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  • 1
    Electronic Resource
    Electronic Resource
    Preparation of nonreactive surfaces for reaction-rate studies (1976)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 8 (1976), S. 23-24 
    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.550080104
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  • 2
    Electronic Resource
    Electronic Resource
    Collisional deactivation of O2(1Σg+) (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 175-185 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relaxation rates for O2(1Σg+) by nonradiative pathways have been determined using the fast-flow technique. O2(1Σg+) is formed from O2(1Δg) by an energy pooling process. O2(1Δg) is generated by passing purified oxygen through a microwave discharge. Oxygen atoms are removed by distilling mercury vapor through the discharge zone. It has been observed that the wall loss rate for O2(1Σg+) decreases with increasing pressure of oxygen and thus appears to be diffusion controlled. Quenching rate constants for O2, N2, and He have been determined and found to be (1.5 ± 0.1) × 104, (1.0 ± 0.05) × 106 and (1.2 ± 0.1) × 105 l./mol·sec, respectively.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110209
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  • 3
    Electronic Resource
    Electronic Resource
    Bimolecular self-reactions of phenyl-substituted phenoxyl radicals studied by flash photolysis (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 357-374 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate, equilibrium, and thermodynamic data for reaction (1) of 2,6-diphenyl-4R-phenoxyl radicals, where R==OCH3 (I), Ph (II), OC2H5 (III), O-n-C18H37 (IV), and 2,6-dicyclohexyl-4-phenylphenoxyl radical (V), in various solvents are obtained. The k1 values of radicals I to V are within (5.5 ± 1.0) × 107-(1.4 ± 0.3) × 109M-1·sec-1 in propanol. The solvent effect on k1 for radicals I and II was studied. The dimerization of radical I is diffusion-controlled in all solvent studies. The dimerization of radical II is viscosity-dependent but not diffusion-controlled. Plots of k1 against ET have a V shape. Specific solvent-solute interactions are seeming to be responsible for numerical k1 values of radicals I and II. The solvent effect is more pronounced for “slow” dimerization of radicals II than for “fast” dimerization of radicals I. The minimum k1 values correspond to pyridine and chloroform. The reaction (1) rate strongly depends upon the composition of a chloroform (S)-cosolvent binary mixture. Besides reaction (1) the following reactions proceed in binary mixture: \documentclass{article}\pagestyle{empty}\begin{document}$$ K_{14} = 0.18 \pm 0.05M^{ - 1},k_{15} = (2.0 \pm 1.0) \times 10^8 M^{ - 1} \cdot \sec ^{ - 1} $$\end{document} (radical I, S-CCL4 mixture) \documentclass{article}\pagestyle{empty}\begin{document}$$ K_{14} = 0.9 \pm 0.2M^{ - 1},k_{15} = (1.2 \pm 0.5) \times 10^7 M^{ - 1} \cdot \sec ^{ - 1} $$\end{document}(radical II, S-C6H14 mixture) \documentclass{article}\pagestyle{empty}\begin{document}$$ K_{14} = 0.45 \pm 0.10M^{ - 1},k_{15} = (9.0 \pm 2.0) \times 10^6 M^{ - 1} \cdot \sec ^{ - 1} $$\end{document}(radical II, S-CCL4 mixture)In all cases k16 ≪ k15. Factors influencing dimerization rates in strongly nonideal mixtures CH3OH-CCL4 and CH3OH-CHCl3 are discussed.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110403
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  • 4
    Electronic Resource
    Electronic Resource
    The kinetics of the anation reaction of aquopentaamminecobalt(III) by malonate in acidic aqueous solution (1976)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 8 (1976), S. 411-423 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Co(NH3)5OH23+ ion reacts with malonate to form Co(NH3)5O2CCH2CO2H2+ or Co(NH3)5O2CCH2CO2+, depending on the pH of the reaction solution. The kinetics of this anation reaction have been studied as a function of [H+] for the acidity range 1.5 ≤ pH ≤ 6.0 in the temperature range of 60 to 80°C, the [total malonate] ≤ 0.5 M, and the ionic strength 1.0M. The anation by malonic acid follows second-order kinetics, the rate constant being 8.0 × 10-5 M-1·sec-1 at 70°C, and the anations by bimalonate (Q1, k1) and malonate ion (Q2, k2) are consistent with an Id mechanism. Typical values at 70°C for the ion pair formation constants are Q1 = 1.3, Q2 = 5.4M-1; and for the interchange rate constants k1 = 5.3 × 10-4; k2 = 7.3 × 10-4 sec-1. The activation parameters for the various rate constants are reported and the results discussed with reference to previously reported data for similar systems.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550080308
