Library

Your email was sent successfully. Check your inbox.

An error occurred while sending the email. Please try again.

Proceed reservation?

Export
Filter
  • 1985-1989  (627)
  • 1980-1984  (593)
  • 1925-1929
  • Physical Chemistry  (1,220)
  • 101
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 465-476 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrogallol (1,2.3-benzentriol, 1) reacts with dioxygen in weakly alkaline solutions to form purpurogallin (2,3,4,6-tetrahydroxy-5H-benzocycloheptene-5-one, 2) which then reacts to form purpurogalloquinone (3) which then decays to a product absorbing at 440 nm. The formation of 3 requires 1.5 mol O2 per mol 1, and 1.0 mol per mol 2. No O2 is consumed during the decay of 3, and this reaction, being insensitive to O2 concentrations and the presence of both superoxide dismutase (SOD) and catalase, does not appear to be an oxidation. The first-order rate of decay of 3 decreases with increasing pH. 1 and 3 react at pH 9.0 with a second-order rate constant of ca. 100 M-1 s-1. SOD inhibits the oxidation of 1 and 2. Slight and variable apparent inhibition of the oxidation of 2 and 3 by SOD may be due to trace impurities in 2, but not contamination by 1. The peak concentration of 3 is attained more rapidly during the oxidation of 1 than during the oxidation of 2. A kinetic scheme based on parallel oxidation of 1 by dioxygen and superoxide, and it which the semiquinone of 1 oxidizes 2, is partially successful in simulating the observed kinetic behavior.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 102
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 103
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 104
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 105
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 611-619 
    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 alkanes and ethers. The SO4- radical was produced by the laser-flash photolysis of persulfate, S2O82-. For methane, only an upper limit of 1 × 106 M-1 s-1 could be determined. For ethane, propane, and 2-methylpropane, rate constants of 0.44, 4.0, and 10.5 × 107 M-1 s-1 were found. For ethyl and n-propyl ether, rate constants of 1.3 × 108 and 2.2 × 108 M-1 s-1 were found and for 1,4-dioxane and tetrahydrofuran, rate constants of 7.2 × 107 and 2.8 × 108 were obtained. The reaction of SO4- with allyl alcohol was also studied and found to have a rate constant of 1.4 × 109 M-1 s-1.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 106
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 107
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 108
    ISSN: 0538-8066
    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.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 109
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 110
    Electronic Resource
    Electronic Resource
    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
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 111
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 233-243 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that kinetic data on the polymerization of acetylene to vinyl acetylene and benzene can be reconciled with the formation of a 1,4 biradical which can isomerize by a 1-3, H-atom shift to the molecular product. Since the biradicals have a negligibly small life-time in the system the overall process appears to be a concerted bimolecular reaction. The labile isomer CH2 = C: which had been suggested as being the reactive intermediate, is argued on energy considerations not to be a plausible intermediate.Data on the reverse pyrolysis of vinyl acetylene to acetylene are consistent with the model. Extending the model to butadiene explains the observed molecular nature of its decomposition to ethylene and acetylene.Reactions of other oligomers of acetylene are discussed.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 112
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies of the kinetics of thermal unimolecular decomposition of methylcyclopentane, methylcyclohexane, ethynylcyclopentane, and ethynylcyclohexane have been carried out at temperatures in the range 861-1218 K using the technique of very low-pressure pyrolysis (VLPP). Multiple reaction pathways and secondary decomposition of primary products results in a complex array of reaction products. VLPP rate data (fall-off regime) were obtained for the overall decompositions and interpreted via the application of RRKM theory. The data for methylcyclopentane and methylcyclohexane were interpreted in terms of ring-opening bond fission pathways and bond fission to methyl and cycloalkyl radicals. By selecting Arrhenius parameters consistent with the analogous pathways in open-chain alkanes, a good fit to the overall decomposition is obtained. The data for ethynylcyclopentane and ethynylcyclohexane were interpreted in terms of ring-opening bond fission and alkyne to allene isomerization. The A factors for ring opening were based on known values for C-C fission in open-chain alkynes and the Arrhenius parameters for isomerization were chosen to be consistent with previously reported alkyne to allene isomerizations. The VLPP data are consistent with the following high-pressure rate expressions (at 〈 T 〉 = 1100 K) for the dominant primary reaction channel of ring opening adjacent to the