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  • 101
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 5 Ill.
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  • 102
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 375-386 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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).
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  • 103
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 431-437 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 104
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 485-498 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 105
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 547-560 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 7 Ill.
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  • 106
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 621-633 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 107
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 677-687 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 108
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 737-747 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction of MoOS2(S2CNR2)2 (R = CH3, C2H5, n-C3H7) with PPh3 have been studied using a Stopped-flow method. It was found that these MoOS2(S2CNR2)2 complexes react with PPh3 in the form of an irreversible second-order reaction. The rate constants at 25°C are respectively 48.4, 23.8, and 20.8 mol-1 dm3 s-1 and the activation energies are 4.8, 4.9, and 5.0 Kcal/mol with R = CH3, C2H5, and n-C3H7.
    Additional Material: 8 Ill.
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  • 109
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    International Journal of Chemical Kinetics 21 (1989), S. 775-799 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The nitroarene products of the gas-phase reactions of acenaphthylene, acenaphthene, phenanthrene, and anthracene-d10 with N2O5 and the OH radical (in the presence of NOx) are reported. The calculated atmospheric lifetimes of these polycyclic aromatic hydrocarbons (PAH), as well as those of naphthalene, 1- and 2-methylnaphthalene, biphenyl, fluoranthene, pyrene, and acephenanthrylene, show that reaction with the OH radical is the dominant loss process for these PAH, with the exception of acenaphthylene, acenaphthene, and acephenanthrylene which contain an external cyclopenta-fused ring. For these latter PAH, reaction with the NO3 radical, and for acenaphthylene and acephenanthrylene reaction with O3, are also expected to be important atmospheric loss processes.The nitroarenes observed as products of the atmospherically-important gas-phase reactions of the PAH in environmental chamber studies are compared with the nitroarenes measured in ambient air samples collected in California. It is concluded that although nitroarenes are formed in low yields (≲5%) from the OH radical-initiated reactions of the PAH, atmospheric formation of nitroarenes may contribute significantly to ambient nitroarene concentrations.
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  • 110
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 847-858 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 111
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    International Journal of Chemical Kinetics 21 (1989), S. 959-966 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 112
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1101-1112 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 113
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 114
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1095-1100 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 115
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 315-330 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 116
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    International Journal of Chemical Kinetics 21 (1989), S. 331-341 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 117
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    International Journal of Chemical Kinetics 21 (1989), S. 367-371 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 118
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    International Journal of Chemical Kinetics 21 (1989), S. 399-421 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 119
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    International Journal of Chemical Kinetics 21 (1989), S. 1123-1129 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 120
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    International Journal of Chemical Kinetics 21 (1989), S. 1161-1172 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions Br + NO2 + M → BrNO2 + M (1) and I + NO2 + M → INO2 + M (2) have been studied at low pressure (0.6-2.2 torr) at room temperature and with helium as the third body by the discharge-flow technique with EPR and mass spectrometric analysis of the species. The following third order rate constants were found k1(0) = (3.7 ± 0.7) × 10-31 and k2(0) = (0.95 ± 0.35) × 10-31 (units are cm6 molecule-2 s-1). The secondary reactions X + XNO2 → X2 + NO2 (X = Br, I) have been studied by mass spectrometry and their rate constants have been estimated from product analysis and computer modeling.
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  • 121
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Calculations were carried out on several data sets to study the mechanism of hydrogen abstraction from phenols by peroxy radicals: Rate constants, k values, were collected for the reactions of cumyl-, 1-phenylethyl- and tert-butyl-peroxy radicals with ortho-para-substituted phenol inhibitors. The rate constants were recalculated for the same temperature. Solvent effects were neglected because the solvents used were similar in nature. The phenol ortho substituents were characterized by an indicator variable ItBu accounting for the presence or absence of di-tert-butyl groups. The phenol para substituents were characterized by Charton's σI, σR, and σR+ substituent constants.The dependence of log k values on Itbu, σI, σR, σR+ was investigated using stepwise linear regression analysis. The combined data set of 32 reactions gives: \documentclass{article}\pagestyle{empty}\begin{document}$$\log \,\,k_{(333{\rm K)}} = - 0.801\sigma _I - 2.483\sigma _{\rm R} + 3.766\,\,\,\,\,\,\,\,\,(r = 0.851)$$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$\log \,\,k_{(333{\rm K)}} = - 0.932\sigma _1 - 2.302\sigma _R^ + + 3.802\,\,\,\,\,\,\,\,\,(r = 0.848)$$\end{document}The results suggest that hydrogen abstraction from phenols by peroxy radicals proceeds by an electrophilic mechanism, and that neither the peroxy-radical nor the ortho-di-tert-butyl groups have considerable effect on the rate of reaction (1).
