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  • Physical Chemistry  (67)
  • Wiley-Blackwell  (67)
  • Berlin : Akad.-Verl.
  • Berlin : Verl. Technik
  • Marine Biological Laboratory (Woods Hole, Mass.)
  • 1980-1984  (67)
Collection
Keywords
Publisher
  • Wiley-Blackwell  (67)
  • Berlin : Akad.-Verl.
  • Berlin : Verl. Technik
  • Marine Biological Laboratory (Woods Hole, Mass.)
Years
Year
  • 1
    Electronic Resource
    Electronic Resource
    Rate constants for the reaction of ground-state oxygen atoms with methanol from 297 to 544 KN.R.C.C. No. 19814. (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 371-379 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant for the reaction of ground-state oxygen atoms with methanol has been determined between 297 and 544 K by a phase-shift technique using mercury photosensitized decomposition of N2O to generate oxygen atoms. The relative oxygen atom concentration was monitored by the chemiluminescence from the reaction of oxygen atoms with nitric oxide. The results are accommodated by the Arrhenius expression k1 = (9.79 ± 2.71) × 1012 exp[(-2267 ± 111)/T]cm3/mol·s, where the indicated uncertainties are 95% confidence limits for 10 degrees of freedom. As an incidental part of this work, the third-body efficiency of CH3OH relative to N2O for the reaction O + NO + M → NO2 + M (M = CH3OH) was determined to be 3.1 at 298 K.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140405
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  • 2
    Electronic Resource
    Electronic Resource
    Kinetics of recombination, dismutation, and disproportionation reactions involving neutral ketyl radicals and radical anions (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 379-396 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of fast elementary recombination of neutral ketyl radicals of benzophenone and its four derivatives (BPH⋅), the dismutation of benzophenone radical anions, the disproportionation between BPH⋅ and stable nitroxyl radicals, (), and the electron transfer have been investigated in both individual solvents and binary mixtures of different viscosities. Reaction (1) for unsubstituted BPH in water, water glycerol, and n-hexane is controlled by diffusion with 2k1 ≃ kdiff. In aliphatic alcohols and toluene, which form solvation complexes with BPH⋅, reaction (1) is diffusion-enhanced and activation-controlled, respectively, with 2k1 〈 kdiff. In a viscous solvent such as 1-propanol-glycerol mixture (100 ≲ η ≲ 450 cP) reaction (1) is diffusion-controlled. Reaction (2) in alkaline 1-propanol and alkaline 1-propanol-glycerol mixture is activation controlled. The rates of reactions (3) and (4) for benzophenone radicals and nitroxyl radicals of the imidazoline series decrease as the viscosity of the water-glycerol and 1-propanol-glycerol mixtures is increased. The reactions are molecular mobility limited; nevertheless, the numerical values of k3 (k4) are 2-6 times as small as the corresponding kdiff values due to the low steric factor of the reactions (therefore called pseudodiffusion-controlled reactions). The theoretical estimates of k3 (k4) are in good agreement with the experimental results. The elimination of spin forbiddance in the process of radical recombination in viscous solvents is discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160408
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  • 3
    Electronic Resource
    Electronic Resource
    Acid-catalyzed hydrolysis of some diazoacetophenones in aqueous dioxan (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 25-35 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants and activation parameters for the acid-catalyzed hydrolysis of eight ring-substituted diazoacetophenones have been measured in three dioxan-water mixtures. An isokinetic relationship applies to the results obtained using a 50% dioxan-water mixture as solvent. Solvent and substituent effects are discussed together with some mechanistic aspects. Substituent constants are reported for the —COCHN2 group.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150104
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  • 4
    Electronic Resource
    Electronic Resource
    Thermal decomposition of 2,2-propane-d2. CH3CDCH3 radical isomerization (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 113-122 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of CH3CD2CH3 was studied from 713 to 853 K at pressures of 98-466 torr. The values of k1/k2 = 2.08 ± 0.05 and k3/k4 = 2.04 ± 0.66 were found independent of temperature by measuring the ratios of CH4/CH3D and CH3CHD2/CH3CD3, respectively, for the following reactions:. Isomerization of CH3CDCH3 was detected by measuring CHDCH2 formed from the isomerized radical. The expression of k21/k22 was found to be where k21 and k22 are the rate constants of. The results and conclusions are discussed and compared with previous works.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120205
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  • 5
    Electronic Resource
    Electronic Resource
