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  • 1985-1989  (190)
  • 1920-1924
  • 1810-1819
  • 1987  (190)
  • Genetics  (99)
  • Physical Chemistry
  • 101
    Electronic Resource
    Electronic Resource
    The kinetics and mechanism of alkaline hydrolysis of N-substituted phthalimides (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 143-153 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aqueous cleavage of N-(2-bromoethyl)phthalimide (NBEPH), N-(3-bromopropyl)phthalimide (NBPPH), and N-carbethoxyphthalimide (NCPH) have been studied within the [ŌH] range of 5 × 10-4 M to 2 × 10-3 M, pH range of 8.82 to 10.62 and 8.06 to 8.66, respectively. The observed pseudo-first-order rate constants, kobs, reveal a linear relationship with [ŌH] with essentially zero intercept. The alkaline hydrolysis of N-(hydroxymethyl)phthalimide (NHMPH) has been studied within the [ŌH] range of 5.64 × 10-6 M to 2.0 M. The [OH]-rate profile reveals that both ionized and nonionized NHMPH are reactive toward ŌH. The second-order rate constant, kOH, for the reaction of ŌH with non-ionized NHMPH is ca. 104 times larger than that with ionized NHMPH. The values of kOH obtained for NBEPH, NBPPH, NCPH, and nonionized NHMPH show a reasonable linear relationship with Taft substituent constants, and the slope (ρ*) of the plot is 1.01 ± 0.10. The low value of ρ* of 1.01 is attributed to nucleophilic attack as the rate-limiting. The kOH value for ionized NHMPH reveals nearly 103-fold negative deviation from the linear Taft plot.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550190206
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  • 102
    Electronic Resource
    Electronic Resource
    Masthead (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987) 
    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.550190301
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  • 103
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of electron transfer from phenolate anion to hexacyanoferrate (III) in aqueous alkaline media (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 155-170 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic reinvestigation of the title redox system in aqueous alkaline media at 35°C and an ionic strength of 0.5 mol dm-3 shows that the reaction follows a pseudosecond-order Fe(CN)63- disappearance. While varying [phenol]0 and [OH-] exhibit a linear influence on the pseudo-second-order rate constant, varying[Fe(CN)63-]0 and [Fe(CN)64-]0, initially taken, have a complicated inhibitory effect on the same. The major phenoloxidation products isolated under a chosen condition are 2,2′- and 4,4′- dihydroxydiphenyl. Results are interpreted in terms of a probable mechanism which envisages a reversible formation, by the first one-electron transfer, of a reactive phenoxy radical (PhO·) which on the second one-electron transfer forms a less reactive ion-pair intermediate (stabilized by the Fe(CN)64- produced) to decompose rate-determiningly to phenoxonium cation (PhO+) and Fe(CN)64-, the product-formation steps being very rapid and kinetically indistinguishable.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550190207
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  • 104
    Electronic Resource
    Electronic Resource
    On the errors of Arrhenius parameters and estimated rate constant values (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 171-181 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed statistical study is presented, based on simulated experimental data, on the estimation of activation parameters using the Arrhenius equation: k = A exp(B/T). The close correlation of the two parameters is shown, which requires the computation of the covariance matrix for the representation of uncertainties. This matrix facilitates the correct estimation of the confidence interval for interpolated (or extrapolated) values of rate coefficients. It is proposed that the full correlation matrix should be published in any article dealing with the determination of Arrhenius parameters.The importance of correct weighting is emphasized. Nonlinear fitting to the Arrhenius equation can be carried out without weighting only in case the (absolute) error of rate coefficient is independent of the temperature. Simulated experiments show that noncorrect weighting shifts the average values of fitted parameters and increases the variance of the parameters as well.With respect to the modified Arrhenius equation: k = A · Tn exp(B/T), statistical analysis shows that the physically meaningful estimation of all three parameters is impossible. Nonlinear fitting of three parameters is suggested for interpolation (and extrapolation) of rate coefficients, whereas in case of activation parameter estimation, the fixing of “n” on the basis of theoretical considerations is advised followed by the estimation of the remaining two parameters.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550190302
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  • 105
    Electronic Resource
    Electronic Resource