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  • 122
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    International Journal of Chemical Kinetics 21 (1989), S. 71-81 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The permanganate oxidation of L-valine has been studied by visible spectrophotometry in neutral aqueous solutions. Under these conditions, both the zwitterionic and anionic forms of the amino acid are oxidized, the reaction being autocatalyzed by soluble colloidal manganese dioxide. Kinetic data for both the uncatalyzed and autocatalytic reaction pathways have been obtained, and reaction sequences consistent with the experimental findings are proposed.
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  • 123
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    International Journal of Chemical Kinetics 21 (1989), S. 355-365 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 124
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    International Journal of Chemical Kinetics 21 (1989) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 125
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    International Journal of Chemical Kinetics 21 (1989), S. 387-397 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of 1-chloro-1,1-difluoroethane by a radical chain reaction has been studied in a flow reactor in the temperature range from 503 to 773 K. For the initiation of the chain small amounts of added chlorine were photolyzed with a XeCl laser (λ = 308 nm). The formation of the dehydrochlorination and chlorination products, vinylidene fluoride, and 1,2-dichloro-1,1-difluoroethane respectively, is described by a kinetic model. Arrhenius parameters for the two abstraction reactions \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CI + CH}_{\rm 3} {\rm CCIF}_{\rm 2} {\hbox to 25pt{\rightarrowfill}} {\hskip-18pt ^{K_2 }}{\hskip1em} {\rm HCI + CH}_{\rm 2} {\rm CCIF}_{\rm 2}$$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CI + CH}_{\rm 2} {\rm CICCIF}_{\rm 2} {\hbox to 25pt{\rightarrowfill}} {\hskip-18pt ^{K_7 }}{\hskip1em} {\rm HCI + CHCICCIF}_{\rm 2}$$\end{document} were determined by a competition method: \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} (k_2 /cm^3 {\rm mol}^{{\rm - 1}} {\rm s}^{{\rm - 1}} = (13.6 \pm 0.1) - (9200 \pm 300)/4.576T$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} (k_7 /cm^3 {\rm mol}^{{\rm - 1}} {\rm s}^{{\rm - 1}} = (13.7 \pm 0.1) - (6500 \pm 200)/4.576T$$\end{document} Experimental and modeling results are discussed with respect to former studies on the thermal reaction of 1-chloro-1,1-difluoroethane.
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  • 126
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of reaction of substituted 2-aminobenzothiazoles and phenacyl bromide have been followed conductometrically and in some cases, argentometrically. Both the methods produced almost the same rate constants. Substituents at position 5 of the benzothiazole nucleus behave like para substituents of the benzene ring. A correlation with Hammett σp substituent constants has been obtained with a rho value of -1.04. The rate data of quaternization reaction of 4, 5, and 6 substituted 2-aminobenzothiazoles with phenacyl bromide have been correlated with Fk, Rk, and Vw values by multiple regression analysis with the equation suggested by Williams and Norrington and modified by us. The values are found to correlate well with the equation, log k = -4.4979 - 0.4815fjFk + 0.5933rjRk - 0.0277Vw.
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  • 127
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3-Methylfuran has been identified as a product of the gas-phase reaction of the OH radical with isoprene, and under simulated atmospheric conditions a formation yield of 0.044 ± 0.006 was determined. In an analogous manner, the OH radical reaction with 1,3-butadiene formed furan with a yield of 0.039 ± 0.011. Using a relative rate method, a rate constant for the reaction of the OH radical with 3-methylfuran of 9.35 × 10-11 cm3 molecule-1 s-1 (with an estimated overall uncertainty of ±20%) at 296 ± 2 K was also determined. These data show that 3-methylfuran is a reactive compound which will be present in the troposphere at concentrations ≤5% of those of its isoprene precursor.
