylenes, and the trimethylbenzenes. Using the recommended literature rate constant for the reaction of OH radicals with propene of (2.66 ± 0.40) × 10-11 cm3 molecule-1 s-1, the following rate constants (in units of 10-12 cm3 molecule-1 s-1) were obtained: toluene, 5.48 ± 0.84; o-xylene, 12.2 ± 1.9; m-xylene, 23.0 ± 3.5; p-xylene, 13.0 ± 2.0; 1,2,3-trimethylbenzene, 32.7 ± 5.3; 1,2,4-trimethylbenzene, 32.5 ± 5.0; and 1,3,5-trimethylbenzene, 57.5 ± 9.2. These data are compared with the literature values.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 121
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 993-1001 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Ethers are being increasingly used as motor fuel additives to increase the octane number and to reduce CO emissions. Since their reaction with hydroxyl radicals (OH) is a major loss process for these oxygenated species in the atmoshpere, we have conducted a relative rate study of the kinetics of the reactions of OH radicals with a series of ethers and report the results of these measurements here. Experiments were performed under simulated atmospheric conditions; atmospheric pressure (≃ 740 torr) in synthetic air at 295 K. Using rate constants of 2.53 × 10-12, and 1.35 × 10-11 cm3 molecule-1 s-1 for the reaction of OH radicals with n-butane and diethyl ether, the following rate constants were derived, in units of 10-11 cm3 molecule-1 s-1: dimethylether, (0.232 ± 0.023); di-n-propylether, (1.97 ± 0.08); di-n-butylether, (2.74 ± 0.32); di-n-pentylether, (3.09 ± 0.26); methyl-t-butylether, (0.324 ± 0.008); methyl-n-butylether, (1.29 ± 0.03); ethyl-n-butylether, (2.27 ± 0.09); and ethyl-t-butylether, (0.883 ± 0.026). Quoted errors represent 2σ from the least squares analysis and do not include any systematic errors associated with uncertainties in the reference rate constants used to place our relative measurements on an absolute basis. The implications of these results for the atmospheric chemistry of ethers are discussed.
    Zusätzliches Material: 2 Ill.
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  • 122
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989) 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 123
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 423-430 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of oxidation of a number of ortho, meta, and para substituted S-phenylmercaptoacetic acids by N-Chloro-3-Metyl-2,6-Diphenylpiperidin-4-one (NCP) has been studied in buffered ethanol-water (75:25 v/v) of pH 5.46. The reaction is of first order each in [oxidant] and [substrate]. The rate constant decreases with increase in pH from 5.22 to 5.70. The reaction is accelerated by electron releasing and retarded by electron withdrawing substitutents. The ρ value obtained for this reaction is -1.88 at 10°C with a good correlation coefficient of 0.99 showing an electron deficient transition state. The effect of ortho substitutents also is discussed in detail.
    Zusätzliches Material: 5 Tab.
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  • 124
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989) 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 125
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 499-517 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rate constants of Br atom reactions have been determined using a relative kinetic method in a 20 l reaction chamber at total pressures between 25 and 760 torr in N2 + O2 diluent over the temperature range 293-355 K. The measured rate constants for the reactions with alkynes and alkenes showed dependence upon temperature, total pressure, and the concentration of O2 present in the reaction system.Values of (6.8 ± 1.4) × 10-15, (3.6 ± 0.7) × 10-14, (1.5 ± 0.3) × 10-12, (1.6 ± 0.3) × 10-13, (2.7 ± 0.5) × 10-12, (3.4 ± 0.7) × 10-12, and (7.5 ± 1.5) × 10-12 (units: cm3 s-1) have been obtained as rate constants for the reactions of Br with 2,2,4-trimethylpentane, acetylene, propyne, ethene, propene, 1-butene, and trans-2-butene, respectively, in 760 torr of synthetic air at 298 K with respect to acetaldehyde as reference, k = 3.6 × 10-12 cm3 s-1.Formyl bromide and glyoxal were observed as primary products in the reaction of Br with acetylene in air which further react to form CO, HBr, HOBr, and H2O2. Bromoacetaldehyde was observed as an primary product in the reaction of Br with ethene. Other observed products included CO, CO2, HBr, HOBr, BrCHO, bromoethanol, and probably bromoacetic acid.
    Zusätzliches Material: 2 Ill.
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  • 126
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 561-574 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A chemical kinetic model was constructed for the pyrolysis of butylbenzene. The mechanism was based on free radical reactions. All relevant reactions were considered, and a final selection of 60 reactions involving 29 molecules and free radicals was made. The rate constants and thermodynamic parameters were taken from the literature or estimated using accepted literature methods such as group additivity. The results from the model were compared to experimental rates and product selectivity for butylbenzene pyrolysis over a temperature range of 778 K to 868 K and to an experimental rate at 923 K. The rates agreed within a factor of two and were usually much closer. The experimental and theoretical yields of the major products, styrene, ethane, toluene, and propylene, agreed within two percentage points. The agreement for seven minor products was not quite as good, with the worst case being an overprediction of the yield of allylbenzene by a factor of 2.6.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 127
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 611-619 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rate constants have been determined for the reactions of SO4- with a series of alkanes and ethers. The SO4- radical was produced by the laser-flash photolysis of persulfate, S2O82-. For methane, only an upper limit of 1 × 106 M-1 s-1 could be determined. For ethane, propane, and 2-methylpropane, rate constants of 0.44, 4.0, and 10.5 × 107 M-1 s-1 were found. For ethyl and n-propyl ether, rate constants of 1.3 × 108 and 2.2 × 108 M-1 s-1 were found and for 1,4-dioxane and tetrahydrofuran, rate constants of 7.2 × 107 and 2.8 × 108 were obtained. The reaction of SO4- with allyl alcohol was also studied and found to have a rate constant of 1.4 × 109 M-1 s-1.
    Zusätzliches Material: 3 Ill.
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  • 128
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 667-676 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The rate constants for the reaction of NO3· with sulfur compounds in acetonitrile have been determined by the flash photolysis method. The rate constant for dimethyl sulfone (2.7 × 104 M-1s-1 at -10°C) is larger than that of the deuterium derivative, indicating that NO3· abstracts the hydrogen atom from dimethyl sulfone. In the case of dimethyl sulfide, the rate constant was evaluated to be 1.5 × 109 M-1 s-1 at -10°C; the transient absorption band attributable to the cation radical was observed after the decay of NO3·, suggesting the electron transfer reaction from the sulfide to NO3·. For diphenyl sulfide and dimethyl disulfide, the electron transfer reactions were also confirmed. For dimethyl sulfoxide, the reaction rate constant of 1.2 × 109 M-1 s-1 (at -10°C) was not practically affected by the deuterium substitution, suggesting that NO3· adds to sulfur atom forming (CH3)2Ṡ(O)-ONO2. On the other hand, for diphenyl sulfoxide, the electron transfer reaction occurs. By the comparison of these rate constants in acetonitrile solution with the reported rate constants in the gas phase, the change of the reaction paths was revealed.
    Zusätzliches Material: 4 Ill.
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  • 129
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 703-714 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Radical reactions involving two or more intermediates and many mutual reaction channels may lead to the specific formation of one cross-reaction product if one species is rather persistent and if transient and persistent species are produced with equal rates. A previous kinetic analysis of the phenomenon revealed that the concentrations of the intermediates and the selectivities of product formation depend critically on the relative initiation rates. The present experimental ESR studies on systems involving simultaneously generated phenoxyl radicals as persistent and alkyl radicals as transient species confirm the predicted behavior. They also lead to absolute rate constants for reactions of alkyl with phenoxyl radicals and for hydrogen atom transfer from phenols to alkyl radicals.
    Zusätzliches Material: 5 Ill.
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  • 130
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 749-755 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Intermediate product of the reaction of MoOS2(S2CNR2)2 and PPh3 in dichloroethane has been detected by ESR spectroscopy. Two ESR signals have been observed at low temperature in the reaction system which was stopped by quenching it in liquid nitrogen. The g values are 2.020 ± 0.001 and 1.972 ± 0.001 respectively. The signal at g = 2.020 is attributed to a reaction intermediate with pentavalent molybdenum. A reaction mechanism has been proposed which is consistent with the observation of pentavalent molybdenum as the intermediate in the process of reaction.