substitutent group: \documentclass{article}\pagestyle{empty}\begin{document}$$\log (k/s^{ - 1} ) = (16.4 \pm 0.3) - (341 \pm 10)/\theta {\rm for methylcyclopentane,}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log (k/s^{ - 1} ) = (16.4 \pm 0.3) - (345 \pm 10)/\theta {\rm for methylcyclopentane,}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log (k/s^{ - 1} ) = (16.0 \pm 0.3) - (304 \pm 10)/\theta {\rm for ethynylcyclpentane, and}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log (k/s^{ - 1} ) = (16.0 \pm 0.3) - (303 \pm 10)/\theta {\rm for ethynylcyclohexane,}$$\end{document} where θ = 2.303RT kJ mol-. Comparison of the activation energies for the ethynyl-cycloalkanes with those for the methyl-cycloalkanes shows that the effect of the ethynyl substituent is consistent with the propargyl resonance energy. This evidence supports the assumption of a biradical mechanism for ring opening in these cycloalkanes.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 113
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 297-314 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Starting from Smoluchowski's hypothesis, a simple algorithm is developed in order to obtain the apparent rate constant at large values of time, t, with some physical and chemical processes, as in the case of diffusion controlled reactions. Some practical examples are illustrated, assuming nonuniform distribution function, space-dependent diffusion coefficient or short-range interaction leading to an asymptotic analytical expression of the form α + β/√t, where α and β are constants function of the system of interest.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 114
    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.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 115
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 7 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 116
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 117
    ISSN: 0538-8066
    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.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 118
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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}
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 119
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 120
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1131-1139 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pressure-jump method has been used to determine the rate constants for the formation and dissociation of nickel(II) and cobalt(II) complexes with cinchomeronate in aqueous solution at zero ionic strength. The forward and reverse rate constants obtained are kf = 2.27 × 106 M-1 s-1 and kr = 3.81 × 101 s-1 for the nickel(II) complex and kf = 1.23 × 107 M-1 s-1 and kr = 2.66 × 102 s-1 for the cobalt(II) complex at 25°C. The activation parameters of the reactions have also been obtained from the temperature variation study. The results indicate that the rate determining step of the reaction is a loss of a water molecule from the inner coordination sphere of the cation for the nickel(II) complex and the chelate ring closure for the cobalt(II) complex. The influence of the pyridine ring nitrogen atom of the cinchomeronate ligand on the complexation of cobalt(II) ion is also discussed.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 121
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 122
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 535-546 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The near U-V photolysis of t-butyl nitrite has been studied over the temperature range 303-393 K. Under these conditions t-butyl nitrite was shown to be a very clean photochemical source of t-butoxy radicals. This allows a study of the decomposition of the t-butoxy radical to be made over this temperature range (3). Extrapolation of the rate constants k3 to high pressure and combination with our previous thermal data give the results: \documentclass{article}\pagestyle{empty}\begin{document}$$k_3 (\infty)/{\rm s}^{{\rm - 1}} = 10^{14.04 \pm 0.37} \exp (- 7519 \pm 70.5/T)$$\end{document}
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 123
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 124
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 125
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 126
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 689-701 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of propane was studied behind reflected shock waves over the temperature range 1100-1450 K and the pressure range 1.5-2.6 atm, by both monitoring the time variations of absorption at 3.39 μm and analyzing the concentrations of the reacted gas mixtures. The rate constants of the elementary reactions were discussed from the results. The rate constant expressions, k1 = 1.1 × 1016 exp (-84 kcal/RT) s-1 and k4 = 9.3 × 1013 exp(-8 kcal/RT) cm3 mol-1 s-1, of reactions C3H8 → CH3 + C2H5 and C3H8 + H → n-C3H7 + H2 were evaluated, respectively.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 127
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 128
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 129
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 130
    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.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 131
