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  • 1
    Electronic Resource
    Electronic Resource
    Rate constants for hydrogen abstraction reactions of the sulfate radical, SO4-. Alkanes and ethers (1989)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 611-619 
    Details
    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
    URL: http://dx.doi.org/10.1002/kin.550210802
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  • 2
    Electronic Resource
    Electronic Resource
    Rate constants for Hydrogen abstraction reactions of NO3 in aqueous solution (1990)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 505-512 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants have been measured by pulse radiolysis for the reactions of the NO3 radical with five cyclic ethers and a series of alcohols. Rate constants ranged from 3.5 × 104 M×1 s×1 for deuterated methanol to 1.1 × 107 M-1 s-1 for tetrahydrofuran. The rate constants for the reactions of NO3 with the alcohols 1-propanol to 1-heptanol were found to be linearly dependent on the number of CH3 groups with a group reactivity of 6.4 × 105 M-1 s-1.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550220507
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  • 3
    Electronic Resource
    Electronic Resource
    On the application of an oxygen probe in chemical kinetics: The influence of the probe response on kinetic measurement (1995)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 27 (1995), S. 829-842 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Membrance covered oxygen probes are frequently used to monitor the progress of chemical reactions involving dissolved oxygen. For reactions that are comparable in rate to the response of the oxygen probe it is difficult to obtain the correct kinetic constants directly from the probe signal with traditional kinetic data manipulation methods. In this article, we apply the method of impulse response function to describe the probe signal of an oxygen probe for three different types of simple chemical reactions. The impulse response function is obtained experimentally. Using the impulse response function we have obtained the relationships between the probe signal and the kinetic parameters of these reactions. The slow response of the probe has two effects on the kinetic curves of the reaction studied: a time-lag and distortion of the shape of the kinetic curve throughout the reaction. The latter effect becomes significant when the reaction is fast. Procedures to obtain the correct kinetic information from the oxygen probe signal are described. © 1995 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550270809
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  • 4
    Electronic Resource
    Electronic Resource
    Kinetics of the reaction of the sulfate radical with the oxalate anion (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 195-199 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction of the sulfate radical, SO4-, with the oxalate anion C2O42- was studied in aqueous solution and second-order rate constants, corrected for the effects of ionic strength, derived. Measurements were carried out over the temperature range 24-60°C resulting in the expression k0 = 2.10 ± 0.96 × 108 exp(-1080 ± 140/T) L mol-1 s-1. © 1996 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.5
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  • 5
    Electronic Resource
    Electronic Resource
    Rates of reaction of atomic oxygen with C2H3F, C2H3Cl, C2H3Br, 1,1-C2H2F2, and 1,2-C2H2F2 (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 521-527 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the reactions of atomic oxygen (O3P) with C2H3F, C2H3Cl, C2H3Br, 1,1-C2H2F2, and 1,2-C2H2F2 have been measured at 307°K using a discharge-flow system coupled to a mass spectrometer. The rate constants for these reactions are (in units of 1011 cm3 mole-1 s-1) 2.63 ± 0.38, 5.22 ± 0.24, 4.90 ± 0.34, 2.19 ± 0.18, and 2.70 ± 0.34, respectively. For some of these reactions, the product carbonyl halides were identified.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550040506
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  • 6
    Electronic Resource
    Electronic Resource
    Rate constants for one-electron oxidation by methylperoxyl radicals in aqueous solutions (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1185-1191 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for one-electron oxidation by the methylperoxyl radicals (CH3O2, HOCH2O2, -O2CCH2O2, and CCI3O2) in aqueous solutions have been measured by pulse radiolysis and found to be in the range of 3 × 105 to 6 × 108 M-1 s-1 for compounds with redox potentials between 0.6 and 0.1 V. Substitution on the methylperoxyl radical with OH or CO2- has only a minor effect on the rate of oxidation but substitution with three chlorines increases the rate constants by two orders of magnitude. The redox potential of the CH3O2 radical is estimated to be 0.6-0.7 V.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550181007
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  • 7
    Electronic Resource
    Electronic Resource
    Rate constants for hydrogen abstraction reactions of the sulfate radical, SO4-. Alcohols (1989)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 677-687 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants have been determined for the reactions of SO4- with a series of alcohols, including hydrated formaldehyde. The SO4- radical was produced by the laser-flash photolysis of persulfate, S2O82-. Rate constants for the reactions of SO4- with alcohols range from 1.0 × 107 for methanol to 3.4 × 108 M-1 s-1 for 1-octanol. Rate constants for the reactions of SO4- with deuterated methanol and ethanol are lower by about a factor of 2.5. For methanol, ethanol, and 2-propanol, the temperature dependence of the rate constant was determined over the range 10-45°C.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550210807
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  • 8
    Electronic Resource
    Electronic Resource
    Kinetics of the reactions of singlet molecular oxygen (O21Δg) with organic compounds in the gas phaseSupported in part by the Measures of Air Quality Program of the National Bureau of Standards. Presented at Symposium on Oxidation by Singlet Oxygen, American Chemical Society, Washington, D.C., September 1971. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 197-211 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of singlet molecular oxygen (O21Δg) with a series of organic compounds have been studied in the gas phase at 298°K. The concentration of singlet molecular oxygen was determined by titration with 2,5-dimethylfuran. The titration technique was checked using a photoionization technique. Absolute rate constants were measured on the basis of the loss of organic reactant and, in some cases, of singlet molecular oxygen. It was found that the usual method of producing singlet molecular oxygen in the gas phase can also, under some conditions, allow reactive species other than singlet molecular oxygen to enter the reactor, leading to serious errors in the determination of rate constants. This problem was eliminated by carrying out the rate measurements in the presence of a small amount of nitrogen dioxide a radical scavenger.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050204
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  • 9
    Electronic Resource
    Electronic Resource
    Stopped-flow studies of the mechanisms of ozone-alkene reactions in the gas phase propene and isobutene (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1019-1041 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of ozone with propene and isobutene have been studied in the gas phase at 298°K and 530 Pa (4 torr) using a stopped-flow reactor coupled to a photoionization mass spectrometer. Reactant and product concentrations were followed as a function of reaction time. The major reaction products monitored were CH2O, CH3CHO, CO2, and H2O from the propene reaction, and CH2O, (CH3)2CO, CO2, and H2O from the isobutene reaction. The observations were interpreted on the basis of the Criegee mechanism for ozonolysis in solution: for which we find kA≈kB.In the gas phase the carbene peroxy radical is postulated to isomerize and decompose into molecular and free-radical products.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550101003
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  • 10
    Electronic Resource
    Electronic Resource
    Kinetics and energetics of the criegee intermediate in the gas phase. I. The criegee intermediate in ozone-alkene reactions (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 201-224 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chemistry and energetics of the Criegee intermediate, a primary product of the ozonolysis of alkenes, are discussed in terms of recent ab-initio calculations and laboratory studies. The experimental observations in O3-alkene systems can be rationalized on the basis of a general mechanism: where the
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140302
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