    Zusätzliches Material: 5 Ill.
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  • 131
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 801-827 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The aromatic ring-retaining products formed from the gas-phase reactions of the OH radical with benzene and toluene, in the presence of NOx, have been identified and their formation yields determined. These products, and their formation yields, are as follows: from benzene - phenol, 0.236 ± 0.044; nitrobenzene, {(0.0336 ± 0.0078) + (3.07 ± 0.92) × 10-16[NO2]}; from toluene - benzaldehyde, 0.0645 ± 0.0080; benzyl nitrate, 0.0084 ± 0.0017; o-cresol, 0.204 ± 0.027; m- + p-cresol, 0.048 ± 0.009; m-nitrotoluene, {(0.0135 ± 0.0029) + (1.90 ± 0.25) × 10-16[NO2]}, where the NO2 concentration is in molecule cm-3 units. The formation yields of o- and p-nitrotoluene from toluene were ca. 0.07 and 0.35 that of m-nitrotoluene, respectively. The observations that the nitro-aromatic yields do not extrapolate to zero as the NO2 concentration approaches zero are not consistent with current chemical mechanisms for these OH radical-initiated reactions, and suggest that under the experimental conditions employed in this study the hydroxycyclohexadienyl radicals formed from OH radical addition to the aromatic ring react with NO2 rather than with O2. However, these data concerning the nitroaromatic yields are consistent with our previous conclusions that many of the nitrated polycyclic aromatic hydrocarbons present in ambient air are formed, at least in part, in the atmosphere from OH radical reactions.
    Zusätzliches Material: 7 Ill.
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  • 132
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A modified laser photolysis/laser-induced fluorescence technique has been used to measure atmospheric pressure absolute rate coefficients for the reaction of hydroxyl (OH) radicals with the chlorinated methanes (CH3Cl, CH2Cl2, and CHCl3). Data have been obtained for these compounds over the widest temperature range (292-800 K) that has been reported in the literature using a single experimental apparatus. The temperature dependence of the rate data is best represented by the following three-parameter expressions: \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CH}_{\rm 3} {\rm Cl:}\,{\rm 8}{\rm .38}\,\, \pm \,\,1.07\,\, \times \,\,10^{ - 16} \,{\rm T}^{{\rm 1}{\rm .38} \pm {\rm 2}{\rm .01/0}{\rm .71}} \exp [- 2387.4\,\, \pm \,\,142.8/RT]({\rm cm}^3 /{\rm molec - s)}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CH}_{\rm 2} {\rm Cl}_{\rm 2} {\rm :}\,\,1.{\rm 52}\,\, \pm \,\,0.16\,\, \times \,\,10^{ - 16} \,{\rm T}^{{\rm 1}{\rm .58} \pm 0.45} \exp [- 1236.3\,\, \pm \,\,119.5/RT]({\rm cm}^3 /{\rm molec - s)}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CHCl}_{\rm 3} {\rm :}\,\,1.{\rm 92}\,\, \pm \,\,0.21\,\, \times \,\,10^{ - 20} \,{\rm T}^{{\rm 2}{\rm .78} \pm 0.34/0.42} \exp [- 188.3\,\, \pm \,\,119.3/RT]({\rm cm}^3 /{\rm molec-s)}$$\end{document} Uncertainties in the pre-exponential and exponential term are expressed as 95% confidence intervals. For the temperature exponent, error limits represent a ±10% change in the total error of best fit.The degree of curvature in the Arrhenius plots appeared to increase with increasing Cl substitution of the reactant. However, the uncertainty in the temperature exponent for the CH3Cl data was large in comparison with the other chlorinated methanes. Thus, data of greater precision at elevated temperatures are necessary to further explore this relationship. The rate coefficients were compared with recent semiempirical and transition state theory models for haloalkane-OH hydrogen transfer reactions over a temperature range of 250-800 K. The transition state model of Cohen and Benson was in excellent agreement with the CH3Cl and CH2Cl2 data. The semiempirical structure activity relationship developed by Atkinson represented the best fit of the CHCl3 data, although it underestimated the experimental data by more than a factor of 2 at 800 K. The extreme care used to remove and alayze for reactive impurities along with the agreement with other experimental studies suggests that transition state and semi-empirical models for CHCl3 must be modified to account its reaction behavior at high temperature.
    Zusätzliches Material: 6 Ill.
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  • 133
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 233-243 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: It is shown that kinetic data on the polymerization of acetylene to vinyl acetylene and benzene can be reconciled with the formation of a 1,4 biradical which can isomerize by a 1-3, H-atom shift to the molecular product. Since the biradicals have a negligibly small life-time in the system the overall process appears to be a concerted bimolecular reaction. The labile isomer CH2 = C: which had been suggested as being the reactive intermediate, is argued on energy considerations not to be a plausible intermediate.Data on the reverse pyrolysis of vinyl acetylene to acetylene are consistent with the model. Extending the model to butadiene explains the observed molecular nature of its decomposition to ethylene and acetylene.Reactions of other oligomers of acetylene are discussed.
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  • 134
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 251-266 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Studies of the kinetics of thermal unimolecular decomposition of methylcyclopentane, methylcyclohexane, ethynylcyclopentane, and ethynylcyclohexane have been carried out at temperatures in the range 861-1218 K using the technique of very low-pressure pyrolysis (VLPP). Multiple reaction pathways and secondary decomposition of primary products results in a complex array of reaction products. VLPP rate data (fall-off regime) were obtained for the overall decompositions and interpreted via the application of RRKM theory. The data for methylcyclopentane and methylcyclohexane were interpreted in terms of ring-opening bond fission pathways and bond fission to methyl and cycloalkyl radicals. By selecting Arrhenius parameters consistent with the analogous pathways in open-chain alkanes, a good fit to the overall decomposition is obtained. The data for ethynylcyclopentane and ethynylcyclohexane were interpreted in terms of ring-opening bond fission and alkyne to allene isomerization. The A factors for ring opening were based on known values for C-C fission in open-chain alkynes and the Arrhenius parameters for isomerization were chosen to be consistent with previously reported alkyne to allene isomerizations. The VLPP data are consistent with the following high-pressure rate expressions (at 〈 T 〉 = 1100 K) for the dominant primary reaction channel of ring opening adjacent to the substitutent group: \documentclass{article}\pagestyle{empty}\begin{document}$$\log (k/s^{ - 1} ) = (16.4 \pm 0.3) - (341 \pm 10)/\theta {\rm for methylcyclopentane,}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log (k/s^{ - 1} ) = (16.4 \pm 0.3) - (345 \pm 10)/\theta {\rm for methylcyclopentane,}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log (k/s^{ - 1} ) = (16.0 \pm 0.3) - (304 \pm 10)/\theta {\rm for ethynylcyclpentane, and}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log (k/s^{ - 1} ) = (16.0 \pm 0.3) - (303 \pm 10)/\theta {\rm for ethynylcyclohexane,}$$\end{document} where θ = 2.303RT kJ mol-. Comparison of the activation energies for the ethynyl-cycloalkanes with those for the methyl-cycloalkanes shows that the effect of the ethynyl substituent is consistent with the propargyl resonance energy. This evidence supports the assumption of a biradical mechanism for ring opening in these cycloalkanes.
    Zusätzliches Material: 4 Ill.
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  • 135
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 297-314 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Starting from Smoluchowski's hypothesis, a simple algorithm is developed in order to obtain the apparent rate constant at large values of time, t, with some physical and chemical processes, as in the case of diffusion controlled reactions. Some practical examples are illustrated, assuming nonuniform distribution function, space-dependent diffusion coefficient or short-range interaction leading to an asymptotic analytical expression of the form α + β/√t, where α and β are constants function of the system of interest.
    Zusätzliches Material: 12 Ill.