    Neighboring group participation in the pyrolysis kinetics of 4-chloro-1-butanol in the gas phase (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 183-189 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of 4-chloro-1-butanol has been studied in a static system, seasoned with allyl bromide, and in the presence of the free radical suppressor toluene. The working temperature and pressure ranges were 400-450°C and 43-164 Torr, respectively. The reaction is homogeneous, unimolecular, and follows a first-order rate law. The temperature dependence of the rate coefficients is given by the following Arrhenius equation: log k1(s-1) = (13.34 ± 0.50) - (221.1 ± 6.7) kJ mol-1 (2.303RT)-1. The products tetrahydrofuran, formaldehyde, and propene, arise by the participation of the neighboring OH group in 4-chloro-1-butanol pyrolysis. The reaction is best explained in terms of an intimate ion pair type of mechanism.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550190303
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  • 106
    Electronic Resource
    Electronic Resource
    Erratum (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 487-487 
    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.550190507
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  • 107
    Electronic Resource
    Electronic Resource
    Kinetics, mechanism, and stereochemistry of Diels-Alder reactions of carbonyl-substituted ethenes with cyclohexa-1,3-diene in the gas phase (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 1063-1072 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the Diels-Alder additions of CH2 — CHCHO, CH2—C(CH3)CHO, and CH2—CHC(CH3)O to cyclohexa-1,3-diene (CHD) have been studied in the gas phase. The stereochemistry and the mechanism of these reactions are discussed. In contrast with other Diels-Alder additions involving CHD as diene, a biradical mechanism does not fit the experimental results.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550191203
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  • 108
    Electronic Resource
    Electronic Resource
    Photoenhancement of the nitrous acid formation in the surface reaction of nitrogen dioxide and water vapor: Extra radical source in smog chamber experiments (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 539-551 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The surface reaction of NO2 and H2O vapor to emit HONO into the gas phase was studied in the evacuable and bakeable photochemical chamber under the irradiation of UV-visible light (≳ 290 nm). Kinetic analysis of the NO, NO2, and HONO with the aid of computer modeling strongly suggested that the formation of HONO by the surface reaction is photoenhanced. When a linear regression was assumed, the photoenhancement factor defined by {(k′21/k21) - 1} was expressed as (6.8 ± 2.5)k1 under our experimental conditions, where k1 is the primary photolysis rate of NO2, and k21, k′21 are the second-order-equivalent rate constants of the HONO formation reaction in dark and under irradiation, respectively. The discussion was made that this photocatalitic enhancement of HONO formation would explain the nature of the extra OH radical flux in the smog chamber experiments, which has been discussed as “unknown radical source” and has still been unexplained by the surface dark reaction of NO2 and H2O to emit HONO.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550190606
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  • 109
    Electronic Resource
    Electronic Resource
    Masthead (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987) 
    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.550190701
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  • 110
    Electronic Resource
    Electronic Resource
    Kinetic study of gas-phase reactions with CF2Cl2 and CFCl3. Analysis using the transition state theory (TST) of the chlorine atom transfer reactions by CF3 and CH3 radicals from halomethanes (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 627-638 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The following gas-phase reactions: were studied by the competitive method with CF3I as the source of radicals. The kinetic parameters obtained in the temperature range 533-613 K and 503-613 K respectively for chlorine atom transfer reactions are given by: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_1 /k_c ^{1/2} ({\rm cm}^{\rm 3}\, {\rm mol}^{{\rm - 1/2}} s^{ - 1/2}) = (6.19 \pm 0.10) - (16900 \pm 100)/\theta $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_2 /k_c ^{1/2} ({\rm cm}^{\rm 3}\, {\rm mol}^{{\rm - 1/2}} s^{ - 1/2}) = (6.52 \pm 0.10) - (14890 \pm 100)/\theta $$\end{document} where θ = 2.303 RT (cal mol-1).The Arrhenius A values were calculated for seven chlorine atom transfer reactions (CF2Cl2, CFCl3, CCl4 with CF3 radicals; CF3Cl, CF2Cl2, CFCl3 and CCl4 with CH3 radicals) by using the thermochemical kinetic version of the Transition State Theory (TST).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550190705
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  • 111
    Electronic Resource
    Electronic Resource