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 132
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 133
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 134
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 135
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1141-1152 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase reaction of methyl vinyl ketone with the OH radical, in the presence of NOx, was investigated at 298 ± 2 K and atmospheric pressure of air. Glycolaldehyde and methylglyoxal were observed to be the major products, with a combined yield of 0.89 ± 0.16. The sum of the yields of the two other main products, formaldehyde and peroxyacetyl nitrate, were found to be essentially unity. The product yield data for glycolaldehyde and methylglyoxal indicate that OH radical addition to the terminal carbon atom of the 〉C=C〈 bond accounts for 72 ± 21% of the overall reaction, with the remaining 28 ± 9% proceeding via addition to the inner carbon atom of the double bond.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 136
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 207-218 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photo-oxidation of n-heptane in synthetic air containing methyl nitrite and nitric oxide has been ivestigated in an atmospheric flow reactor. By measuring the total yields of heptyl nitrate products, relative to the depletion of the n-heptane, the rate constant ratio, k3b/k3a has been determined for the reactions: Over the temperature range 253-325 K and at a total pressure of 730 Torr, the following relative Arrhenius equation has been obtained from the present study together with literature data: \documentclass{article}\pagestyle{empty}\begin{document}$$k_{3b} /k_{3a} = (1.4 \pm 1.1) \times 10^{ - 3} \exp [1640 \pm 250)/T]$$\end{document} These results confirm that the formation of alkyl nitrates from the photo-oxidation of n-alkanes arise from a primary reaction between the alkylperoxy radicals and nitric oxide. Furthermore the present experiments show that the lifetime of the intermediate in this type of reaction, presumed to be an alkyl peroxynitrite, ROONO, must be less than a few seconds.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 137
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 138
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 139
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 140
    ISSN: 0538-8066
    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.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 141
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 519-533 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic study of uncatalyzed and Ru(III) catalyzed oxidation of indigo carmine(IC) (disodium 3,3′-dioxobi-indolin-2,2′-ylidene-5,5′-disulphonate) by iodate ion in aqueous sulphuric acid solution is reported. The uncatalyzed reaction order was found to be four; one each with respect to IC and iodate ion and second order with H+ ion. The Ru(III) catalyzed reaction was of fifth order, second order with respect to H+ and first order with respect to reductant, oxidant, and catalyst. Stoichiometric ratios of both reactions were the same with a 3:2 reductant-oxidant ratio. In both uncatalyzed and catalyzed reactions isatin-5-monosulphonic acid (2,3-dioxoindoline-5-sulphonic acid) was observed as the oxidation product. Rate constants for both the reactions are reported. Reaction mechanisms consistent with the experimental data are suggested.Further, a fixed time method is described for the determination of Ru(III), based on its ability to catalyze the oxidation of IC by acidic iodate. Using [H+] 2.25M, [iodate] 1.00 × 10-3M and [IC] 5.0 × 10-5M, in presence of Ru(III), the reaction followed first order kinetics with respect to IC. The interference of various cations, neutral salts, and potassium iodide on the determination of Ru(III) was studied using synthetic mixtures. The selectivity of the method and the recommended procedure are described.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 142
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 143
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 144
    Electronic Resource
    Electronic Resource
    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
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 145
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1113-1122 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using Fourier transform infrared spectroscopy, the ethene yield from the reaction of C2H5 radicals with O2 has been determined to be 1.50 ± 0.09%, 0.85 ± 0.11%, and 〈0.1% at total pressures of 25, 50, and 700 torr, respectively. Additionally, the rate constant of the reaction of C2H5 radicals with molecular chlorine was measured relative to that with molecular oxygen. A ratio k6/k7 = 1.99 ± 0.14 was measured at 700 torr total pressure which, together with the literature value of k7 = 4.4 × 10-12 cm3 molecule-1s-1, yields k6 = (8.8 ± 0.6) × 10-12 cm3 molecule-1s-1. Quoted errors represent 2σ. These results are discussed with respect to previous kinetic and mechanistic studies of C2H5 radicals.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 146
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 147
    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).