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  • 128
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    International Journal of Chemical Kinetics 21 (1989), S. 715-727 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 129
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    International Journal of Chemical Kinetics 21 (1989), S. 765-774 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 130
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    International Journal of Chemical Kinetics 21 (1989), S. 729-732 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 131
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    International Journal of Chemical Kinetics 21 (1989), S. 923-945 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Single-channel hindered Gorin model RRKM calculations were performed on reaction (1). Good agreement between theory and experiment was obtained for the temperature and pressure dependence of reaction (1). Isotopic data for the reverse association reaction, (-1), reported previously, are consistent with the model. Rate constants were cast in the form of an analytical expression and appropriate parameters were tabulated.
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  • 132
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    International Journal of Chemical Kinetics 21 (1989), S. 947-958 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of acetylene polymerization initiated by neopentane (Np) or acetone (Ac) decompositions has been investigated in a static reactor dynamically coupled to a modulated beam mass spectrometer between 850-950 K. Overall rates follow the expression: R = -d[C2H2]/dt = ks[X]1/2[C2H2] + ku[C2H2]2 (I), where X represents Np or Ac and ks, ku the rate constants of the sensitized and unsensitized reactions, respectively. The rate law of the sensitized reaction clearly suggests a chain polymerization mechanism with ks = kp(ki/kt)1/2 (i, t, and p stand for initiation, termination, and propagation, respectively). Remarkably, the derived values of kp are nearly independent of the sensitizer, although Ac acts as a source of methyl radicals whereas Np also produces hydrogen atoms, and fall in the expected range for the addition of vinylic radicals to acetylene. It is shown that a chain transfer process involving the fast [1,5] intramolecular hydrogen atom shift in 4-methyl-buta-1,3-dien-1-yl radicals (CH3—CH = CH—CH =ĊH) followed by further addition to C2H2 and aromatization, transforms methyl radicals into hydrogen atoms and is able to account for the presence of toluene among the products of the sensitized reactions. Based on current thermochemical data for the but-1-en-3-yn-2-yl radical (CH2=Ċ—C≡CH) and present rates of propagation it is argued that if the unsensitized polymerization of acetylene also proceeded by a vinyl radical chain, then even the most favorable self-initiation reaction: 2C2H2 = C4H3 + H (a), would be far too slow. Finally, present results also show that acetone at impurity levels (≤ 0.1%) can not provide fast enough spurious initiation rates in chain mechanisms for the “unsensitized” acetylene pyrolysis at pressures above 10 torr.
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  • 133
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    International Journal of Chemical Kinetics 21 (1989), S. 1015-1027 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 134
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    International Journal of Chemical Kinetics 21 (1989), S. 1153-1160 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 135
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    International Journal of Chemical Kinetics 21 (1989), S. 499-517 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 136
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    International Journal of Chemical Kinetics 21 (1989), S. 561-574 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 137
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    International Journal of Chemical Kinetics 21 (1989) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 138
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    International Journal of Chemical Kinetics 21 (1989), S. 635-642 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 139
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    International Journal of Chemical Kinetics 21 (1989), S. 703-714 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 140
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 141
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    International Journal of Chemical Kinetics 21 (1989), S. 801-827 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 142
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    International Journal of Chemical Kinetics 21 (1989), S. 885-908 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Generalized models for steady state catalytic processes are presented in matrix form. Multistep reaction rate control is assumed. Numerical algorithms for solving of the created linear and nonlinear equation systems are developed and tested. Four examples are considered: an Eley-Rideal-mechanism, a Langmuir-Hinshelwood mechanism, a dual route, dual site mechanism, and a monomolecular decomposition with steady state multiplicity. The overall reaction rates are simulated as a function of the reactant concentrations.A maximum reaction rate is obtained in the case of a Langmuir-Hinshelwood mechanism (example 2), the location of the rate maximum in the concentration domain is shifted towards the concentration of the reactant with the lowest adsorption constants. An Eley-Rideal mechanism (example 1) has always monotonously increasing rate curves. In the case of steady state multiplicity (example 4) all steady states could be simulated with the proposed algorithm. The computation of reaction rate surfaces is important in investigating the behavior of complicated catalytic systems (e.g., systems with multistep rate control and/or steady state multiplicity), in planning of experiments and in chemical reactor simulation.