    Self-inhibition or the lack of it in the pyrolyses of neopentane and n-hexane (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 649-658 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Published data show that in its early stages (up to 3% decomposition), the pyrolysis of n-hexane in the ranges 723-823 K and 10-100 Torr is not inhibited by the olefin products, in contrast with neopentane pyrolysis which is very strongly inhibited in similar conditions. Detailed consideration of the chain mechanisms for the two pyrolyses shows that the reactivity of the chain terminating radical towards hydrogen abstraction from an allylic C—H bond in product olefin is the factor which determines whether or not observable self-inhibition occurs. Thus, n-hexane pyrolysis, whose chain decomposition is terminated by recombination and disproportionation of ethyl, is not significantly self-inhibited, whereas that of neopentane which is terminated by recombination of methyl is very strongly inhibited because methyl is 14× more reactive than ethyl. The implications for other alkanes are briefly discussed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550190707
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  • 112
    Electronic Resource
    Electronic Resource
    The kinetics and mechanisms of the gas phase elimination of 4-(methylthio)-1-butyl acetate and 1-chloro-4-(methylthio)-butane (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 683-690 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase elimination of 4-(methylthio)-1-butyl acetate and 1-chloro-4-(methylthio)-butane has been investigated in a seasoned, static reaction vessel over the temperature range of 310-410°C and the pressure range of 46-193 Torr. The presence of the inhibitors propene, cyclohexene, and/or toluene had no effect on the rates. The reactions are homogeneous, unimolecular, and obey a first-order rate law. The rate coefficients are given by the following Arrhenius equations: for 4-(methylthio)-1-butyl acetate, log k1(s-1) = (12.32 ± 0.29) - (192.1 ± 3.6) kJ/mol/2.303RT; for 1-chloro-4-(methylthio)-butane, log k1(s-1) = (12.23 ± 0.59) - (175.7 ± 6.8) kJ/mol/2.303RT. The CH3S substituent in 1-chloro-4-(methylthio)-butane has been found to participate in the elimination reaction, where tetrahydrothiophene and methyl chloride formation may result from an intimate ion-pair type of mechanism. The yield of a cyclic product in gas phase reactions provides additional evidence of an intimate ion pair mechanism through neighboring group participation in gas phase elimination of special types of organic halides.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550190802
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  • 113
    Electronic Resource
    Electronic Resource
    Kinetics of the permanganate oxidation of formic acid in aqueous solution (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 741-755 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the permanganate oxidation of formic acid in aqueous perchloric acid at 30°C were examined by the spectrophotometric method. The chemical reaction 2MnO4- + 3HCOOH + 2H+ → 2MnO2 + 3CO2 + 4H2O, appears to proceed via several parallel reactions. The overall rate equation has been obtained by using statistical multilinear regression analysis of the 660 cases studied, and the presence in the rate equation of two new terms in relation to previous studies shows that both permanganate autocatalytic effects and acid media inhibition must be taken into account when the reaction proceeds at constant ionic strength.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550190807
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  • 114
    Electronic Resource
    Electronic Resource
    On the mechanism of the azide-bromine reaction in aqueous medium (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 777-780 
    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.550190809
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  • 115
    Electronic Resource
    Electronic Resource
    A structure-activity relationship for the estimation of rate constants for the gas-phase reactions of OH radicals with organic compounds (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 799-828 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A previous technique for the calculation of rate constants for the gas-phase reactions of the OH radical with organic compounds has been updated and extended to include sulfur- and nitrogen-containing compounds. The overall OH radical reaction rate constants are separated into individual processes involving (a) H-atom abstraction from C—H and O—H bonds in saturated organics, (b) OH radical addition to 〉C=C〈 and —C≡C— unsaturated bonds, (c) OH radical addition to aromatic rings, and (d) OH radical interaction with —NH2, 〉NH, 〉N—, —SH, and —S— groups. During its development, this estimation technique has been tested against the available database, and only for 18 out of a total of ca. 300 organic compounds do the calculated and experimental room temperature rate constants disagree by more than a factor of 2. This suggests that this technique has utility in estimating OH radical reaction rate constants at room temperature and atmospheric pressure of air, and hence atmospheric lifetimes due to OH radical reaction, for organic compounds for which experimental data are not available. In addition, OH radical reaction rate constants can be estimated over the temperature range ca. 250-1000 K for those organic compounds which react via H-atom abstraction from C—H and O—H bonds, and over the temperature range ca. 250-500 K for compounds containing 〉C=C〈 bond systems.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550190903