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  • 136
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 399-421 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of oxidation of 2,2′-azinobis-(3-ethylbenzothiazole-6-sulphonate) (ABTS) by the inorganic peroxides, peroxomonosulphate, peroxodisulphate, peroxodiphosphate, and hydrogen peroxide were investigated in aqueous solution. The kinetics of formation of the radical cation, ABTS.+, on one-electron abstraction by these peroxides and the further reaction of ABTS.+ with higher concentrations of these peroxides at longer time scale were studied by following the growth and decay of the radical cation, ABTS.+ at 417 nm. The rate of formation of ABTS.+ was found to obey a total second-order, first-order each in [ABTS] and [peroxide], except for H2O2, which reacted through Michaelis-Menten kinetics. All the peroxides investigated were found to react with ABTS.+; however peroxodisulphate alone oxidized ABTS.+ to the dication (ABTS++), the other peroxides reacted via ionic mechanism, probably forming sulphoxide and sulphone as products. The kinetics of decay of the radical cation, ABTS.+, was also found to follow a total second-order, first-order each in [ABTS.+] and [peroxide], except peroxodiphosphate the reaction of which obeyed Michaelis-Menten kinetics. The effect of pH and temperature were also investigated in all the systems and the kinetic and thermodynamic parameters were evaluated and discussed with suitable reaction mechanisms.
    Zusätzliches Material: 12 Ill.
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  • 137
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 445-464 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An earlier correlation between isolated CH stretching frequencies, visCH, and experimental CH bond dissociation energies, in hydrocarbons, fluorocarbons, and CHO compounds, is updated. A stabilization energy, EvS, which reflects only the properties of the radical, is defined by the deviation of a point from the above correlation. EvS values for a variety of radicals are listed and discussed. In H—C—N and H—C—O compounds EvS is low or negligible, due to the low visCH found in these compounds. The conventional definition of ES then represents a serious misnomer, which distracts attention from the probable source of discrepancies between experimental and ab initio values of DH°(C—H), namely, the parent molecules. Stereo electronic effects concerned with the breaking of CH bonds are predicted in a variety of situations.Some experimental determinations of DH°(C—H), viz., in C2H4, HCOOH, CH3CHO, CH3NH2, are considered to be probably in error.Schemes for partitioning energies of atomization into ‘standard’ or ‘intrinsic’ bond energies are criticized.
    Zusätzliches Material: 4 Ill.
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  • 138
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 547-560 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Phenol pyrolysis has been studied in a turbulent flow reactor by analyzing concentration-time profiles of three major decomposition products: carbon monoxide, cyclopentadiene, and benzene. Experimental conditions were P = 1 atm, T = 1064 - 1162 K, and initial phenol concentrations of 500-2016 ppm. The major experimental observations were that the decomposition product profiles were nearly linear as a function of time and that the overall rate of carbon monoxide production was greater than that of cyclopentadiene. The rate difference is explained by a mechanism which includes a radical combination reaction of cyclopentadienyl and phenoxy. With literature and approximate rate coefficient data, the mechanism reproduced the experimental observations very well. The mechanism and data provide estimates of rate coefficients for the phenol decomposition initiation step, abstraction of hydrogen from phenol by cyclopentadienyl, and the phenoxy-cyclopentadienyl combination, all of which have not been available in the literature.
    Zusätzliches Material: 7 Ill.
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  • 139
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989) 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 140
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 677-687 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rate constants have been determined for the reactions of SO4- with a series of alcohols, including hydrated formaldehyde. The SO4- radical was produced by the laser-flash photolysis of persulfate, S2O82-. Rate constants for the reactions of SO4- with alcohols range from 1.0 × 107 for methanol to 3.4 × 108 M-1 s-1 for 1-octanol. Rate constants for the reactions of SO4- with deuterated methanol and ethanol are lower by about a factor of 2.5. For methanol, ethanol, and 2-propanol, the temperature dependence of the rate constant was determined over the range 10-45°C.
    Zusätzliches Material: 4 Ill.
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  • 141
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989) 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 142
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 967-976 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Selectivity-reactivity correlations are shown to support a biradical pathway for the gas phase thermal Diels-Alder reactions of cyclohexa-1,3-diene with substituted ethenes except for those involving a carbonyl group.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 143
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rate coefficients were calculated for vibrational relaxation and collision-induced dissociation of ground state xenon fluoride in neon at temperatures between 300 and 1000 K for each of nine vibrational levels. These coefficients were calculated using a pairwise additive potential energy surface, which consists of a Morse function for the XeF interaction and Lennard-Jones functions for the NeXe and NeF interactions. Rate coefficients are provided for both temperature and v- dependences. The vibrational relaxation and dissociation processes occur by multiquanta transitions. Dissociation can take place from all v-levels provided that the internal energy of the XeF molecule is close to the rotationless dissociation limit. The order of increase effectiveness of the various forms of energy in promoting dissociation in XeF was found to be translation-rotation-vibration. At room temperature, neon atoms were found to be more efficient than helium atoms in the dissociation processes; helium atoms were found to be more efficient than neon atoms in the vibrational relaxation of XeF. Strong vibration-rotation coupling in both vibrational relaxation and in the dissociation processes is demonstrated.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 144
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1049-1067 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The high temperature kinetics of NH in the pyrolysis of isocyanic acid (HNCO) have been studied in reflected shock wave experiments. Time histories of the NH(X3Σ-) radical were measured using a cw, narrow-linewidth laser absorption diagnostic at 336 nm. The second-order rate coefficients of the reactions: were determined to be: \documentclass{article}\pagestyle{empty}\begin{document}$$k_{1{\rm a}} = 9.84\,\, \times \,\,10^{15} \,\,\exp (- 43000/T,{\rm K})\,\,\,\,\,\,(f = 0.65,F = 1.50)\,\,\,\,\,\,T = 1830 - 3340\,\,{\rm K,}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm 2} = 5.1\,\, \times \,\,10^{13} \,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,(f = 0.7,F = 1.3)\,\,\,\,\,\,T = 2070 - 2730\,\,{\rm K,}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm 3} = 2.65\,\, \times \,\,10^{14} \,\,\,\exp (- 38000/T,{\rm K})\,\,\,\,\,\,(f = 0.5,F = 1.4)\,\,\,\,\,\,T = 3140 - 3320\,\,{\rm K,}$$\end{document} cm3-mol-1-s-1, where f and F define the lower and upper uncertainty limits, respectively. The data for k1a are somewhat better fit by: \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm 1a}} = 3.26\,\, \times \,\,10^{35} T^{ - 5.11} \,\,\exp (- 55300/T,{\rm K})\,\,\,{\rm cm}^{\rm 3} {\rm - mol}^{{\rm - 1}} {\rm - s}^{{\rm - 1}} .$$\end{document}
    Zusätzliches Material: 12 Ill.