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  • 5
    Electronic Resource
    Electronic Resource
    Excited-state kinetics in the photolysis of azoethane and hexafluoroazomethane at 366 nm, up to one atmosphere pressure, and from room temperature to 150°CAlthough the Stern-Volmer equation originally relates to the electronic quenching of an excited electronic state, it is convenient to use the terminology for vibrational relaxation; more than one (distinguishing equilibrated states) electronic state is involved in any case (1976)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 8 (1976), S. 959-969 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photochemistry of azoethane and hexafluoroazomethane at 366 nm has been reinvestigated up to 1 atm pressure, and over a range of temperature from 27 to 150°C. The Stern-Volmer type quenching plots primarily demonstrate the decomposition of a single electronic and vibrationally excited state for azoethane, but competitive photodissociation from two different electronic and vibrationally excited states, which was previously postulated for hexafluoroazomethane and azoisopropane, is confirmed for hexafluoroazomethane. It is concluded, however, that two different electronic and vibrationally excited photodissociating states are present in azoethane photolysis, but that one of them is difficult to detect, at least by the present approachPhotosensitization with biacetyl at 436 nm also causes the dissociation of azoethane, and this is probably from the vibrationally equilibrated first triplet state. The energy barrier for this process was found to be 5.0 kcal/mol.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550080613
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  • 6
    Electronic Resource
    Electronic Resource
    The production and subsequent relaxation of vibrationally excited OH in the reaction of atomic oxygen with HBr (1977)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 9 (1977), S. 97-109 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A fast discharge flow apparatus equipped for EPR detection of radicals has been used to investigate the reaction O + HBr → OH + Br. At 295°K, measurements showed that more than 97% of all OH produced in this reaction was formed initially in its first vibrationally excited state. Rate constants for physical deactivation of OH(v = 1) by O(3P), Br(2P3/2), H2O, and HBr were measured as (1.45 ± 0.25) × 10-10, (6.4 ± 2.4) × 10-11, (1.35 ± 0.50) × 10-11, and 〈 10-12 cm3/molec·sec, respectively.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550090109
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  • 7
    Electronic Resource
    Electronic Resource
    Consecutive, irreversible first-order reactions. Ambiguities and practical aspects of kinetic analyses (1977)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 9 (1977), S. 535-548 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The general problem of eliciting reliable rate constants from experimental data is considered in detail for consecutive reactions. Practical aspects are emphasized.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550090404
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  • 8
    Electronic Resource
    Electronic Resource