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  • 116
    Electronic Resource
    Electronic Resource
    The mechanism of thermal eliminations part XXIII: [1] The thermal decomposition of pyruvic acid (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 709-713 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of pyruvic acid into carbon dioxide and acetaldehyde is a unimolecular first-order reaction and takes place according to the rate equation, logk = 13.53-41,250/4.575 K. These parameters contrast markedly with those recently reported, viz. logk = 7.19-27,700/4.575 K and confirm that the latter, which gave an unacceptably low value for the frequency factor, are anomalous. The lower reactivity of pyruvic acid compared to oxalic acid is interpreted in terms of normal electronic effects.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550190804
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  • 117
    Electronic Resource
    Electronic Resource
    Masthead (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987) 
    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.550190401
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  • 118
    Electronic Resource
    Electronic Resource
    Laser pyrolysis studies of OH reaction rates with several butenes at 1200 K (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 269-276 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a laser pyrolysis/laser fluorescence method, we have measured the rate constants for OH reacting with 1-butene, t-2-butene, isobutene, and 2,3-dimethyl-2-butene near 1200 K. The butene rate constants are large, ranging from 2.0-3.7 × 10-11 cm-3 s-1, and increase with the number of allylic hydrogens. Transition-state theory considerations indicate these allylic hydrogens are easily abstracted, in contrast to prior observations on propene.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550190402
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  • 119
    Electronic Resource
    Electronic Resource
    Kinetics of cerium(IV) oxidation of macrocyclic complexes of chromium(III) and fate of chromium(IV) intermediates (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 277-298 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics and mechanism of the cerium(IV) oxidation of Cr(III) complexes of a series of macrocyclic (or pseudomacrocyclic) ligands with [14]-membered intraligand ring-sizes have now been investigated at I = 1.0 M (LiClO4) Temp. 30°C. The complexes of the formulation Cr(macrocycle)(X)(H2O)(3-n)+ where X = CHCl2 and H2O, n = 0 or 1 undergo oxidation to Cr(VI) with the formation of chromium(IV) intermediates. The observed kinetic parameters for the Ce(IV) oxidation of Cr(III) macrocyclic complexes have been discussed in terms of changes brought about by the macrocyclic ligands on the Cr(III) - Cr(IV) redox potentials and in specific rates for Cr(IV) - Cr(V) conversion. On the basis of this study, it has been suggested that the trapping of Cr(IV) is easier when a macrocyclic ligand having a symmetrical intra-ligand ring size and unsaturation in the cyclic structure is coordinated equatorially. Cyclic voltammetric studies indicate the formation of Cr(IV) transient in the case of electrochemical oxidation of trans-Cr(Me4[14]tetraene)(H2O)23+.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550190403
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  • 120
    Electronic Resource
    Electronic Resource
    Kinetics of the gas-phase reactions of NO3 radicals with a series of alkynes, haloalkenes, and α,β-unsaturated aldehydes (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 299-307 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the gas-phase reactions of NO3 radicals with a series of alkynes, haloalkenes, and α,β-unsaturated aldehydes have been determined at 298 ± 2 K using a relative rate technique. Using rate constants for the reactions of NO3 radicals with ethene and propene of (1.1 ± 0.5) × 10-16 cm3 molecule-1 s-1 and (7.5 ± 1.6) × 10-15 cm3 molecule-1 s-1, respectively, the following rate constants (in units of 10-16 cm3 molecule-1 s-1) were obtained: acetylene, ≤0.23; propyne, 0.94 ± 0.44; vinyl chloride, 2.3 ± 1.1; 1,1-dichloroethene, 6.6 ± 3.1; cis-1,2-dichloroethene, 0.75 ± 0.35; trans-1,2-dichloroethene, 0.57 ± 0.27; trichloroethene, 1.5 ± 0.7; tetrachloroethene, 〈0.4; allyl chloride, 2.9 ± 1.3; acrolein, 5.9 ± 2.8; and crotonaldehyde, 41 ± 9. The atmospheric implications of these data are discussed.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550190404