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 148
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 149
    Electronic Resource
    Electronic Resource
    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
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 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.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 151
    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.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 152
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 153
    Electronic Resource
    Electronic Resource
    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.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 154
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 155
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 156
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 157
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 993-1001 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ethers are being increasingly used as motor fuel additives to increase the octane number and to reduce CO emissions. Since their reaction with hydroxyl radicals (OH) is a major loss process for these oxygenated species in the atmoshpere, we have conducted a relative rate study of the kinetics of the reactions of OH radicals with a series of ethers and report the results of these measurements here. Experiments were performed under simulated atmospheric conditions; atmospheric pressure (≃ 740 torr) in synthetic air at 295 K. Using rate constants of 2.53 × 10-12, and 1.35 × 10-11 cm3 molecule-1 s-1 for the reaction of OH radicals with n-butane and diethyl ether, the following rate constants were derived, in units of 10-11 cm3 molecule-1 s-1: dimethylether, (0.232 ± 0.023); di-n-propylether, (1.97 ± 0.08); di-n-butylether, (2.74 ± 0.32); di-n-pentylether, (3.09 ± 0.26); methyl-t-butylether, (0.324 ± 0.008); methyl-n-butylether, (1.29 ± 0.03); ethyl-n-butylether, (2.27 ± 0.09); and ethyl-t-butylether, (0.883 ± 0.026). Quoted errors represent 2σ from the least squares analysis and do not include any systematic errors associated with uncertainties in the reference rate constants used to place our relative measurements on an absolute basis. The implications of these results for the atmospheric chemistry of ethers are discussed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 158
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1173-1180 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the flash photolysis resonance fluorescence technique, absolute rate constants were determined for the gas phase reactions of hydroxyl radicals with a series of aliphatic polyethers. At 298 K, the measured rate constants (in units of 10-12 cm3 molecule-1 s-1) were: 2,2-dimethoxypropane, (3.9 ± 0.2); 2,2-diethoxypropane, (11.7 ± 1.3); 1,2-dimethoxypropane, (14.3± 1.5); 2-methoxyethylether, (17.5 ± 1.1); 2-ethoxyethlyether, (26.8 ± 2.4); 1,1-dimethoxyethane, (8.9 ± 1.0); and 1,1,3-trimethoxypropane, (16.7 ± 1.0).The temperature dependencies of the rate constants for 2,2-dimethoxypropane and 2,2-diethoxypropane, reactions (1) and (2), were studied over the temperature range 240-440 K and are expressed by the Arrhenius equations: \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm 1} = (3.55\,\, \pm 0.39)\,\, \times \,\,10^{ - 12} \,\,\exp [(30 \pm 35)\,/T]\,\,{\rm cm}^{\rm 3} \,\,{\rm molecule}^{{\rm - 1}} {\rm s}^{{\rm - 1}}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm 2} = (1.06\,\, \pm 0.25)\,\, \times \,\,10^{ - 11} \,\,\exp [(15 \pm 75)\,/T]\,\,{\rm cm}^{\rm 3} \,\,{\rm molecule}^{{\rm - 1}} {\rm s}^{{\rm - 1}}$$\end{document} Implications of the results are discussed in terms of reaction mechanisms and the prediction of gas phase OH radical reaction rates for aliphatic polyethers.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 159
    Electronic Resource
    Electronic Resource
    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
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 160
    Electronic Resource
    Electronic Resource
    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
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 161
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 162
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 163
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 175-191 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Methylbut-1-ene-3-yne and Propyne mixtures were pyrolyzed at 350-450°C in the absence and presence of O2 and NO. The major product of the reaction is a polymer, but m-xylene and p-xylene are also produced and were studied as the species of interest. The C8H10 formation rate is first-order in C3H4 and C5H6. The rate coefficient is best fitted by \documentclass{article}\pagestyle{empty}\begin{document}$$\log [k({\rm C}_{\rm 8} {\rm H}_{{\rm 10}}),M^{ - 1} s^{ - 1}] = (11.2 \pm 1.0) - (166 \pm 13)/2.3RT$$\end{document} though it is not inconsistent with \documentclass{article}\pagestyle{empty}\begin{document}$$\log [k({\rm C}_{\rm 8} {\rm H}_{{\rm 10}}),M^{ - 1} s^{ - 1}] = (8.17) - (125.9)/2.3RT$$\end{document} where R is the ideal gas constant in kJ/mol-K. Experiments in the presence of NO show that m-xylene and p-xylene formation occur by two processes: a concerted molecular mechanism (≃ 41%) and a singlet diradical mechanism (≃ 59%).