    Materialart: Digitale Medien
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  • 145
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1095-1100 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics and products of the decomposition of 9-diazofluorene by tris (p-bromophenyl) aminium hexachloroantimonate in acetonitrile solvent has been investigated. The reaction is first order with respect to the concentration of both 9-diazofluorene and tris (p-bromophenyl) aminium hexachloroantimonate. A reaction mechanism has also been proposed.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 146
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1131-1139 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The pressure-jump method has been used to determine the rate constants for the formation and dissociation of nickel(II) and cobalt(II) complexes with cinchomeronate in aqueous solution at zero ionic strength. The forward and reverse rate constants obtained are kf = 2.27 × 106 M-1 s-1 and kr = 3.81 × 101 s-1 for the nickel(II) complex and kf = 1.23 × 107 M-1 s-1 and kr = 2.66 × 102 s-1 for the cobalt(II) complex at 25°C. The activation parameters of the reactions have also been obtained from the temperature variation study. The results indicate that the rate determining step of the reaction is a loss of a water molecule from the inner coordination sphere of the cation for the nickel(II) complex and the chelate ring closure for the cobalt(II) complex. The influence of the pyridine ring nitrogen atom of the cinchomeronate ligand on the complexation of cobalt(II) ion is also discussed.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
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  • 147
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 315-330 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of oxidation of aliphatic amines viz., ethylamine, n-butylamine, isopropylamine (primary amines), diethylamine (secondary amine), and triethylamine (tertiary amine) by chloramine-T have been studied in NaOH medium catalyzed by osmium (VIII) and in perchloric acid medium with ruthenium(III) as catalyst. The order of reaction in [Chloramine-T] is always found to be unity. A zero order dependence of rate with respect to each [OH-] and [Amine] has been observed during the osmium(VIII) catalyzed oxidation of diethylamine and triethylamine while a retarding effect of [OH-] or [Amine] on the rate of oxidation is observed in case of osmium(VIII) catalyzed oxidation of primary aliphatic amines. The ruthenium(III) catalyzed oxidation of amines follow almost similar kinetics. The order of reactions in [Amine] or [Acid] decreases from unity at higher amine or acid concentrations.The rate of oxidation is proportional to {k′ and k″ [Ruthenium(III)] or [Osmium(VIII)]} where k′ and k″ (having different values in case of ruthenium(III) and osmium(VIII)) are the rate constants for uncatalyzed and catalyzed path respectively. The suitable mechanism consisting with the kinetic data is proposed in each case and discussed.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 148
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1069-1076 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The relative rate technique has been used to determine rate constants for the reaction of bromine atoms with a variety of organic compounds. Decay rates of the organic species were measured relative to i-butane or acetaldehyde or both. Using rate constants of 1.74 × 10-15 and 3.5 × 10-12 cm3 molecule-1 s-1 for the reaction of Br with i-butane and acetaldehyde respectively, the following rate constants were derived, in units of cm3 molecule-1 s-1: 2, 3-dimethylbutane, (6.40 ± 0.77) × 10-15; cyclopentane, (1.16 ± 0.18) × 10-15, ethene, (≤2.3 × 10-13); propene, (3.85 ± 0.41) × 10-12; trans-2-butene, (9.50 ± 0.76) × 10-12, acetylene, (5.15 ± 0.19) × 10-15; and propionaldehyde, (9.73 ± 0.91) × 10-12. Quoted errors represent 2σ and do not include possible systematic errors due to errors in the reference rate constants. Experiments were performed at 295 ± 2 K and atmospheric pressure of synthetic air or nitrogen. The results are discussed with respect to the mechanisms of these reactions and their utility in serving as a laboratory source of alkyl and alkyl peroxy radicals.
    Zusätzliches Material: 1 Ill.
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  • 149
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1123-1129 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Using a relative rate method, rate constants for the gas-phase reactions of the OH radical with 1- and 2-propyl nitrate, 1- and 2-butyl nitrate and 1-nitrobutane have been determined in the presence of one atmosphere of air at 298 ± 2 K. Using rate constants for the reactions of the OH radical with propane and cyclohexane of 1.15 × 10-12 and 7.49 × 10-12 cm3 molecule-1 s-1, respectively, following rate constants (in units of 10-12 cm3 molecule-1 s-1) were obtained: 1-propyl nitrate, 0.62; 2-propyl nitrate, 0.41; 1-butyl nitrate, 1.78; 2-butyl nitrate, 0.93; and 1-nitrobutane, 1.35. These rate constants are compared and discussed with the literature data.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 150
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1153-1160 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Uncertainty sometimes exists in determining initial reaction rates from experimental data. A method, originally proposed by Wilkinson [9] for estimating orders and rate constants for simple batch nth order reactions, has been generalized to complex kinetic systems. This method yields very accurate initial rates for all systems and extends the conversion range of experimental investigation of initial rates well beyond the “zero-order” region. Accurate initial rates are required in analytical methods used for screening alternate reaction mechanisms.
    Zusätzliches Material: 2 Tab.
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  • 151
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1173-1180 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Using the flash photolysis resonance fluorescence technique, absolute rate constants were determined for the gas phase reactions of hydroxyl radicals with a series of aliphatic polyethers. At 298 K, the measured rate constants (in units of 10-12 cm3 molecule-1 s-1) were: 2,2-dimethoxypropane, (3.9 ± 0.2); 2,2-diethoxypropane, (11.7 ± 1.3); 1,2-dimethoxypropane, (14.3± 1.5); 2-methoxyethylether, (17.5 ± 1.1); 2-ethoxyethlyether, (26.8 ± 2.4); 1,1-dimethoxyethane, (8.9 ± 1.0); and 1,1,3-trimethoxypropane, (16.7 ± 1.0).The temperature dependencies of the rate constants for 2,2-dimethoxypropane and 2,2-diethoxypropane, reactions (1) and (2), were studied over the temperature range 240-440 K and are expressed by the Arrhenius equations: \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm 1} = (3.55\,\, \pm 0.39)\,\, \times \,\,10^{ - 12} \,\,\exp [(30 \pm 35)\,/T]\,\,{\rm cm}^{\rm 3} \,\,{\rm molecule}^{{\rm - 1}} {\rm s}^{{\rm - 1}}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm 2} = (1.06\,\, \pm 0.25)\,\, \times \,\,10^{ - 11} \,\,\exp [(15 \pm 75)\,/T]\,\,{\rm cm}^{\rm 3} \,\,{\rm molecule}^{{\rm - 1}} {\rm s}^{{\rm - 1}}$$\end{document} Implications of the results are discussed in terms of reaction mechanisms and the prediction of gas phase OH radical reaction rates for aliphatic polyethers.
    Zusätzliches Material: 2 Ill.
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  • 152
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 115-150 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 153
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 157-163 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The heat of formation of benzophenone oxide, Ph2CO2, was measured using photoacoustic calorimetry. The enthalpy of the reaction Ph2CN2 + O2 → Ph2CO2 + N2 was found to be -48.0 ±0.8 kcal mol-1 and ΔHf(Ph2CN2) was determined by measuring the reaction enthalpy for Ph2CN2 + EtOH → Ph2CHOEt + N2 (-53.6 ±1.0 kcal mol-1). Taking ΔHf(PhCHOEt) = -10.6 kcal mol-1 led to ΔHf(Ph2CN2) = 99.2 ± 1.5 kcal mol-1 and hence to ΔHf(Ph2CO2) = 51.1 ± 2.0 kcal mol-1. The results imply that the self-reaction of benzophenone oxide i.e., 2Ph2CO2 → 2Ph2CO + O2 is exothermic by -76.0 ±4.0 kcal mol-1.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 154
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 175-191 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 2-Methylbut-1-ene-3-yne and Propyne mixtures were pyrolyzed at 350-450°C in the absence and presence of O2 and NO. The major product of the reaction is a polymer, but m-xylene and p-xylene are also produced and were studied as the species of interest. The C8H10 formation rate is first-order in C3H4 and C5H6. The rate coefficient is best fitted by \documentclass{article}\pagestyle{empty}\begin{document}$$\log [k({\rm C}_{\rm 8} {\rm H}_{{\rm 10}}),M^{ - 1} s^{ - 1}] = (11.2 \pm 1.0) - (166 \pm 13)/2.3RT$$\end{document} though it is not inconsistent with \documentclass{article}\pagestyle{empty}\begin{document}$$\log [k({\rm C}_{\rm 8} {\rm H}_{{\rm 10}}),M^{ - 1} s^{ - 1}] = (8.17) - (125.9)/2.3RT$$\end{document} where R is the ideal gas constant in kJ/mol-K. Experiments in the presence of NO show that m-xylene and p-xylene formation occur by two processes: a concerted molecular mechanism (≃ 41%) and a singlet diradical mechanism (≃ 59%).
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 155
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 227-232 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Flash Vaccum Pyrolysis of (α-phenylethyl) and (β-phenylethyl)-pyrazole were studied. Pyrazole and Styrene were found as only products of both reactions. The kinetic parameters obtained reinforce the results previously found about the poor influence of the substitutents on the α and β carbons of the ethyl group in the FVP of N-alkyl pyrazoles and (β-haloethyl) pyrazoles.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 156
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 343-354 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: N-chloro-3-aminopropanol was obtained in aqueous solution by mixing the amine with the hypochlorite. The first order decomposition kinetics of the N-chloramine in strongly alkaline media are explained by a mechanism in which the rate controlling step is the formation of an imine which is subsequently hydrolyzed. Spectrophotometry of the reaction in acid media showed that under these conditions dichloramines are formed: the second order experimental kinetics of this process are explained by a mechanism in which the rate-controlling step is a reaction between the protonated and free forms of the N-chloramine.