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  • 121
    Electronic Resource
    Electronic Resource
    Kinetics, mechanism, and stereochemistry of Diels-Alder reactions of CN-substituted ethenes with cyclohexa-1, 3-diene in the gas phase (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 363-371 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the Diels-Alder additions of CH2 = CHCN, CH2 = C(CH3) CN, and cis- and trans-CH3CH = CHCN to cyclohexa-1, 3-diene have been studied in the gas phase. The stereochemistry of these reactions is discussed. In terms of a biradical mechanism, a minimum value of 4.1 ± 0.8 kcal mol-1 for the stabilizing effect of a CN group vis-à-vis a methyl group is shown to fit the experimental activation energies.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550190407
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  • 122
    Electronic Resource
    Electronic Resource
    Absolute rate constants for hydrogen abstraction from hydrocarbons by the trichloromethylperoxyl radical (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 309-317 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate constants have been measured for the reactions of trichloromethylperoxyl radicals with cyclohexane, cyclohexene, and hexamethylbenzene. The CCl3O2 radicals were produced by pulse radiolysis of air-saturated CCl4 solutions containing various amounts of the hydrocarbons. The rate constants were determined by competition with the one-electron oxidation of metalloporphyrins, using the rate of formation of the metalloporphyrin radical cation absorption to monitor the reaction by kinetic spectrophotometry. The rate constants for hydrogen abstraction from cyclohexane, cyclohexene, and hexamethylbenzene were found to be 1 × 103, 1.0 × 105, and 7.5 × 104 M-1 s-1, respectively.
    Additional Material: 4 Ill.
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    The O + NH3 reaction: A review (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 319-362 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Experimental data for the reaction of O atoms with NH3 have been reviewed with particular attention to the possible effects of secondary reactions on the deduced rate coefficient. A reaction mechanism was assembled and computer calculations carried out to simulate several sets of experiments. The sensitivity of the calculations to uncertainties in the various rate coefficients was assessed. Transition-state theory calculations were carried out on the rate coefficient k1 for the O + NH3 → OH + NH2 reaction. These studies suggest that the reaction stoichiometry is dependent on temperature, initial reagent ratios, and extent of reaction; that available data are not sufficient to determine whether the initial step is H-atom abstraction (producing OH and NH2 radicals) or O-atom addition (producing an NH3O* complex): and that the low temperature values of k1 (T ≤ 400 K) are not consistent with values deduced at higher temperatures if the reaction proceeds by H-atom abstraction. Taking all the evidence into account, it is recommended that the expression 1.1 × 103 T2.1 exp(-2620/T) L mol-1 s-1 be used for k1 until more definitive experimental measurements are made at low temperatures.
    Additional Material: 2 Ill.
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    Masthead (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987) 
    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.550190501
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    Decomposition of the t-butoxy radical  -  I. Studies over the temperature range 402-443 K (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 391-400 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By allowing the t-butoxy radical to decompose in the presence of nitric oxide, it has been possible to determine rate constants for decomposition by the measurements of the relative rates (2) and (3) Process (3) is clearly pressure dependent. The value of k3(∞) has been determined in the presence of several inert gases (CF4, SF6, N2, and Ar) and a value of k3 interpolated for atmospheric conditions. The results may be compared with those for other relevant alkoxy radicals at room temperature. Extrapolated values for k3 in the presence of CF4 lead to the result \documentclass{article}\pagestyle{empty}\begin{document}$$ k_3 (\infty)/s^{ - 1} = 10^{14.6 \pm 0.6} \exp (- 8052 \pm 604/T) $$\end{document}
    Additional Material: 5 Ill.
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    Disproportionation-combination rate constant ratios for haloalkyl radicals: Evidence for heterogeneous disproportionation (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 401-413 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Disproportionation-combination rate constant ratios, kd/kc, have been determined for R + RCH2CHCl and for the auto disproportionation-combination of RCH2CHCl radicals, R = CF3, C2F5, and C3F7. The kd/kc for R = CF3 and to a lesser degree for R = C2F5 and C3F7 were very sensitive to the surface/volume ratio of the reaction vessel suggesting a heterogeneous component for disproportionation.