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 164
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    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.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 165
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 267-291 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pressure and temperature dependences of association reactions involving atoms and/or radicals is discussed and illustrated by reference to the reactions CH3 + CH3 → C2H6, CH3 + O2 → CH3O2, CH3 + H → CH4, and H + C2H4 → C2H5. Recent experimental measurements of the rate coefficients, k([M], T) are described, particular attention being paid to experiments designed to measure the rate coefficient over wide ranges of pressure and temperature. Methods of fitting the experimental data, to obtain estimates of the limiting rate coefficients, k0 and k∞, and to permit extrapolation to regions beyond the experimental range, are discussed. These methods include the Troe factorization technique, a combination of master equation and variational RRKM theory, and recent calculations by Wagner and Wardlaw using the technique developed by Wardlaw and Marcus to describe loose transition states.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 166
    Electronic Resource
    Electronic Resource
    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.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 167
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 423-430 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of oxidation of a number of ortho, meta, and para substituted S-phenylmercaptoacetic acids by N-Chloro-3-Metyl-2,6-Diphenylpiperidin-4-one (NCP) has been studied in buffered ethanol-water (75:25 v/v) of pH 5.46. The reaction is of first order each in [oxidant] and [substrate]. The rate constant decreases with increase in pH from 5.22 to 5.70. The reaction is accelerated by electron releasing and retarded by electron withdrawing substitutents. The ρ value obtained for this reaction is -1.88 at 10°C with a good correlation coefficient of 0.99 showing an electron deficient transition state. The effect of ortho substitutents also is discussed in detail.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 168
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 115-117 
    ISSN: 0894-3230
    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.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 169
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    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.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 170
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    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.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 171
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    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
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 172
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 123-131 
    ISSN: 0894-3230
    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.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 173
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    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.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 174
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    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
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 175
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    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.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 176
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 209-223 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The equilibrium acidities of phenylacetonitrile, and 20 of its m- and p-substituted derivatives have been measured in Me2SO solution. Their pKa′s plot linearly with those of the corresponding anilines. Combination of the pKa′s of these acids with their oxidation potentials, Eox(HA), and those of their conjugate bases, Eox(A-), provide an estimate of the acidities of the corresponding radical cations. The pKHA+ values for ArCH2CN+., where Ar is Ph, 1- and 2-naphthyl, and 9-anthryl, are -32, -18·5, -17·5, and -11, respectively, compared to 21·9, 20·85, 20·65, and 19·8 for the corresponding ArCH2CN acids. Acidities of PhCH(Me)CN+., Ph2CHCN+., 9-CN-FlH+., and 9-CN-XnH+. are -33, -35, -25, and -27, respectively, compared to 23·0, 17·5, 8·3, and 13·6 for the corresponding acids from which they were derived. The homolytic bond dissociation energies (BDEs) for the benzylic C—H bonds in these arylacetonitriles, estimated by combining pKHA with Eox(A-), fall in the range of 69 kcal/mol for 9-CN-XnH to 82 kcal/mol for PhCH2CN. For GC6H4CH2CN+. radical cations the acidities are decreased, relative to G=H, when G is an electron donor substituent and increased when G is an acceptor. The BDEs of the benzylic C—H bonds in GC6H4CH2CN are weakened by up to 4 kcal/mol by para donors and strengthened by up to 1·2 kcal/mol by m- or p-acceptors. The significance of these changes in BDEs with regard to the use of σ. scales and the ΔAOP method for estimating substituent effects on radical stabilities is discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 177
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 259-265 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 1-(Phenylazo)-1-(2-pyridyl)ethyl hydroperoxide, 1, 1-(phenylazo)-1-(2-furyl)ethyl hydroperoxide, 2, phenylazo(2-furyl)methyl hydroperoxide, 3, 1-(phenylazo)-1-(4-anisyl)ethyl hydroperoxide, 4, were synthesized in moderate yield by autoxidation of the phenylhydrazones in benzene. The ionic oxidation of benzyl methyl sulfide in benzene by 1-4 yielded the sulfoxide and the metastable α-azo hydroxides in essentially quantitative yield. The reaction was of the first order in α-azo hydroperoxide and sulfide, respectively. The relative reactivity series found was: 1(1.0) 〈4(1.4) 〈 phenylazo(4-anisyl)methyl hydroperoxide 5 (2·9) 〈2 (3·8) 〈 3 (9·6). α-Methyl substitution was found to slow the rate of oxygen-atom trasfer by a factor of 2 to 2.5. The low relative reactivity of 1 was opposite that expected based on electronic effects. Competitive intramolecular hydrogen bonding of the hydroperoxy proton to the pyridyl nitrogen in 1 accounted for the observed result.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 178