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  • 143
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    International Journal of Chemical Kinetics 21 (1989), S. 967-976 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 144
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 145
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    International Journal of Chemical Kinetics 21 (1989), S. 1029-1047 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of V → R, T energy relaxation following pulsed ir laser excitation is measured by employing an optoacoustic single pulse method. Under present experimental conditions the operation of convolution applies. The experimental optoacoustic waveform can be viewed as the convolution of the kinetic relaxation waveform with an optoacoustic waveform obtained under very fast energy relaxation conditions. A discrete Fourier transform deconvolution method is applied to optoacoustic measurements on SF6 in argon to obtain the time constant, τ, for energy transfer. The present method gives τP = 182 ± 15 μs torr, in good agreement with other methods. These results were obtained without requiring either a theoretical description of the pressure waveform or an assumed laser irradiation geometry. For convolution to apply, the differential equation describing the pressure pulse must be linear under the conditions of the experiment. The linearity of the system can usually be tested experimentally.
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  • 146
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    International Journal of Chemical Kinetics 21 (1989) 
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 147
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    International Journal of Chemical Kinetics 21 (1989), S. 31-50 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 148
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    International Journal of Chemical Kinetics 21 (1989), S. 51-61 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 149
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    International Journal of Chemical Kinetics 21 (1989), S. 157-163 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 150
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 151
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    International Journal of Chemical Kinetics 21 (1989), S. 227-232 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 152
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    International Journal of Chemical Kinetics 21 (1989), S. 245-250 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the reactions of tert-butoxy radicals (generated by the thermal decomposition of di-tert-butylperoxyoxalate) with several sulfur containing compounds have been measured at 310 K in benzene. Hexanethiol (k = 6.5 × 107M-1s-1) reacts considerably faster than alkyl sulfides and disulfides. For these compounds the reaction rate constants are slightly dependent on the α-hydrogen type, changing (when it is expressed per hydrogen atom) only a factor 5 for sulfides and 3 for disulfides when the α-hydrogen is changed from primary (methyl) to tertiary (isopropyl). The data obtained are compared to those found for the deactivation of the benzophenone triplet. Values of ktert-butoxy/kbenzophenone range from ca 10-3 (di-tert-butyl disulfide) to 7.5 (hexanethiol). The results obtained are rationalized in terms of bond strength, steric hindrance, and charge transfer contributions to the critical configuration energies.
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  • 153
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    International Journal of Chemical Kinetics 21 (1989), S. 21-29 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants and activation parameters of direct reaction of oxirane with certain alkyl-2-hydroxyethyl sulfides and/or successive oxyethylene adducts in the presence of basic catalyst were studied at temperatures 323-353 K. The reactions were found to be of the first order with respect to oxirane, sulfide, and catalyst concentrations. The kinetics are consistent with a termolecular mechanism.
    Additional Material: 3 Ill.
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  • 154
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    International Journal of Chemical Kinetics 21 (1989), S. 575-591 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 155
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    International Journal of Chemical Kinetics 21 (1989), S. 643-666 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 156
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    International Journal of Chemical Kinetics 21 (1989), S. 667-676 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 157
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 158
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    International Journal of Chemical Kinetics 21 (1989) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 159
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    International Journal of Chemical Kinetics 21 (1989), S. 757-763 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 160
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    International Journal of Chemical Kinetics 21 (1989) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 161
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 162
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    International Journal of Chemical Kinetics 21 (1989), S. 909-922 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermochemical kinetics formulation of conventional transition state theory for bimolecular reactions allows for a separate contribution from each degree of freedom (translation, rotation, vibration, etc.) in the activated complex to the entropy and heat capacity of activation, and thus to the preexponential terms in the Arrhenius rate expression, k = ATn exp(-B/T). The number of vibrations and (possibly hindred) internal rotations varies depending on the nature of the reaction: atom + diatom, diatom + linear polyatom, etc. The temperature exponent n can be evaluated explicitly for each type of reaction if the harmonic oscillator-rigid free rotor approximation is valid for the reagents and activated complex and if the contribution from tunneling is small. Various reaction types are examined successively, and n is evaluated for each case. The possible contributions of other factors (vibrational anharmonicity, hindered internal rotation, tunneling, “looseness” of activated complex) to the value of n are also considered.