    Zusätzliches Material: 5 Ill.
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  • 157
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 367-371 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The elimination kinetics of 2-chloropropionic acid have been studied over the temperature range of 320-370.2°C and pressure range of 79-218.5 torr. The reaction in seasoned vessel and in the presence of the free radical suppressor cyclohexene, is homogeneous, unimolecular, and obeys a first-order rate law. The dehydrochlorination products are acetaldehyde and carbon monoxide. The rate coefficient is expressed by the following Arrhenius equation: log k1(s-1) = (12.53 ± 0.43) - (186.9 ± 5.1) kJ mol-1 (2.303RT)-1. The hydrogen atom of the carboxylic COOH appears to assist readily the leaving chloride ion in the transition state, suggesting an intimate ion pair mechanism operating in this reaction.
    Zusätzliches Material: 7 Tab.
    Materialart: Digitale Medien
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  • 158
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 635-642 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Relaxation rate constants for the collisional deactivation of I (2P1/2) by halogen cyanides were measured by time resolved atomic absorption. The values obtained were (1.2 ± 0.1) × 10-15, (5.2 ± 0.7) × 10-15, and (2.6 ± 0.4) × 10-14 cm3 molecule-1 s-1 for ClCN, BrCN, and ICN, respectively. Quenching efficiencies are discussed in view of the stability of linear molecules to form the transient complex as well as the similarities assumed between halogen cyanides and interhalogen diatomic molecules.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 159
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 757-763 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The catalytic activity of iodine monobromide and iodine monochloride were investigated in the reaction, Et3SiOBun + BusOH ⇌ Et3SiOBus + BunOH. Pseudo first-order rate constants were measured by gas chromatography, at 10°, 20°, 30°, and 40°C for iodine monobromide and at 10°, 20°, and 30°C for iodine monochloride, on reaction mixtures containing both butanols in excess. The catalytic coefficients of both catalysts were evaluated from the observed rate constants as follows: \documentclass{article}\pagestyle{empty}\begin{document}$$k_{2{\rm IBr}} = 9.5 \pm 10^8 \exp \,(- 54.8 \times 10^3 /RT)$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$k_{ - 2{\rm IBr}} = 12.3 \pm 10^8 \exp \,(- 53.3 \times 10^3 /RT)$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$k_{2{\rm ICI}} = 10.7 \pm 10^8 \exp \,(- 54.6 \times 10^3 /RT)$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$k_{ - 2{\rm ICI}} = 13.2 \pm 10^8 \exp \,(- 53.1 \times 10^3 /RT)$$\end{document}The activation paramaters were estimated from these data, and were compared with the values for iodine catalysis. These results are consistent with the mechanism previously proposed.
    Zusätzliches Material: 5 Tab.
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  • 160
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 765-774 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Pulsed laser photolysis/laser-induced fluorescence (LIF) is utilized to measure absolute rate constants of CH radical reactions as a function of temperature and pressure. Multiphoton dissociation of CHBr3 at 266 nm is employed for the generation of CH (X2Π) radicals. The CH radical relative concentration is monitored by exciting fluorescence on the R1(2) line of the (A2Δ - X2Π) transition at 429.8 nm. A resistively heated cell allows temperature studies to be performed from room temperature to ≈670 K. The following Arrhenius equations are derived: \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CH}\,{\rm + }\,{\rm N}_{\rm 2} {\rm O,}\,\,\,\,\,\,\,\,k = (1.59 \pm 0.20)\, \times \,\,10^{ - 11} \,\,\exp [(500 \pm 45)/T]{\rm cm}^{\rm 3} {\rm s}^{{\rm - 1}};$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CH}\,{\rm + }\,{\rm SO}_{\rm 2} {\rm ,}\,\,\,\,\,\,\,\,k = (1.32 \pm 0.17)\, \times \,\,\,10^{ - 10} \,\,\exp [(250 \pm 45)/T]\,\,{\rm cm}^{\rm 3} {\rm s}^{{\rm - 1}};$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CH}\,{\rm + }\,{\rm OCS,}\,\,\,\,\,\,\,\,k = (1.99 \pm 0.11)\, \times \,\,\,10^{ - 10} \,\,\exp [(190 \pm 20)/T]\,\,{\rm cm}^{\rm 3} {\rm s}^{{\rm - 1}};$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CH}\,{\rm + }\,{\rm CS}_{\rm 2} {\rm ,}\,\,\,\,\,\,\,\,k = (3.49 \pm 0.36)\, \times \,\,\,10^{ - 10} \,\,\exp [- (40 \pm 35)/T]\,\,{\rm cm}^{\rm 3} {\rm s}^{{\rm - 1}};$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CH}\,{\rm + }\,{\rm SF}_{\rm 6} {\rm ,}\,\,\,\,\,\,\,\,k 〈 5\,\,\, \times \,\,\,10^{ - 17} {\rm cm}^{\rm 3} {\rm s}^{{\rm - 1}} .$$\end{document} With the exception of SF6, the reactions of sulfur containing species proceed at rates that are near the theoretical gas kinetic collision frequency. Additionally, these reactions all have activation energies that are near zero or slightly negative. These observations are consistent with an insertion-decomposition mechanism being dominant under these conditions.
    Zusätzliches Material: 3 Ill.
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  • 161
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 847-858 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Second order rate constants for C2H2 or C2D2 polymerizations into vinylacetylene and higher CnHn products have been measured in a static reactor by dynamic mass spectrometry between 770-980 K. They are nearly identical within experimental error (±50%). It is shown that these results are consistent with the participation of thermally equilibrated vinylidene H2C = C: as a reactive intermediate: since this assumption only introduces a modest reverse equilibrium isotope effect (KiH/KiD ca. 0.48 in this range) into overall rate constants. At the same time they seem to discriminate in general against alternative mechanisms in which the required H-atom transfers take place in rate determining steps. Present evidence, in conjunction with an updated analysis of relevant issues such as experimental and theoretical vs. termochemical estimates of the heat of formation of H2C=C:, the nature of the transition states of singlet vinylidene addition reactions and the likelihood of discrete biradical intermediates in C2H2 dimerization, seems to lend further support to the notion that acetylene behaves as a singlet carbene at high temperatures.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 162
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Measurements from previous studies have shown that when hydroxyl radicals react with various chlorinated hydrocarbons under atmospheric conditions, free chlorine atoms can be produced. In one such study (Edney et al., [3]) from an analysis of the rate equations under a strict set of assumptions, Cl-atom yields could be inferred. Since the approach was indirect, a more direct method for obtaining these yields has been developed. The technique described in this study involves scavenging Cl atoms produced by the reaction (using ethylene or propylene as the scavenger) and then measuring the yield of the stable chlorinated product generated. Cl-atom yields were determined for allyl chloride, vinyl chloride, vinylidene chloride, trichloroethylene, and benzyl chloride. The experiments were performed by irradiating mixtures of CH3ONO/NO/chlorinated hydrocarbon/alkene in air in 150-L Teflon chambers. The yields for the reaction of Cl atoms with the alkenes generating the stable products were determined in seperate experiments. Yields for the formation of Cl atoms upon reaction with hydroxyl radicals are as follows (with 1 σ deviation): allyl chloride: 0.37 ± 0.10, vinyl chloride: 0.04 ± 0.01, vinylidene chloride: 0.23 ± 0.09, trichloroethylene: 0.63 ± 0.34, and benzyl chloride: 0.08 ± 0.03.
    Zusätzliches Material: 2 Ill.