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 281-285 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal and photochemical decompositions of 5 have been studied. Both reactions lead to CBr2 transfer in good to high yields. With the 2-pentenes as substrates, CBr2 transfer is stereospecific in the classical singlet carbene manner.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 179
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 305-308 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Decomposition of the tosylhydrazone salts formed from cubyl carboxaldehyde and homocubanone, potential precursors of cubylcarbene (5) and homocubanylidene (6), leads in each case to products derived from 6. It is suggested that homocub-1(9)-ene (7) is the active ingredient in the formation of 6 from both precursors. The hydrazones formed from N-aziridylamines are useful photochemical sources of 6, and presumably other carbenes. Flash vacuum pyrolysis of the tosyl hydrazone salts and hydrazones at 600°C leads to indene.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 180
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    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.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 181
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 359-362 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reaction rates for solvolysis of a mustard analogue are accurately correlated by the solvatochromic equation without inclusion of a nucleophilicity term, and thus the equation is shown to reveal mechanistically significant information.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 182
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    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
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 183
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 247-257 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate of hydrolysis of the aromatic vinyl ether o-carboxy-α-methoxy-β,β-dimethylstyrene was found to be accelerated 25-fold by ionization of its carboxylic acid group, but the effective molarity which may be calculated if all of this rate acceleration is ascribed to intramolecular general acid catalysis is only EM = 1 · 1 m. This is similar to the small effective molarities found before for intramolecular catalysis by carboxylic acid groups of aliphatic vinyl ethers, which shows that, unlike the situation in other intramolecular reactions, e.g. ketone enolization, the extra rigidity of aromatic over aliphatic systems does not improve the efficiency of intramolecular catalysis in vinyl ether hydrolysis.It is suggested that this behaviour is the result of reduced conjugation between the vinyl ether group and the aromatic ring in the transition state of the vinyl ether hydrolysis reaction, which retards the rate and offsets any improvement effected by increased rigidity of the aromatic system.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 184
    ISSN: 0894-3230
    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.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 185
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 287-298 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ab initio STO-3G and 6-31G minimized geometries of 5-oxo- (9), 6-oxo-7-oxabicyclo[2.2.1]hept-2-yl cation (12) and 7-oxabicyclo[2.2.1]hept-2-yl cation (15) were obtained. The energy barriers for their Wagner-Meerwein rearrangements to the more stable 5-oxo- (11), 6-oxo-3-oxabicyclo[2.2.1]hept-2-yl (13) and 3-oxabicyclo[2.2.1]hept-2-yl (17) cations, respectively, have been evaluated and compared with those calculated for the rearrangement of the 5-oxo (18) and 6-oxobicyclo[2.2.1]hept-2-yl cations (20). In agreement with experimental data, the ‘true migratory aptitude’ of an acyl group is higher than that of β-oxoalkyl group in competitive Wagner-Meerwein rearrangments that are ‘energetically unbiased’. The ease of the acyl group 1,2-shift toward an electron-deficient center is related to the electron-donating ability of the carbonyl group due to favorable n(CO) ↔ σ σ ↔ p(C+) hyperconjugative interaction.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 186
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 299-303 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Iodide ion promotes the free radical reaction of isopropylmercury idide with bromotrichloromethane to yield isopropyl bromide with rate enhancement in the order of 104. The reaction involves electron transfer from i-PrHgI2- to the trichloromethyl radical in a long kinetic chain process. Iodide ion also promotes the free radical chain conjugate addition of tert-butylmercury chloride to α,β-unsaturated ketones, esters, phosphonate esters and sulfones. Competitive reactivity studies indicate that lithium di-tert-butylcuprates or tri-tert-butylzincates react with 2-cycloalkenones by a mechanism involving attack by tert-butyl radicals. No evidence for radical attack is observed for the corresponding n-butyl ate complexes of copper or zinc.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 187
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    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.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 188
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    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.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 189
    ISSN: 0894-3230
    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.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 190