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  • 163
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    International Journal of Chemical Kinetics 21 (1989), S. 1049-1067 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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}
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  • 164
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    International Journal of Chemical Kinetics 21 (1989), S. 1077-1089 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 165
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    International Journal of Chemical Kinetics 21 (1989), S. 1069-1076 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 166
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    International Journal of Chemical Kinetics 21 (1989), S. 1-20 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is described for the measurement of relative rate constants for abstraction of hydrogen from ethylene at temperatures in the region of 750 K. The method is based on the effect of the addition of small quantities of propane and isobutane on the rates of formation of products in the thermal chain reactions of ethylene. On the assumption that methane and ethane are formed by the following reactions, measurements of the ratio of the rates of formation of methane and ethane in the presence and absence of the additive gave the following results: \documentclass{article}\pagestyle{empty}\begin{document}$$\log (k_7 /k_2) = (- 0.50 \pm 0.4) + (3200 \pm 1000)/2.3T$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log (k_8 /k_3) = (- 0.20 \pm 0.4) + (2800 \pm 1000)/2.3T$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log (k_{11} /k_2) = (- 0.97 \pm 0.4) + (4600 \pm 1000)/2.3T$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log (k_{12} /k_3) = (- 2.0 \pm 0.4) + (6300 \pm 1000)/2.3T$$\end{document} Values for k2 and k3 obtained from these ratios are compared with previous measurements.
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  • 167
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    International Journal of Chemical Kinetics 21 (1989), S. 115-150 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 168
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    Journal of Physical Organic Chemistry 1 (1988) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 169
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    Journal of Physical Organic Chemistry 1 (1988), S. 317-332 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 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.
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  • 170
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 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.
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  • 171
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    Journal of Physical Organic Chemistry 1 (1988), S. 333-349 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 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.
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  • 172
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    Journal of Physical Organic Chemistry 1 (1988) 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 173
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    Journal of Physical Organic Chemistry 1 (1988), S. ii 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 174
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    Journal of Physical Organic Chemistry 1 (1988), S. 1-20 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Substrates with neutral leaving groups undergo unimolecular solvolysis in nonpolar solvents. Whereas t-alkyl substrates invariably solvolyze by a unimolecular mechanism, s-alkyl and primary alkyl substrates can undergo both uni and bimolecular reactions, and the bimolecular step can take place on either the substrate itself or on an intimate ion-molecule pair formed in either a pre-equilibrium or in a rate determining step. Study of reactions at borderlines indicates that the individual reaction types remain distinct and do not merge.
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  • 175
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    Journal of Physical Organic Chemistry 1 (1988), S. 21-27 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of radical intermediates appearing in the reactions of MeMgBr with aromatic monoketones was investigated by using ESR and visible spectroscopy. Stable radical intermediates in the reacting solutions were assigned to the dimeric radical ion pairs.
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  • 176
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    Journal of Physical Organic Chemistry 1 (1988), S. 29-31 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Disparity reaction proposed in a recent application of Marcus-Grunwald theory to nitroalkane ionization is shown to put the reaction's transition state in an energy-diagram region where electronic rearrangement leads proton transfer, contrary to experimental evidence; it is suggested that addition of solvent reorganization to electronic rearrangement as the second reaction progress variable would remedy this situation.
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  • 177
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    Journal of Physical Organic Chemistry 1 (1988), S. 33-38 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several Cotton effects are developed within absorption bands of trinuclear organotransitionmetal complexes in the presence of acids, diols, amines and aminoalcohols even in the case of bulky substituents on nitrogen; with monohydroxy compounds no circular dichroism could be detected.
