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  • Physical Chemistry  (20)
  • Wiley-Blackwell  (20)
  • Annual Reviews
  • Oxford University Press
  • Springer
  • 1980-1984
  • 1975-1979  (20)
  • 1950-1954
  • 1979  (20)
Collection
Keywords
Publisher
  • Wiley-Blackwell  (20)
  • Annual Reviews
  • Oxford University Press
  • Springer
Years
  • 1980-1984
  • 1975-1979  (20)
  • 1950-1954
Year
  • 1
    Electronic Resource
    Electronic Resource
    Combination and disproportionation reactions of allylic radicals with ethyl, propyl, and t-Butyl Radicals (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1055-1069 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-Methylallyl, 1,1-dimethylallyl, 1,2-dimethylallyl, 1,3-dimethylallyl, 1,1,2-trimethylallyl, and 1-ethylallyl radicals have been generated in the gas phase at 20 ± 1°C by addition of H atoms, formed by Hg(63P1) photosensitization of H2, to appropriate dienes. Their combination reactions with ethyl radicals have been studied and the relative reactivities of the reaction centers in each allylic radical determined. Similar measurements have been made for some combination reactions of n-propyl, i-propyl, and t-butyl with 1-methylallyl and 1,1,2-trimethylallyl radicals. The more substituted reaction centers are found to be the less reactive. In addition the self-combination and disproportionation of 1-methylallyl radicals has been investigated, as has cross disproportionation of each allylic radical with ethyl. The results establish a general pattern of reactivity for these radicals, which is interpreted primarily in terms of the effects of steric interaction during reaction.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550111004
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  • 2
    Electronic Resource
    Electronic Resource
    A kinetics study of the temperature dependence of the reactions of OH(2Π) with CF3CHCl2, CF3CHClF, and CF2ClCH2Cl (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 187-197 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The flash photolysis resonance fluorescence technique has been utilized to determine the rate constants for three reactions involving the hydroxyl radical [OH(2≅)] and three halogenated C2 alkanes. The nominal temperature range covered was 250-375 K. The compounds studied and the resulting Arrhenius expressions in units of cm3/molec·sec are The error limits in these expressions are such that they include any possible systematic errors due to the presence of impurities in the halocarbon samples. Tropospheric lifetimes have been calculated for the above species by combining the above rate constant data with global seasonally and diurnally averaged hydroxyl radical concentrations.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110210
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  • 3
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism for the iodination of methylmalonic acid (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 131-145 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction\documentclass{article}\pagestyle{empty}\begin{document}$ CH\left({CH_3 } \right)\left({COOH} \right)_2 + I_2 \rightleftharpoons CI(CH_3)\left({COOH} \right)_2 + H^ + + I^ - $\end{document} was followed spectrophotometrically at 353 nm and 470 nm at 25°C under various conditions of pH and methylmalonic acid concentration. The equilibrium constant for the reaction is 0.11 ± 0.02. An iterative technique was used to integrate postulated rate equations. Agreement between experimental and calculated absorbance versus time curves was generally better than 0.005 A (approximately 5% of maximum) at both wavelengths for a mechanism where the rate-determining step is formation of an enolate (k = 1.63 Θ 10-4 ± 0.03 Θ 10-4 sec-1). The enolate may be rapidly transformed to the enol or enol carboxylate anion depending on the pH. All three forms are rapidly iodinated. The mechanism of general base catalysis is supported by rate increases proportional to base concentration in buffer solutions. The bases, acetate ion, chloracetate ion, sulfate ion, dichloracetate ion, and water, follow a Brønsted relationship with β = 0.7.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110205
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  • 4
    Electronic Resource
    Electronic Resource