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    Collisional energy transfer in highly vibrationally excited molecules: A very low-pressure pyrolysis study of acetyl chloride (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 373-389 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The average downward energy transfer (〈Δ Edown〉) is obtained for highly vibrationally excited acetyl chloride with Ne and C2H4 bath gases at ca. 870 K. Data are obtained by the technique of very low-pressure pyrolysis (VLPP). Fitting these data by solution of the appropriate reaction-diffusion integrodifferential master equation yields the gas/gas collisional energy transfer parameters: 〈Δ Edown〉 values are 220 ± 10 cm-1 (Ne bath gas) and 330 ± 20 cm-1 (C2H4).These energy transfer quantities are much less than those predicted by statistical theories, or those observed for similar sized molecules such as CH3CH2Cl. These results are explained by the qualitative predictions of the biased random walk model wherein the fundamental mechanism of energy transfer is the multiple interactions between the bath gas and the individual atoms of the reactant molecule, during the course of the collision event. The charge distribution of acetyl chloride decreases the number of such interactions, thereby reducing the amount of energy transferred per collision.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550190408
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    Artificial-intelligence-based interpretation of feature sensitivities of the Belousov-Zhabotinsky reaction (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 435-455 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new approach is presented for analyzing kinetic models of relaxation-type oscillatory systems on the basis of numerical data. Feature sensitivities of the length of the two kinetic states of the Belousov-Zhabotinsky (BZ) reaction with respect to the rate constants of the model are explained by means of a logic-based inference system. The main kinetic roles of the individual reaction steps on the relaxing components are revealed, and a consistent interpretation of the kinetic states is given by this process. Both the high and the low set of rate constants were studied. According to our analysis, the bromous acid-hypobromous acid reaction is an important Br- producing step of the model, and in the case of the low set, the bromate-bromous acid reaction is not the rate-determining step of the bromous acid autocatalysis.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550190505
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    The mechanisms of the homogeneus, unimolecular elimination kinetics of ethyl 4-chlorobutyrate and 4-chlorobutyric acid in the gas phase (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 789-797 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ethyl 4-chlorobutyrate, which is reexamined, pyrolyzes at 350-410°C to ethylene, butyrolactone, and HCl. Under the reaction conditions, the primary product 4-chlorobutyric acid is responsible for the formation of γ-butyrolactone and HCl. In seasoned vessels, and in the presence of a free-radical inhibitor, the ester elimination is homogeneous, unimolecular, and follows a first-order rate law. For initial pressures from 69-147 Torr, the rate is given by the following Arrhenius expression: log k1(s-1) = (12.21 ± 0.26) - (197.6 ± 3.3) kJ mol-1 (2.303RT)-1. The rates and product formation differ from the previous work on the chloroester pyrolysis.4-Chlorobutyric acid, an intermediate product of the above substrate, was also pyrolyzed at 279-330°C with initial pressure within the range of 78-187 Torr. This reaction, which yields γ-butyrolactone and HCl, is also homogeneous, unimolecular, and obeys a first-order rate law. The rate coefficient, is given by the following Arrhenius equation: log k1(s-1) = (12.28 ± 0.41) - (172.0 ± 4.6) kJ mol-1 (2.303RT)-1. The pyrolysis of ethyl chlorobutyrate proceeds by the normal mechanism of ester elimination. However, the intermediate 4-chlorobutyric acid was found to yield butyrolactone through anchimeric assistance of the COOH group and by an intimate ion pair-type of mechanism. Additional evidence of cyclic product and neighboring group participation is described and presented.
    Additional Material: 3 Ill.