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  • 178
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    Journal of Physical Organic Chemistry 1 (1988), S. 39-46 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Triethylsilyl radical was generated by laser flash photolysis of a 1:1 (v/v) solution of triethylsilane and di-tert-butyl peroxide. The silicon centered radical was reacted with sulfides to give carbon centered radicals by displacement at sulfur. The carbon radicals were readily detected by their transient absorption spectra. The absolute rate of reaction of triethylsilyl radical with 9-fluorenylphenylsulfide, di-n-butylsulfide, di-sec-butyl sulfide, di-tert-butyl sulfide and di-n-butyl disulfide are 2.40 ± 0.12 × 108 M-1S-1, 1.1 × 107±0.89×106M-1S-1, 8.79± 0.73×106M-1S-1, 3.29±0.18×106 M-1S-1, and 3.41±0.09×108 M-1S-1, respectively.
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  • 179
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    Journal of Physical Organic Chemistry 1 (1988), S. 47-51 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper describes the synthesis and electrochemical behavior of dicationic salts of ethenediylidene-2,2′ -bis(1,3-dithiole) (3) and butatriene-1,4-diylidene-2,2′ -bis(1,3-dithiole) (4). These are expected as donor components for developing organic conducting and superconducting materials, on the grounds of high electron donating ability and of rigid skeletal structure with two and four cumulenic carbons inserted between two 1,3-dithioles. These salts were obtained in good overall yields by several steps starting from (2-morpholino-4,5-dimethyl or -diphenyl)-1,3-dithiolylium salt. From the 1H and 13C NMR, and electronic spectra it is suggested that the π conjugation between two 1,3-dithiolylium ions through an acetylenic bond is less effective than that through an olefinic bond of the corresponding salts of ethanediylidene-2,2′ -bis(1,3-dithiole) (1) and 2-butene-1,4-diylidene-2,2′-bis(1,3-dithiole) (2). The cyclic voltammetric study shows that the corresponding radical cations, and in particular 3 and 4, are less stable even at -40°C, thus providing reasons for our current lack of success in isolation of 3 and 4. From comparison of the first redox potentials of neutral species, it is deduced that the donating ability increases in the order of TTF 〈 1 ⋍ 2 ≲ 3 ≪ 4.
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  • 180
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    Journal of Physical Organic Chemistry 1 (1988), S. 53-57 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction of sulfur ylides with elemental sulfur or selenium initially affords thio- or seleno-carbonyl compounds, which then react with starting ylides to give episulfides or episelenides from which the heteroatom (sulfur or selenium) is extruded to give olefins as the final product. In the case of carbonyl-stabilized ylides, the resulting thio- or seleno-carbonyl compounds react with starting ylides to afford 1,3-oxathioles or 1,3-oxaselenoles as previously reported. Supporting evidence for the intermediacy of thio(seleno)-carbonyl compounds and episulfides (episelenides) is presented.
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  • 181
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    Journal of Physical Organic Chemistry 1 (1988) 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 182
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    Journal of Physical Organic Chemistry 1 (1988), S. 59-61 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Treatment of α, α′ -diketo selenides, which recently became readily obtainable, with base affords α-oxo selenoaldehydes and ketones. The seleno-carbonyl compounds thus formed are reactive transient species, but can be trapped by Diels-Alder reaction to give 3,6-dihydro-2H-selenapyran derivatives in moderate to good yields.
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  • 183
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    Journal of Physical Organic Chemistry 1 (1988), S. 63-73 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Novel structural features of 5, 15-dialkylporphyrins in solution are described. The 1H-NMR spectra of these compounds showed broad signals at room temperature, which split into two sets of signals at lower temperatures. This unusual phenomenon was ascribed to a dynamic interconversion between tow distorted structures. The 5, 15-dialkylporphyrin has a distorted ring due to the steric hindrance between the 5(or 15)-alkyl group and the 3, 7(or 13, 17)-alkyl groups and, depending on the position of the 5, 15-alkyl groups relative to the average ring plane, can exist in two conformations; syn (where the two alkyl groups are on the same side of the ring plane) and anti (on the opposite sides). Preliminary kinetic study of this interconversion using the NMR line shape analyses is also reported.