    Demetallation of α,β,γ,δ-tetrakis(p-sulfophenyl) porphiniron(III) in mineral acid-alcohol-water media (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 97-105 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Demetallation rates of α,β,γ,δ-tetrakis(p-sulfophenyl)porphiniron(III) in hydrochloric acid-ethanol-water, perchloric acid-ethanol-water, and sulfuric acid-alcohol-water media were determined. For a given acidity value H0 the order of the rates for the three acids was HCl 〉 H2SO4 〉 HClO4. This is also the order for complex formation between acid anion and iron(III). Consequently ligands as well as protons are involved in the breaking of bonds between the metal and the porphyrin leading to the formation of the activated complex. The log k values for HCl and HClO4 media were not linearly related to the Hammett acidity function as they were for sulfuric acid-ethanol-water media. The average ΔH
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120203
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  • 6
    Electronic Resource
    Electronic Resource
    The azoethane-initiated thermal reaction of isobutene. Heat of formation of the 2-methyl-2-pentyl radical (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1133-1145 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The azoethane-sensitized thermal reaction of isobutene has been studied at 526-565 K. The initial concentrations of azoethane and isobutene were in the ranges of 1.40-10.5 × 10-4 and 6.78-26.6 × 10-4 mol/dm3, respectively. From the initial rates of formation of ethane and 2-methylpentane the heat of formation of the 2-methyl-2-pentyl radical was determined. The result obtained is ±Hf0(2-methyl-2-pentyl) = 0.8 ± 2.0 kcal/mol. The entropy of the radical, obtained from statistical mechanical calculations and experimentally, is S0(2-methyl-2 pentyl) = 92.8 ± 1.5 cal/mol°K. The results support the high heat of formation of the t-butyl radical suggested by different authors.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151103
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  • 7
    Electronic Resource
    Electronic Resource
    Temperature and third-body dependence of the rate constant for the reaction O + O2 + M → O3 + M (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 417-434 
    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 was used to measure the rate constants of the reaction O + O2 + M → O3 + M (M = N2, O2, Ar, and He) as a function of temperature. The results for the rate constants are given by The activation energies with N2, O2, and Ar as third bodies are equal within the experimental error, (-1370 → 340 cal/mol), and the relative third-body efficiencies at 298 K for N2, O2, Ar, and He are 1.00, 0.99, 0.69, and 0.60, respectively.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140408
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  • 8
    Electronic Resource
    Electronic Resource
    Origin of the oxygen in the oxidation of triphenylphosphine by potassium persulfate - application of the 18O isotope effect in 31P NMR (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1167-1173 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Potassium persulfate oxidizes triphenylphosphine to triphenylphosphine oxide in 60% aqueous acetonitrile. It has been suggested that the oxygen of the product, triphenylphosphine oxide, might originate from solvent water, following nucleophilic attack on an intermediate phosphonium ion. We have investigated the origin of the oxygen in the oxidation of triphenylphosphine by potassium persulfate in 60% aqueous acetonitrile containing 20% [18O]water. The product was analyzed by using the 18O isotope effect in 31P NMR spectroscopy. The magnitude of the 18O isotope-induced shift was determined by synthesizing triphenylphosphine [18O]oxide and was found to be 0.038 ppm upfield. The product of the oxidation reaction in 20% [18O]water displayed no 18O isotope effect. The origin of the oxygen in the oxidation reaction is the persulfate ion, consistent with an alternative mechanism involving nucleophilic attack by water at the sulfur atom of a phosphonium peroxysulfate intermediate.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160912
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  • 9
    Electronic Resource
    Electronic Resource
    Reply to “comments on ‘a smog chamber and modeling study of the gas phase NOx-air photooxidation of toluene and the cresols’” (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 813-814 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140709
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  • 10
    Electronic Resource
    Electronic Resource
    Rate constants for the gas-phase reaction of OH radicals with a series of ketones at 299 ± 2 K (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 839-847 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate constants for the reaction of OH radicals with a series of ketones have been determined at 299 ± 2 K, using methyl nitrite photolysis in air as a source of hydroxyl radicals. Using a rate constant for the reaction of OH radicals with cyclohexane of 7.57 × 10-12 cm3 molecule-1 s-1, the rate constants obtained are (× 1012 cm3 molecule-1 s-1): 2-pentanone, 4.74 ± 0.14; 3-pentanone, 1.85 ± 0.34; 2-hexanone, 9.16 ± 0.61; 3-hexanone, 6.96 ± 0.29; 2,4-dimethyl-3-pentanone, 5.43 ± 0.41; 4-methyl-2-pentanone, 14.5 ± 0.7; and 2,6-dimethyl-4-heptanone, 27.7 ± 1.5. These rate constants indicate that while the carbonyl group decreases the reactivity of C—H bonds in the α position toward reaction with the OH radical, it enhances the reactivity in the β position.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140804
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