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  • 163
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 959-966 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The transient diaryl disulfide radical anions (RSSR-) were produced in nonaqueous solutions at room temperature by the flash photolysis of a solution of arylthiolate ion pair in the presence of the excess corresponding disulfide. The transient spectra were almost identical with those obtained from γ-radiolysis of the disulfides in 77 K 2-methyl-tetrahydrofuran (MTHF) glassy matrix. The spectra of disulfide radical anions in nonaqueous solutions were changed by cations, solvents, and para-substituents depending on the ion pair properties. The tighter ion pairs showed a shift of absorption band to the shorter wavelength. The disulfide radical anions decay by a unimolecular dissociation reaction to yield thiolate anion and thiyl radical. The decay kinetics were first-order in the initial time region. The rate constants obtained were changed by the counter cations in the order Na+ 〉 K+ 〉 Cs+ 〉 Li+, and by solvents. The tighter ion pairs of the disulfide radical anions showed faster dissociation reaction. This is due to stabilization of a transition state with the counter cation.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 164
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1015-1027 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The thermal reaction of CH2O with NO2 has been investigated in the temperature range of 393-476 K by means of FTIR product analysis. Kinetic modeling of the measured CH2O, NO, CO, and CO2 concentration time profiles under varying reaction conditions gave rise to the rate constants for the following key reactions: and The error limits shown represent only the scatter (±1 σ) of the modeled values. In the modeling, the total rate constant for the CHO + NO2 reaction, k2 + k3, was not varied and the value reported by Gutman and co-workers (ref. [8]) was used for the whole temperature range investigated here. The proposed reaction mechanism, employing these newly established rate constants, can quantitively account for nearly all measured product yields, including the [CO]/([CO] + [CO2]) ratios reported by earlier workers.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 165
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1077-1089 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Fourier transform infrared spectroscopy was used to identify and quantify products of the self reaction of ethylperoxy radicals, C2H5O2, formed in the photolysis of Cl2/C2H6 mixtures in 700 torr total pressure of synthetic air at 295 K. From these measurements, branching ratios for the reaction channels of k1a/(k1a + k1b) = 0.68 and k1c/(k1a + k1b + k1c) ≤ 0.06 were established. Additionally, using the relative rate technique, the rate constant for the reaction of Cl atoms with C2H5OOH was determined to be (1.07 ± 0.07) × 10-10 × cm3 molecule-1 s-1. Results are discussed with respect to the previous kinetic and mechanistic studies of C2H5O2 radicals.
    Zusätzliches Material: 3 Ill.
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  • 166
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1101-1112 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The gas phase reaction of OH radicals with dimethyl sulfide (CH3SCH3, DMS) has been studied using both an absolute and a relative technique at 295 ± 2 K and a total pressure of 1 atm. The absolute rate technique of pulse radiolysis combined with kinetic spectroscopy was applied. Using this technique a rate constant of (3.5 ± 0.2) × 10-12 cm3 molecule-1 s-1 was obtained. For the relative rate method, rate constants for the reaction of OH with DMS were found to increase with increasing concentrations of added NO. These results are compared with the large body of kinetic and mechanistic data previously reported in the literature.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 167
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1141-1152 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The gas-phase reaction of methyl vinyl ketone with the OH radical, in the presence of NOx, was investigated at 298 ± 2 K and atmospheric pressure of air. Glycolaldehyde and methylglyoxal were observed to be the major products, with a combined yield of 0.89 ± 0.16. The sum of the yields of the two other main products, formaldehyde and peroxyacetyl nitrate, were found to be essentially unity. The product yield data for glycolaldehyde and methylglyoxal indicate that OH radical addition to the terminal carbon atom of the 〉C=C〈 bond accounts for 72 ± 21% of the overall reaction, with the remaining 28 ± 9% proceeding via addition to the inner carbon atom of the double bond.
    Zusätzliches Material: 4 Ill.
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  • 168
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988) 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
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  • 169
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 123-131 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Photolysis of N-alkyl-N-(3-aryl-3-butenyl) ureas (1) in acetonitrile gave cyclization products, 3-aryl-3-methyl-pyrrolidines, in good yields, whereas irradiation of 1 in methanol afforded methanol adducts as well as the cyclization products. Both the reactions are singlet reactions, and the cyclization is presumed to proceed via 1,6-hydrogen transfer from exciplexes with charge transfer character.
    Zusätzliches Material: 2 Tab.
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  • 170
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 143-151 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The dependence of the catalytic efficiencies of sodium carboxymethylamylose (NaCMA) for the hydrolysis of N-lauryl-3-acetoxypyridinium iodide (1) and p-nitrophenyl dodecanoate (3) on its degree of substitution (D. S. = 0·00, 0·12, 0·18, 0·24, 0·29 and 0·35) and on the pH values of the solutions (pH = 7·32, 7·80, 8·10 and 9·30) have been studied. At fixed D. S. values, the observed hydrolysis rates of 1 and 3 increase with increasing concentrations of NaCMA and follow saturation kinetics. At fixed concentration of NaCMA, the rates increase with decreasing D. S. values until they reach maxima at D. S. = 0·00. Furthermore, at any D. S. value the catalytic efficiency increases with increasing pH values of the solutions. All these results indicate that the hydroxyl groups are actually the principal catalyzing groups.
    Zusätzliches Material: 5 Ill.
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  • 171
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988) 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
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  • 172
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 191-195 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The photochemical reaction of MAQO with various aromatic amines were studied by ESR. The results show that nitroxide radicals are stable productrs of the photooxidation of both diphenylamines and phenylamines. The photolyzed phenothiazine does not yield nitroxide as the final product, instead it gives the neutral radical as the stable final product.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 173
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 209-223 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The equilibrium acidities of phenylacetonitrile, and 20 of its m- and p-substituted derivatives have been measured in Me2SO solution. Their pKa′s plot linearly with those of the corresponding anilines. Combination of the pKa′s of these acids with their oxidation potentials, Eox(HA), and those of their conjugate bases, Eox(A-), provide an estimate of the acidities of the corresponding radical cations. The pKHA+ values for ArCH2CN+., where Ar is Ph, 1- and 2-naphthyl, and 9-anthryl, are -32, -18·5, -17·5, and -11, respectively, compared to 21·9, 20·85, 20·65, and 19·8 for the corresponding ArCH2CN acids. Acidities of PhCH(Me)CN+., Ph2CHCN+., 9-CN-FlH+., and 9-CN-XnH+. are -33, -35, -25, and -27, respectively, compared to 23·0, 17·5, 8·3, and 13·6 for the corresponding acids from which they were derived. The homolytic bond dissociation energies (BDEs) for the benzylic C—H bonds in these arylacetonitriles, estimated by combining pKHA with Eox(A-), fall in the range of 69 kcal/mol for 9-CN-XnH to 82 kcal/mol for PhCH2CN. For GC6H4CH2CN+. radical cations the acidities are decreased, relative to G=H, when G is an electron donor substituent and increased when G is an acceptor. The BDEs of the benzylic C—H bonds in GC6H4CH2CN are weakened by up to 4 kcal/mol by para donors and strengthened by up to 1·2 kcal/mol by m- or p-acceptors. The significance of these changes in BDEs with regard to the use of σ. scales and the ΔAOP method for estimating substituent effects on radical stabilities is discussed.
    Zusätzliches Material: 5 Ill.
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  • 174
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 281-285 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The thermal and photochemical decompositions of 5 have been studied. Both reactions lead to CBr2 transfer in good to high yields. With the 2-pentenes as substrates, CBr2 transfer is stereospecific in the classical singlet carbene manner.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 175
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 305-308 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Decomposition of the tosylhydrazone salts formed from cubyl carboxaldehyde and homocubanone, potential precursors of cubylcarbene (5) and homocubanylidene (6), leads in each case to products derived from 6. It is suggested that homocub-1(9)-ene (7) is the active ingredient in the formation of 6 from both precursors. The hydrazones formed from N-aziridylamines are useful photochemical sources of 6, and presumably other carbenes. Flash vacuum pyrolysis of the tosyl hydrazone salts and hydrazones at 600°C leads to indene.
    Zusätzliches Material: 1 Tab.
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  • 176
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 317-332 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Light- and heat-induced decompositions and reactions with nucleophiles of 6,6,8,8-tetramethyl-2-selena-3,4-diaza-7-oxabicyclo[3.3.0]octa- 1(5),3-diene have been studied. In contrast with the conversion to the cyclopentyne derivative (9), selenium containing intermediates (6a, 6b, and 7) were efficiently trapped using several reagents to give various kinds of organoselenium compounds. Of particular note is the isolation of a stable selenirane derivative (16) obtained by the cycloaddition of the photochemically generated selenirene intermediate (7) with furan. The character and reactivity of the intermediates are also discussed.
    Zusätzliches Material: 3 Tab.
