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  • Physical Chemistry  (5)
  • Wiley-Blackwell  (5)
  • Institute of Physics
  • 1990-1994  (2)
  • 1985-1989  (3)
  • 1
    Electronic Resource
    Electronic Resource
    Potentiometric evaluation of the ion-selective characteristics of 1,4-bridged cubyl diester crown ethers (1994)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 7 (1994), S. 303-308 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cubane diester crown ethers were tested as ion-selective electrodes in poly(vinyl chloride) (PVC) membranes. The four ionophores studied proved to be good K+ neutral carriers, showing Nernstian and near-Nernstian responses to this ion, in the range 10-4-10-1 M. The fixed interferences method was used to determine relative selectivity coefficients for all the electrodes. The highest selectivity for potassium relative to sodium, lithium, calcium and magnesium ions using potassium tetrakis(p-chlorophenyl)borate (KTpClPB) as a resistance modifier and NPOE as a plasticizer was obtained with the 1,4-cubyl diester-25-crown-7 ether ionophore. The effects of KTpCIPB on membrane selectivity were assessed; its removal was found to increase the selectivity of the four ionophores for potassium relative to cesium, sodium, calcium and magnesium ions with minimal effects on lithium and ammonium ions. The compounds tested exhibited a fast Nernstian response to changes in K+ concentration which was stable to within 〈100 μV h-1.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610070606
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  • 2
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of oxidation of fumarate, acrylate, cinnamate, and maleate anions by hexavalent manganese in aqueous alkaline medium (1985)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 17 (1985), S. 1017-1023 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of oxidation of fumarate, acrylate, cinnamate, and maleate anions by hexavalent manganese has been studied in aqueous alkaline medium. The order in [oxidant] was unity while that in [substrate] was fractional. The order of reactivity of anions is fumarate → acrylate → cinnamate → maleate. The reactions followed Michaelis-Menten kinetics suggesting the formation of a cyclic intermediate between Mn(VI) and the substrate followed by its disproportionation in a slow step. The equilibrium constant (K) for the preequilibrium step and the rate constant (k) for the slow disproportionation step have been calculated from the intercept and the slope values of the linear plot of 1/kobs versus 1/[substrate]. Activation parameters are also presented and discussed. A convenient iodometric method is reported for the estimation of Mn(VI).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550170908
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  • 3
    Electronic Resource
    Electronic Resource
    Formation of H and D atoms in pyrolysis of 1,3-butadiene and 1,3 butadiene-1,1,4,4,-d4 behind shock waves (1988)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 20 (1988), S. 153-164 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Highly dilute mixtures of 1,3-butadiene and 1,3-butadiene-1,1,4,4-d4 were pyrolyzed behind reflected and incident shock waves, respectively. Concentrations of H and D atoms were measured by resonance absorption spectroscopy. In the early stages of the reaction, nearly equal amounts of H and D were formed from CD2CHCHCD2, indicating that loss of H from C2 followed by loss of D from C1 is a more important reaction than breaking of the central C—C bond. Overall, rate constants for atom-forming reactions are much slower than rate constants for disappearance of butadiene in earlier experiments, suggesting that most of the butadiene disappears by processes that do not involve H or D atoms or by radicals that produce them rapidly.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550200208
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  • 4
    Electronic Resource
    Electronic Resource
    Further experiments on pyrolysis of 2,2-dimethylpropane behind shock waves (1988)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 20 (1988), S. 165-175 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrolysis of a dilute mixture of neopentane (2,2-dimethylpropane) has been studied behind incident shock waves at an average pressure of 0.35 atm; the reaction was followed by absorption spectroscopy for H atoms. In the temperature range 1230-1455 K, the rate constant for dissociation of neopentane to t-butyl and methyl radicals is 1.1 E 13 exp(-62 kcal/RT) s-1. These data and some of the literature results, between 1000 and 1450 K, can be fitted by an RRKM model of the hindered Gorin type, with five active internal rotors in the complex. To match our data with other literature data down to 800 K, a vibrational model was more satisfactory, but this did not fit very low pressure pyrolysis data in the 1000-1100 K range. Apparently, the VLPP data are too high because of heterogeneous processes or chain reactions.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550200209
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  • 5
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of oxidation of aspartic acid by bismuth(V) in HClO4-HF medium (1992)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 963-971 
    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 Aspartic acid by bismuth(V) studied in HClO4-HF mixture iodometrically exhibit complex dependence with respect to aspartic acid (AA). The rate law (i) accounts for all the experimental observations. where [Bi(V)] and [AA] are the gross analytical concentration of all fluorobismuth(V) species and the equilibrium concentration of aspartic acid, respectively. The oxidation product of the amino acid was identified to be an aldehyde. HF and F- do not affect the rate of the reaction. © John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550241106
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