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    Nonreciprocal gonadal dysgenesis in Chironomus thummi hybrids: Temperature sensitivity of female sterility (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987), S. 17-26 
    Details
    ISSN: 0192-253X
    Keywords: ovarian dysgenesis ; Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: In nonreciprocal hybrids of Chironomus thummi an environmental factor has been detected which, along with genetic factors, determines gonadal dysgenesis. Female hybrids of the cross Ch' thummi thummi ♂ ♂ × Ch. thummi piger ♀ ♀ show various degrees of rudimentary developed ovaries and sterility. The extent of these abnormalities is dependent on the developmental temperature of the hybrids. At a temperature of 21°C approximately 90% of the females are completely sterile and at 16°C only 30%. The curative effect of a temperature of 16°C on sterility occurs, however, only in those hybrid females which hatch from a specific type of egg mass (class A). Females of another type of egg mass (class B) show nearly as many dysgenic ovaries as do those developed at 21°C. At a developmental temperature of 21°C no such differentiation between the A and B class of egg masses is possible.Ovarian dysgenesis and sterility is induced during atemperature-sensitive period which extends from the beginning of embryonic development through the first two-thirds of the first larva instar stage. The abnormalities observed must be due to a failure in the early development of the germ line and are probably initiated by an inhibition of primordial germ cell divisions.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/dvg.1020080104
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    β-Glucuronidase activity is present in the microscopic epididymis of the Tfm/Y mouse (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987), S. 11-15 
    Details
    ISSN: 0192-253X
    Keywords: testicular feminization ; androgen induction ; meiosis inducing substance ; Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: The sex-linked recessive gene Tfm in the mouse produces a condition of testicular feminization (androgen insensitivity syndrome, AIS) in hemizygotes, comparable to the condition of the same name in humans. The murine mutant was originally believed to have no derivatives of the mesonephric duct system (MDS), and this absence was ascribed to dependence of these derivatives on androgens for survival. However, microscopical epi-didymides, retia testes, and vasa deferentia were identified in these animals in our laboratory. These micro-organs may play a role in meiosis induction in Tfm/Y animals. The present study was designed to determine whether survival of these organs is due to retention of an ability to respond to androgens, or whether they are unique amongst MDS derivatives in being independent of androgens.Previous studies in our laboratory demonstrated that the enzyme β-glucuronidase (βG) is androgen sensitive in the epididymis of the normal mouse. In the present investigation we used this enzyme as a marker to study androgen sensitivity in the microscopical epididymides of Tfm/Y hemizygotes and in the epididymides of control +/Y litter-mate brothers. Both mutant and control animals were studied with and without exogenous androgen stimulation.Tfm/Y hemizygotes demonstrated low levels of diffuse, cytoplasmic βG activity that appears to be unresponsive to exogenous androgen stimulation. In light of our previous studies, this distribution of βG reaction products suggests some degree of androgen sensitivity. The survival of these micro-organs and their partial androgen sensitivity may be related to the role of the MDS in inducing meiosis.
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    URL: http://dx.doi.org/10.1002/dvg.1020080103
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    Ovarian teratocarcinomas in LT/Sv mice carrying t-mutations (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987), S. 1-9 
    Details
    ISSN: 0192-253X
    Keywords: T/t-complex ; LT mice ; parthenogenesis ; recombination ; gene-mapping ; primitive streak ; Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: Ovarian teratomas that result from parthenogenetic activation of oocytes provide a double tool for developmental geneties. First, they provide a way of measuring recombination between a gene and its centromere. Second, in the absence of crossing over there is the potential of producing tumors that are homozygous for genes that would be lethal in the course of in utero embryonic development. We have applied both aspects to several t- haplotypes containing different early acting t-lethal genes. In a study of 26 tumors, genotyped by Southern blot analysis of the major histocompatibility complex (MHC), we measured the distance between the centromere and the start of the t-complex as 5.6 ± 2.3 cM. We found a marked deficiency of t-homozygous genotypes among the tumors we studied, although T/T genotypes formed teratomas at levels comparable to controls. None of the lethal t-haplotypes we studied permit homozygous embryos to develop to the primitive streak stage, while T/T embryos do develop essentially normally through that stage. Thus, although the total number of tumors observed from t-bearing mice was small, the great difference in the incidence of t/t tumors versus the incidence of T/T tumors suggests strongly that the parthenogeretic embryos that convert to teratocarcinomas must first pass through some of the stages of normal early development, including the formation of three germ layers and the primitive streak.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/dvg.1020080102
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    Editorial (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987), S. i 
    Details