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  • 177
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 359-362 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Reaction rates for solvolysis of a mustard analogue are accurately correlated by the solvatochromic equation without inclusion of a nucleophilicity term, and thus the equation is shown to reveal mechanistically significant information.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 178
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 119-121 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Reduction of aromatic aldehydes by benzeneselenol is found to be promoted by molecular oxygen to give corresponding alcohols in good yields. No reduction took place without oxygen.A free radical process involving SH2 reaction at the selenium atom is proposed where the phenylseleno radical attacks the selenium atom of selenohemiacetal, the adduct of benzeneselenol to aldehyde, to give the ketyl radical which then abstracts hydrogen from benzeneselenol. The intermediacy of selenohemiacetal is supported by a quantitative reduction of α-methoxybenzyl phenyl selenide, which is used as a model compound of the intermediate.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 179
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The dependency of the wrapping-up capability of sodium carboxymethylamylose (NaCMA) on its degree of substitution (D. S. = 0·00, 0·12, 0·18, 0·24, 0·29, 0·35 and 0·41) have been studied, using two guest species, iodine and cetyl-trimethylammonium bromide (CTAB). The λmax values of NaCMA-iodine helical inclusion complexes decrease with increasing D. S. values and the amounts of encapsulated iodine by NaCMA as measured by amperometric titrations also decrease with increasing D. S. values. With CTAB as the substrate, the largest number of binding sites, n, and the dissociation constants Kd have been determined by the method of surface tension versus the CTAB concentration plots. The results show that n decreases while Kd increases with increasing D. S. values. All these observations point to the fact that the wrapping-up capability of NaCMA decreases with increasing degrees of substitution. The results are discussed in terms of host-guest and host-solvent hydrophobic-lipophilic interactions as well as intramolecular hydrogen-bonding.
    Zusätzliches Material: 6 Ill.
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  • 180
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 161-167 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The temperature-dependence of the kinetic isotope effects for branched reactions proceeding via a common intermediate has been simulated by calculations. It is shown that, under certain conditions, anomalously small isotope effects on the Arrhenius preexponential factors, as well as unusually large observed isotope effects, may originate from the branching.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 181
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 153-160 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The structures of the allyl anion (1) and two fluoro-substituted derivatives, perfluoro (2) and 1,1-difluoro (3) have been calculated by ab inito molecular orbital theory. Geometries were gradient optimized, and force fields and an MP-2 correlation correction were determined at stationary points. The calculations were done with a double zeta basis set augmented by d functions on carbon (DZ + Dc). Final self-consistent field (SCF) and MP-2 energy calculations were done with the DZ + Dc basis set augmented by diffuse functions. The ground state of 1 is the planar allyl anion (C2v). The rotation barrier in 1 is 21·1 kcal/mol at the MP-2 level. The cyclopropyl carbanion is 27·0 kcal/mol higher in energy at the MP-2 level. The perfluoroallyl anion is not planar, and the rotated structure is 25·7 kcal/mol more stable than the C2v structure at the MP-2 level. The lowest energy structure on the potential energy surface for 2 is the perfluorocyclopropyl carbanion which is 27·8 kcal/mol more stable than the C2v structure at the MP-2 level. The 1,1-difluoroallyl anion is also not planar. Here the most stable structure on the potential energy surface is the rotated allyl anion which is 8·3 kcal/mol more stable than the all-planar allyl anion structure.
    Zusätzliches Material: 1 Tab.
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  • 182
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: 2,2′-Diselenocyanato-1,1′-binaphthyl(1), the first selenium-containing binaphthyl derivative, has been synthesized in optically active form the corresponding diamine by diazotization followed by the reaction with potassium selenocyanate. Its molecular structure is determined by X-ray diffraction method. It is revealed that selenium atoms have hypervalent penta-coordination in the crystal.
    Zusätzliches Material: 4 Ill.
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  • 183
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 185-190 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: From the 1H-NMR spectra of the various pyrrole compounds, 1-substituted 2,5-dimethylpyrroles having two substituent groups on the carbon adjacent to the nitrogen atom were found to be very much hindered compounds. 1-[(1-Substituted)-2-phenylethyl]-2,5-dimethylpyrroles showed the restricted rotation, and the phenyl group of the most stable conformer was in close proximity to the pyrrole group due to dipole interaction. These NMR observations were supported by force field conformational analysis.
    Zusätzliches Material: 1 Ill.
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  • 184
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 333-349 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: New series of platinum complexes of cyclopropenylidenes of the types of PtX2(CP)2 and trans-PtX(PBu3)2(CP) have been synthesized, where CP is di-t-butylcyclopropenylidene (BCP) or bis(diisopropylamino)cyclopropenylidene (ACP). The 13C-NMR chemical shifts, and 13C-195Pt coupling constants (1JPtC) for the complexes are discussed in comparison with those values derived from closely related series of compounds, trans-PtCl(PR3)2L; L — —CH3, —C6H5 and —C≡CBu-t. An excellent linear relationship through the origin was obtained between 1JPtC and the formal ‘s’ % character of the carbon directly bonded to Pt for the series trans-PtCl(PR3)2L in which the Pt—C bond is regarded as a pure σ-linkage, whereas 1JPtC deviates largely from this relationship when pπ—dπ bonding interaction possibly exists in the Pt—C bond. The NMR data suggest the strong nmr trans-influence of the cyclopropenylidenes and that in the Pt—CP bond the σ-interaction is appreciable but the π-interaction is negligible.
    Zusätzliches Material: 3 Ill.
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  • 185
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 103-114 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The effect of solvent additives on the course of TiO2 photocatalyzed oxygenation of α-methylstyrene has been studied. While the addition of small amounts of nonhalogenated alcohols to TiO2 powders suspended in acetonitrile was found to decrease the rate of photooxygenation, added halogenated alcohols increase the rate of reaction. In addition, the solvent additives affect the observed product distribution.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
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  • 186
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 115-117 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A novel oxygen induced reduction of α,β-unsaturated carbonyl compounds is discovered. The reduction of the carbon-carbon double bond of α,β-unsaturated carbonyl compounds by benzeneselenol was caused by an introduction of molecular oxygen into the reaction system. This reduction is likely to proceed via a radical chain pathway involving an SH2 type reaction between a phenylseleno radical and a 1,2-adduct of benzeneselenol to the carbonyl group of the α,β-unsaturated carbonyl compound to give an allylic radical which absracts a hydrogen atom from benzeneselenol to form the reduction product.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 187
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 169-178 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The development of positive charge β to silicon in a saturated five-membered ring has been studied in the cis- and trans-2-(trimethylsilyl)cyclopentyl trifluoroacetates. The cis substrate solvolyzes in 97% trifluoroethanol at 25° C about 5 times faster than the analogous six-membered ring, after correction for differences in ring strain. The trans substrate solvolyzes about 360 times more slowly than the analogous six-membered ring. These changes are in agreement with a hyperconjugative mechanism for interaction between the silyl group and the developing positive charge. The expected cosine-squared dependence of hyperconjugation on the Si—C—C—X dihedral angle suggests that the cis dihedral angle is reduced somewhat from the 60° in the six-membered ring, and the trans dihedral angle is reduced substantially from the 180° in the six-membered ring.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 188
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    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988) 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 189