    Mechanistic details of the Belousov-Zhabotinsky oscillations. II. The organic reaction subset (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 155-164 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Our previous mechanistic model for the Belousov-Zhabotinsky reaction has been revised to include a more realistic set of reactions for the oxidation pathways of the organic intermediates. A few other rate constants have also been modified to include new information. The revised mechanism reproduces the essential experimental observations, although the periods of oscillation are somewhat too long and oscillations cease at malonic acid concentrations about ten times greater than the observed lower limit. However, the essential features of the mechanism are clearly understood.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110207
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  • 5
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of oxidation of dimethyl sulfoxide by chloramine-T in aqueous solution (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 261-273 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of oxidation of dimethyl sulfoxide (DMSO) by chloramine-T (CAT) is studied in HClO4 and NaOH media with OsO4 as a catalyst in the latter medium. In acid medium, the rate law is -d [CAT]/dt = k [CAT][DMSO][H+]. Alkali retards the reaction and the rate law takes the form -d [CAT]/dt = k [CAT][DMSO][OsO4]/[NaOH], but is reduced to -d [CAT]/dt = k [CAT][DMSO] at higher alkali concentrations. The reaction is subjected to changes in (a) ionic strength, (b) concentrations of added neutral salts, (c) concentrations of added reaction product, (d) dielectric constant, and (e) solvent isotope effect, and the subsequent effects on the reaction rate are studied.The reaction mechanism in acid medium assumes an electrophilic attack by the free acid RNHCl (CAT′) at the sulfur site in DMSO, forming a reaction intermediate which subsequently decomposes to dimethyl sulfone on hydrolysis. Formation of a cyclic complex between RNHCl and OsO4 which interacts with the substrate in a slow step explains the observed results in alkaline medium. The simplification of the rate equation at higher alkali concentrations is attributed to a direct reaction between chloramine-T and the substrate.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110304
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  • 6
    Electronic Resource
    Electronic Resource
    Evidence for production of the hydroxycarbonyl radical in the decomposition of formic acid on platinum (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 445-449 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Formic acid molecules highly diluted in argon were passed through a clean platinum screen at 420-730 K and condensed onto an 8-K CsI window. The well-known decomposition products, CO2, CO, and H2O, were observed in the infrared spectra of the resulting matrices. In addition, new absorptions which are attributed to the OCOH free radical were also observed. Experiments with partially deuterated formic acids confirmed that the carbon-hydrogen bond of the formic acid was lost in the formation of the new intermediate species. The activation energy for CO2 production, Ea = 3.5 ± 0.2 kcal/mol, was determined by monitoring its appearance rate at several different catalyst temperatures.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110409
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  • 7
    Electronic Resource
    Electronic Resource
    The interpretation of pressure-dependent very-low-pressure pyrolysis experiments (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 317-331 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Unimolecular rate data from systems such as very-low-pressure pyrolysis (steady-state flow) and static experiments where gas-gas collisions compete with gas-wall collisions must be interpreted in terms of reactant inhomogeneity arising from finite diffusion rates, rather than using the usual assumption of a well-stirred reactor. An integrodifferential equation describing this process is derived, and a numerical variational solution applicable to weak gas-gas collisions is presented. This gives a powerful method for obtaining collisional energy transfer probabilities from such experiments. Previously reported data (on cyclobutane and cycloheptatriene reactions) are reinterpreted to give conventional values for average energy transfer, replacing the anomalously low collisional efficiencies proposed previously.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110308
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  • 8
    Electronic Resource
    Electronic Resource