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  • 184
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    Journal of Physical Organic Chemistry 1 (1988), S. 75-81 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Highly sterically demanding 2,4,6-tri-t-butylphenyllithium (1) reacts with carbon disulfide to give 1,2-dibutylthio-1,2-bis(2,4,6-tri-t-butylphenylthio) ethene (3), l-butylthio-1-(2,4,6-tri-t-butylphenylthio)pent-l-ene (4), and 2-butylthio-3-(2,4,6-tri-t-butylphenylthio)-1,3-dithiole-2-thione (5) when 1 is prepared by the reaction of 1-bromo-2,4,6-tri-t-butylbenzene with n-butyllithium. When the reaction is carried out using 1 prepared from 2 and t-butyllithium and then quenched with l-iodoethane, 2-ethylthio-3-(2,4,6-tri-butylphenylthio)-1,3-dithiole-2-thione and 1,2-diethylthio-1,2-bis(2,4,6-tri-t-butylphenylthio) ethene are produced. The formation of all these products can be explained in terms of initial thiophilic attack of 1 on the sulfur of carbon disulfide and an intermediate with a dual property of carbanion and carbene (i.e., ArSC(Li)(=S) ⇌ ArSC̈SLi) is suggested. The reaction of 1 with thiophosgene affords 1,2-dichloro-1,2-bis(2,4,6-tri-t-butylphenylthio) ethene, bis(2,4,6-tri-t-butylphenylthio)acetylene, and 1-chloro 2,4,6-tri-t-butylbenzene, the first two of which are explained to be formed by thiophilic attack of 1 with thiophosgene.
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  • 185
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    Journal of Physical Organic Chemistry 1 (1988), S. 83-90 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Theoretical studies on the reactions of ammonia with ketene and dimethylketene using the MNDO method are reported. The single step addition of ammonia to the olefinic bond of ketenes was found to provide a lower energy-barrier path than the two step carbonyl addition mechanism. The barrier height was lower in the reaction of keten compared with that of dimethylketene in support of the faster rate of solution phase reactions of aniline and ketenes. The deformation energies of reactants had an overwhelming influence in determining the activation barriers in all the reactions investigated.
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  • 186
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    Journal of Physical Organic Chemistry 1 (1988), S. 91-102 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The photolysis of benzoinalkylethers 1-5 solubilized in detergents show a significant deviation from the course of reaction in isotropic organic solvents. Remarkable difference in photobehaviour is noticed between the short chain (1-3) and the long chain (4 and 5) benzoinalkylethers in the micellar media. However, the influence of the micellar media on the photobehaviour of alkyldeoxybenzoins 6 and 7 was small. The importance of ‘cage effect’ in controlling the product distribution was evident from its dependence on the micellar size and on the occupancy number. More importantly, a comparative analysis of the photobehaviour of the ketone 1-7 reveals that the micellar interface can be used to control the conformations of organic molecules.
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  • 187
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    Journal of Physical Organic Chemistry 1 (1988), S. 103-114 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 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.
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  • 188
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    Journal of Physical Organic Chemistry 1 (1988), S. 115-117 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 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.
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  • 189
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    Journal of Physical Organic Chemistry 1 (1988) 
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    Keywords: Organic Chemistry ; Physical Chemistry
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  • 190
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    Journal of Physical Organic Chemistry 1 (1988), S. 119-121 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 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.
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  • 191
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    Journal of Physical Organic Chemistry 1 (1988), S. 123-131 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 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.
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  • 192
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 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.
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  • 193
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    Journal of Physical Organic Chemistry 1 (1988), S. 143-151 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 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.
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  • 194
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    Journal of Physical Organic Chemistry 1 (1988), S. 153-160 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 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.
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  • 195
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    Journal of Physical Organic Chemistry 1 (1988), S. 161-167 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 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.
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  • 196
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    Journal of Physical Organic Chemistry 1 (1988), S. 169-178 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 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.
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  • 197
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    Journal of Physical Organic Chemistry 1 (1988) 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 198
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 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.
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  • 199
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    Journal of Physical Organic Chemistry 1 (1988), S. 185-190 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 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.
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  • 200
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    Journal of Physical Organic Chemistry 1 (1988), S. 191-195 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 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.
    Additional Material: 4 Ill.
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