    Electrocyclic versus homolytic decompositions of peroxides: Solvent and phase effectsTaken in part from the M.Sc. Thesis of P. M. Rahimi, Brock University, 1975. (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 185-195 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of isopropyl peroxide in solvents is shownto be a competition between unimolecular homolysis (kr) and an electrocyclic reaction yielding H2 plus acetone (kH). The value of kH increases markedly with increasing solvent polarity: PhCH3 〈 i-PrOH 〈 MeOH 〈 H2O. Log kH correlates linearly with Et (or Z). The effect on kr is similar but less pronounced. Log kr's for both i-Pr2O2 and t-Bu2O2 are shown to correlate with the molar solubility parameter δ. The negligible contribution of the electrocyclic reaction to thermal decompositions of peroxides in the vapor phase is thus not due to peculiar behavior of that reaction, which clearly has a polartransition state. It is argued that the transition state for unimolecular homolysis has no polar character despite the apparent sensitivity of homolysis rates to solvent polarity.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100205
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  • 9
    Electronic Resource
    Electronic Resource
    Mechanism of catalytic ascorbic acid oxidation system Cu2+-ascorbic acid-O2 (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 461-494 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Analysis is made of reported results on the kinetics and mechanism of ascorbic acid oxidation with oxygen in the presence of cupric ions. The diversities due to methodological reasons are cleared up. A kinetic study of the mechanism of Cu2+ anaerobic reaction with ascorbic acid (DH2) is carried out. The true kinetic regularities of catalytic ascorbic acid oxidation with oxygen are established at 2.7 ≤ pH 〈 4, 5 × 10-4 ≤ [DH2] ≤ 10-2M, 10-4 ≤ [Cu2+] ≤ 10-3M, and 10-4 ≤ [O2] ≤ 10-3M: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm W}_0 = {}_{K1}[{\rm Cu}^{{\rm 2} +}][{\rm DH}_2][{\rm O}_2]{}^{0.5}/[{\rm H}^ +] $$\end{document} wherek1 (25°C) = 0.13 ± 0.01 M-0.5·sec-1. The activation energy for this reaction is E1 = 22 ± 1 kcal/mol. It is found by means of adding Cu+ acceptors (acetonitrile and allyl alcohol) that the catalytic process is of a chain nature. The Cu+ ion generation at the interaction of the Cu2+ ion with ascorbic acid is the initiation step. The rate of the chain initiation at [Cu2+] ± 10-4M, [DH2] ± 10-2M, 2.5 〈 pH 〈 4, is \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm W}_{\rm i} = {}_{K{\rm i,1}}[{\rm Cu}^{{\rm 2} +}]^2 [{\rm DH}_2]/[{\rm H}^ +] $$\end{document} whereki,1 (25°C) = (1.8 ± 0.3)M-1·sec-1, Ei,1 = 31 ± 2 kcal/mol. The reaction of the Cu+ ion with O2 is involved in a chain propagation, so that the rate of catalytic ascorbic acid oxidation for the system Cu2+—DH2—O2 is \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm W}_{\rm 0} = {}_{k{\rm 1}}[{\rm Cu}^ +][{\rm O}_2] $$\end{document} wherek1 (25°C) = (5 ± 0.5) × 104 M-1·sec-1. The Cu+ ion and a species interacting with ascorbate are involved to quadratic chain termination. By means of photochemical and flow electron spin resonance methods we obtained data characteristic of the reactivities of ascorbic acid radicals and ruled out their importance for the catalytic chain process. A new type of chain mechanism of catalytic ascorbic acid oxidation with oxygen is proposed: .
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110503
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  • 10
    Electronic Resource
    Electronic Resource
    Kinetics and mechanisms of substitution reactions with sulfur-containing nucleophiles in aqueous acid solutions. I - rates of reactions of some tetrahalopalladate (II) anions with thiourea and selenourea (1975)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 87-98 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The activation energy parameters for the reaction of PdX42- (X=Cl-, Br-) in aqueous halide acid solution with thiourea (tu) and selenourea (seu) have been determined. High rates of reaction parallel low enthalpies and appreciable negative entropy of activation. The rate law in each case simplifies to kobs=k[L] where L=tu or seu, and only ligand-dependent rate constants are observed at 25°C. The ligand-dependent rate constants for the first identifiable step in the PdCl42- + X system is (9.1±0.1) × 103 M-1 sec-1 and (4.5±0.1) × 104 M-1 sec-1 for X=tu and seu, respectively, while for the PdBr42- + X system it is (2.0±0.1) × 104 M-1 sec-1 and (9.0±0.1) × 104 M-1 sec-1 for X=tu and seu, respectively.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550070110
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