    A quantitative study of alkyl radical reactions by kinetic spectroscopy III. Absorption spectrum and rate constants of mutual interaction for the ethyl radical (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 995-1005 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Intrinsic spectral and kinetic parameters have been measured for the ethyl radical, which was formed in the gas phase by the flash photolysis of azoethane. Absolute values of the extinction coefficient ε(λ) were derived from complementary measurements of the yield of nitrogen and the absorbance of an equivalent concentration of the ethyl radical. The absorption spectrum is broad, structureless, and comparatively weak; ε(247) = 4.8 × 102 l/mol·cm at the maximum, and the oscillator strength is (9.1 ± 0.5) × 10-3. This is in good qualitative agreement with a spectrum obtained independently using the technique of molecular modulation spectrometry.The biomolecular reactions of mutual interaction were the only significant reactions of the ethyl radical in this system; kinetic analysis of the second-order decline of the absorbance during the dark period yielded a value of k/ε(λ) for each experiment. The rate constant for mutual interaction was evaluated from the product of corresponding measurements of k/ε(λ) and ε(λ) individual values are independent of the wavelength of measurement, and the mean value is k = (1.40 ± 0.27) × 1010 l/mol·sec. The rate constant for mutual combination was derived with the aid of product analysis as k2 = (1.24 ± 0.23) × 1010 l/mol·sec; it stands in close agreement with the set of “high” values obtained by direct measurement using a variety of methods.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110906
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  • 9
    Electronic Resource
    Electronic Resource
    Homogeneous decomposition of vinyl ethers. The heat of formation of ethanal-2-yl (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 715-730 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal unimolecular decomposition of three vinylethers has been studied in a VLPP apparatus. The high-pressure rate constant for the retro-ene reaction of ethylvinylether was fit by log k (sec-1) = (11.47 + 0.25) - (43.4 ± 1.0)/2.303 RT at 〈T〉 = 900 K and that of t - butylvinylether by log k (sec-1) = (12.00 ± 0.27) - (38.4 ± 1.0)/2.303 RT at 〈T〉 = 800 K. No evidence for the competition of the higher energy homolytic bond-fission process could be obtained from the experimental data. The rate constant compatible with the C—O bond scission reaction in the case of benzylvinylether was log k (sec-1) = (16.63 ± 0.30) - (53.74 ± 1.0)/2.303 RT at 〈T〉 = 750 K. Together with ΔHf,3000(benzyl·) = 47.0 kcal/mol, the activation energy for this reaction results in ΔHf,3000(CH2CHO) = +3.0 ± 2.0 kcal/mol and a corresponding resonance stabilization energy of 3.2 ± 2.0 kcal/mol for 2-ethanalyl radical.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110705
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  • 10
    Electronic Resource
    Electronic Resource
    Kinetic flash spectroscopic study of the CH3O2—CH3O2 and CH3O2—SO2 reactions (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 921-933 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methylperoxy radicals were generated by the flash photolysis of azomethane-oxygen mixtures. The observed broadband spectrum of the CH3O2 radical is similar, but not identical to those reported previously. The CH3O2 decay followed second-order kinetics at high CH3O2 concentrations with k4' = (2.5 ± 0.3) × 108 liter/mol·sec (23 ± 2°C); 2CH3O2 → products (4). Because of the potential loss of CH3O2 through the reactions with HO2 and CH3O radicals subsequently formed in this system, simulations suggest that the true k4 is in the range: 2.5 × 108 ≥ k4 ≥ 2.3 × 108 liter/mol·sec. Deviations from linearity of the plot of the reciprocal of the CH3O2 absorbance versus time were seen at long times and were attributed to the reaction (5) with an apparent rate constant k5' ⋍ (1.6 ± 0.4) × 105 liter/mol·sec; CH3O2 + Me2N2 → product (5). The CH3O2-SO2 reaction, CH3O2 + SO2 → products (16), was studied by observing CH3O2 decay in flashed mixtures of Me2N2, O2, and SO2. The results gave the apparent second-order rate constant k16' ⋍ (6.4 ± 1.4) × 106 liter/mol·sec. It appears likely that each occurrence of reaction (5) and (16) is followed by the loss of an additional CH3O2 radical and that k5 ⋍ k5'/2 and k16 ⋍ k16'/2. Our findings suggest that a significant fraction of the SO2 oxidation in a sunlight-irradiated NOx-RH-polluted atmosphere, may occur by reaction with CH3O2 as well as from the HO and HO2 reactions.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110811
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