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    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.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 191
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    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.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 192
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 241-245 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rates of solvolysis of l-aryl-l-phenyl-2,2-dimethylpropyl(1) p-nitrobenzoates and of aryldiphenylmethyl-p-nitrobenzoates (2) were measured in 80% acetone. An inverse order of reactivity, kp-CF3/km- CF3 〉 l was observed for 1 but not for 2. The X-ray crystallogoraphic study of the parent compounds, l,l-diphenyl-2,2-dimethylpropyl-p-nitrobenzoate (1b) and triphenylemethyl benzoate (3b), and of 2-phenyl-2-propyl-p-nitrobenzoate (4) indicated that in the highly congested system 1 both phenyl rings were nonplanar, whereas the phenyl rings in 3 and 4 were essentially planar.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 193
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    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.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 194
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 197-207 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ESR spectra of l-cyano-2-(trimethylsilyl)ethyl and related radicals were recorded. Temperature dependent ESR spectra of these radicals revealed that electron-releasing trimethylsilylmethyl and electron-withdrawing cyano groups synergetically functioned to stabilize the radical centers due to σ-π captodative effects.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 195
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The excellent linearity (R2 = 0·997) of a plot of pKa values for 17 m- and p-substituted benzyl phenyl sulfones, GC6H4CH2SO2Ph, vs. those for the corresponding arylacetonitrile, GC6H4CH2CN, demonstrates that substituent solvation and substituent solvation assisted resonance (SSAR) effects for p-CN, p-COPh, and p-SPh are nearly identical in these two substrates. The PhSO2 group in PhCH2SO2Ph increases the BDE of the α-C—H bond by 2 kcal/mol, relative to toluene. The α-C—H bonds in GC6H4CH2SO2Ph sulfones are stabilized by 1-2 kcal/mol by acceptor G′s (m-CN, p-CN, m-CF3, p-CF3), but weakened by 1 and 5 kcal/mol, respectively, by donors (p-OMe and p-NMe2). The GC6H4CH2SO2Ph+. radical cation with G = H has a pKHA+. = -25. Its acidity is increased when G is an acceptor by as much as 9 to 10 kcal/mol (G = 3-CN, 3-CF3, 4-CF3, 4-NO2), but is decreased when G is a donor by as much as 33 kcal/mol (G = NMe2). When G = 4-SPh the radical cation is stabilized, relative to G = H, by a larger amount (25 kcal/mol) than when G = 4-OMe (18 kcal/mol). Structural changes along the series PhCH2SO2Ph, 2-naphthyl-CH2SO2Ph, 9-anthryl CH2SO2Ph cause negligible changes in the acidities of these acids, but sizable decreases in the acidities of the corresponding radical cations. Introduction of a phenylsulfonyl group into the methyl group of 9-methylanthracene or the 9-position of fluorene or xanthene increase the BDEs by 3, 2, and 7 kcal/mol, respectively. These effects of PhSO2 groups are compared and contrasted with those of CN groups.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 196
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 267-273 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The PE spectra of four stable bicyclic triaziridines with trifluoromethyl, methyl, phenyl, spirocyclopentane and spirocyclohexane substituents are measured. From a comparison of these experimental data with MNDO calculations the energies and the interactions of the nitrogen lone-pair orbitals were obtained. The trifluoromethyl group may be reliably simulated by a fluorine atom. The ionization potentials are unexpectedly high and so are the cyclovoltammetric anodic potentials. The MNDO valence electron densities are in agreement with the comparatively small differences in the chemical shifts of the differently substituted nitrogens of the triaziridine rings.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 197
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 275-280 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to examine the substituent effect of ethylenedithio and trimethylenedithio groups on electron acceptors, the two title compounds were prepared in one step from the corresponding quinones. These species behave as weak π-electron acceptors owing to the electronic and sterical effects of the fused groups. Only the bis(ethylenedithio) derivative formed a charge-transfer complex with tetrathiotetracene, which showed a moderate electric conductivity of 2·0 × 10-2 S cm-1. In addition, both species oxidized copper, sodium, and potassium iodides to give the corresponding deeply colored metal salts, most of which were semiconductive. The naphtho analogs were similarly studied, but hardly served as electron acceptors.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 198
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    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
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 199
    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.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 200
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 351-357 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The title reaction is an instance of a simple nucleophilic attack of neutral nitrogen on aromatic sp2 carbon. The kinetic data (obtained in dimethyl sulphoxide) are compared to the results reported by the literature for the same reaction of aliphatic amines. Some possible interactions (substrate/nucleophile, substrate/salt) preceding the attack of the nucleophile are discussed.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
Close ⊗
This website uses cookies and the analysis tool Matomo. More information can be found here...