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 247-257 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The rate of hydrolysis of the aromatic vinyl ether o-carboxy-α-methoxy-β,β-dimethylstyrene was found to be accelerated 25-fold by ionization of its carboxylic acid group, but the effective molarity which may be calculated if all of this rate acceleration is ascribed to intramolecular general acid catalysis is only EM = 1 · 1 m. This is similar to the small effective molarities found before for intramolecular catalysis by carboxylic acid groups of aliphatic vinyl ethers, which shows that, unlike the situation in other intramolecular reactions, e.g. ketone enolization, the extra rigidity of aromatic over aliphatic systems does not improve the efficiency of intramolecular catalysis in vinyl ether hydrolysis.It is suggested that this behaviour is the result of reduced conjugation between the vinyl ether group and the aromatic ring in the transition state of the vinyl ether hydrolysis reaction, which retards the rate and offsets any improvement effected by increased rigidity of the aromatic system.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 190
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 287-298 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Ab initio STO-3G and 6-31G minimized geometries of 5-oxo- (9), 6-oxo-7-oxabicyclo[2.2.1]hept-2-yl cation (12) and 7-oxabicyclo[2.2.1]hept-2-yl cation (15) were obtained. The energy barriers for their Wagner-Meerwein rearrangements to the more stable 5-oxo- (11), 6-oxo-3-oxabicyclo[2.2.1]hept-2-yl (13) and 3-oxabicyclo[2.2.1]hept-2-yl (17) cations, respectively, have been evaluated and compared with those calculated for the rearrangement of the 5-oxo (18) and 6-oxobicyclo[2.2.1]hept-2-yl cations (20). In agreement with experimental data, the ‘true migratory aptitude’ of an acyl group is higher than that of β-oxoalkyl group in competitive Wagner-Meerwein rearrangments that are ‘energetically unbiased’. The ease of the acyl group 1,2-shift toward an electron-deficient center is related to the electron-donating ability of the carbonyl group due to favorable n(CO) ↔ σ σ ↔ p(C+) hyperconjugative interaction.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 191
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 299-303 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Iodide ion promotes the free radical reaction of isopropylmercury idide with bromotrichloromethane to yield isopropyl bromide with rate enhancement in the order of 104. The reaction involves electron transfer from i-PrHgI2- to the trichloromethyl radical in a long kinetic chain process. Iodide ion also promotes the free radical chain conjugate addition of tert-butylmercury chloride to α,β-unsaturated ketones, esters, phosphonate esters and sulfones. Competitive reactivity studies indicate that lithium di-tert-butylcuprates or tri-tert-butylzincates react with 2-cycloalkenones by a mechanism involving attack by tert-butyl radicals. No evidence for radical attack is observed for the corresponding n-butyl ate complexes of copper or zinc.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 192
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 197-207 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: ESR spectra of l-cyano-2-(trimethylsilyl)ethyl and related radicals were recorded. Temperature dependent ESR spectra of these radicals revealed that electron-releasing trimethylsilylmethyl and electron-withdrawing cyano groups synergetically functioned to stabilize the radical centers due to σ-π captodative effects.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 193
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The excellent linearity (R2 = 0·997) of a plot of pKa values for 17 m- and p-substituted benzyl phenyl sulfones, GC6H4CH2SO2Ph, vs. those for the corresponding arylacetonitrile, GC6H4CH2CN, demonstrates that substituent solvation and substituent solvation assisted resonance (SSAR) effects for p-CN, p-COPh, and p-SPh are nearly identical in these two substrates. The PhSO2 group in PhCH2SO2Ph increases the BDE of the α-C—H bond by 2 kcal/mol, relative to toluene. The α-C—H bonds in GC6H4CH2SO2Ph sulfones are stabilized by 1-2 kcal/mol by acceptor G′s (m-CN, p-CN, m-CF3, p-CF3), but weakened by 1 and 5 kcal/mol, respectively, by donors (p-OMe and p-NMe2). The GC6H4CH2SO2Ph+. radical cation with G = H has a pKHA+. = -25. Its acidity is increased when G is an acceptor by as much as 9 to 10 kcal/mol (G = 3-CN, 3-CF3, 4-CF3, 4-NO2), but is decreased when G is a donor by as much as 33 kcal/mol (G = NMe2). When G = 4-SPh the radical cation is stabilized, relative to G = H, by a larger amount (25 kcal/mol) than when G = 4-OMe (18 kcal/mol). Structural changes along the series PhCH2SO2Ph, 2-naphthyl-CH2SO2Ph, 9-anthryl CH2SO2Ph cause negligible changes in the acidities of these acids, but sizable decreases in the acidities of the corresponding radical cations. Introduction of a phenylsulfonyl group into the methyl group of 9-methylanthracene or the 9-position of fluorene or xanthene increase the BDEs by 3, 2, and 7 kcal/mol, respectively. These effects of PhSO2 groups are compared and contrasted with those of CN groups.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 194
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 267-273 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The PE spectra of four stable bicyclic triaziridines with trifluoromethyl, methyl, phenyl, spirocyclopentane and spirocyclohexane substituents are measured. From a comparison of these experimental data with MNDO calculations the energies and the interactions of the nitrogen lone-pair orbitals were obtained. The trifluoromethyl group may be reliably simulated by a fluorine atom. The ionization potentials are unexpectedly high and so are the cyclovoltammetric anodic potentials. The MNDO valence electron densities are in agreement with the comparatively small differences in the chemical shifts of the differently substituted nitrogens of the triaziridine rings.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 195
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 275-280 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: In order to examine the substituent effect of ethylenedithio and trimethylenedithio groups on electron acceptors, the two title compounds were prepared in one step from the corresponding quinones. These species behave as weak π-electron acceptors owing to the electronic and sterical effects of the fused groups. Only the bis(ethylenedithio) derivative formed a charge-transfer complex with tetrathiotetracene, which showed a moderate electric conductivity of 2·0 × 10-2 S cm-1. In addition, both species oxidized copper, sodium, and potassium iodides to give the corresponding deeply colored metal salts, most of which were semiconductive. The naphtho analogs were similarly studied, but hardly served as electron acceptors.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 196
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 259-265 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: 1-(Phenylazo)-1-(2-pyridyl)ethyl hydroperoxide, 1, 1-(phenylazo)-1-(2-furyl)ethyl hydroperoxide, 2, phenylazo(2-furyl)methyl hydroperoxide, 3, 1-(phenylazo)-1-(4-anisyl)ethyl hydroperoxide, 4, were synthesized in moderate yield by autoxidation of the phenylhydrazones in benzene. The ionic oxidation of benzyl methyl sulfide in benzene by 1-4 yielded the sulfoxide and the metastable α-azo hydroxides in essentially quantitative yield. The reaction was of the first order in α-azo hydroperoxide and sulfide, respectively. The relative reactivity series found was: 1(1.0) 〈4(1.4) 〈 phenylazo(4-anisyl)methyl hydroperoxide 5 (2·9) 〈2 (3·8) 〈 3 (9·6). α-Methyl substitution was found to slow the rate of oxygen-atom trasfer by a factor of 2 to 2.5. The low relative reactivity of 1 was opposite that expected based on electronic effects. Competitive intramolecular hydrogen bonding of the hydroperoxy proton to the pyridyl nitrogen in 1 accounted for the observed result.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 197
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 241-245 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The rates of solvolysis of l-aryl-l-phenyl-2,2-dimethylpropyl(1) p-nitrobenzoates and of aryldiphenylmethyl-p-nitrobenzoates (2) were measured in 80% acetone. An inverse order of reactivity, kp-CF3/km- CF3 〉 l was observed for 1 but not for 2. The X-ray crystallogoraphic study of the parent compounds, l,l-diphenyl-2,2-dimethylpropyl-p-nitrobenzoate (1b) and triphenylemethyl benzoate (3b), and of 2-phenyl-2-propyl-p-nitrobenzoate (4) indicated that in the highly congested system 1 both phenyl rings were nonplanar, whereas the phenyl rings in 3 and 4 were essentially planar.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
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  • 198
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988) 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 199
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 309-315 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Photoresponse of the poly(vinyl chloride) membranes, which contain spirobenzopyran and crown ether, covered with a urease layer was studied in the presence and absence of urea. In the absence of urea, UV light irradiation induced more than 160 mV of membrane potential change, whereas the photoresponse decreased with an increase in the concentration of urea in the solution. The effects of such operating variables as crown loading and pH and ionic strength in the aqueous phase on the potentiometric response were also elucidated in the presence of urea. The results were explicated using the fact that the local concentration on NH4+ and H+ ions changed as a result of the urease-catalyzed decomposition reaction of urea.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 200
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 351-357 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The title reaction is an instance of a simple nucleophilic attack of neutral nitrogen on aromatic sp2 carbon. The kinetic data (obtained in dimethyl sulphoxide) are compared to the results reported by the literature for the same reaction of aliphatic amines. Some possible interactions (substrate/nucleophile, substrate/salt) preceding the attack of the nucleophile are discussed.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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