    ISSN: 0192-253X
    Keywords: Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/dvg.1020080502
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    Auxin (2,4-dichlorophenoxyacetic acid) starvation and treatment with glucan elicitor isolated from Phytophthora megasperma induces similar responses in soybean-cultured cell suspensions (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987), S. 351-364 
    Details
    ISSN: 0192-253X
    Keywords: soybean cell suspension cultures ; phytoalexin production ; 2,4-D starvation ; chitinase ; β 1,3-glucanase ; Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: Auxin (2,4-dichlorophenoxyacetic acid) starvation of soybean cell suspension leads to the arrest of cell division after about 4 days. Readdition of 4 μM of auxin enables cells to divide again after a lag phase of 1 day. Accumulation of a well-known isoflavonoid-derived phytoalexin (glyceollin) and a highly elevated catalytic activity of two of the enzymes associated with glyceollin biosynthesis, phenylalanine ammonia-lyase and chalcone isomerase, is described. Moreover, stimulation of catalytic activity of the enzymes chitinase and β 1,3-glucanase, which are involved in plant defense against pathogens, is observed at the same time. By comparing the patterns of in vitro protein synthesis, we have identified groups of polypeptides whose synthesis is either positively or negatively regulated by auxin. Some of these polypeptides are also induced by fungal elicitor treatment. Our results provide evidence of a dual control by auxin and fungal elicitor working in an opposite manner on the inducibility of enzymes and proteins that play a role in the induced defense response of soybean.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/dvg.1020080506
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    Chromatin structure and plant gene expression (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987), S. 405-434 
    Details
    ISSN: 0192-253X
    Keywords: plant genes ; chromatin ; nucleosomes ; DNAse I-hypersensitive sites ; cytosine methylation ; Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: The nuclear DNA of eukaryotic organisms is associated with a variety of proteins, which together make up what is called “chromatin.” Chromatin serves to package all genes into higher-order structures such as nucleosomes, solenoids, and loop domains. Tight packing of a particular gene and its regulatory sequences does not allow the approach of RNA I or II polymerase proteins. Before or during the activation of such an inactive gene its chromatin has to adopt a relaxed, more “open” configuration. This altered chromatin can be probed by its higher sensitivity toward nucleases, such as DNAse I or S1 nuclease, and the appearance of DNAse I-hypersensitive sites. These sites may constitutively be present or may be induced, and they can be mapped to specific DNA sequence motifs. In many cases, such sites are delimited by non-B-DNA, notably Z-DNA, which in turn may form part of enhancer elements. The Z-DNA configuration may be induced or maintained by methylation of cytosyl residues within underlying sequences.Two plant gene model systems have been selected to probe their chromatin structure. Constitutively expressed T-DNA genes of Agrobacterium induced tobacco crown gall tumor cells have been shown to be organized in canonical nucleosomes, to be more sensitive to DNAse I than the bulk of host chromatin, and to contain a series of six constitutive DNAse I-hypersensitive sites. Inducible ribulose-1,5-bisphosphate carboxyl-ase/oxygenase small subunit (rbcS) genes of pea are rearranged into a nuclease-sensitive format upon activation by light, especially in their promoter region. The rbcS promoter harbors a series of five constitutive DNAse I-hypersensitive sites and one light-inducible site, which is surrounded by potential regulatory sequences (enhancer cores, inverted repeats). The 3′ region of rbcS genes also contains constitutive sites. Methylation/demeth-ylation of Alu I-, Fnu4H1-, HaeIII-, Sau3AI-, and Sau 96I sequences in rbcS promoters does not play any role in rbcS gene inactivation/activation.
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    Masthead (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987) 
    Details
    ISSN: 0192-253X
    Keywords: Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/dvg.1020080101
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    Drosophila: A practical approach. Edited by D.B. Roberts Oxford-Washington, DC: IRL Press, 1986. 295 pp. (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987), S. 59-60 
    Details
    ISSN: 0192-253X
    Keywords: Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/dvg.1020080108
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    Masthead (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987) 
    Details
    ISSN: 0192-253X
    Keywords: Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/dvg.1020080201
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    Tumor formation and morphogenesis on different Nicotiana sp and hybrids induced by Agrobacterium tumefaciens T-DNA mutants (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987), S. 61-71 
    Details
    ISSN: 0192-253X
    Keywords: Agrobacterium insertion mutants ; hormone equilibria ; differentiation ; dedifferentiation ; Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: A series of experiments are presented that have been performed to observe the interactions between Agrobacterium tumefaciens strains mutated in the T-DNA genes involved in indoleacetic acid and cytokinin biosynthesis and several Nicotiana species and hybrids. Infections were induced on leaf cuttings of Nicotiana debneyi, N. knightiana, N. clevelandii, N. bigelovii var bigelovii, N. bigelovii var quadrivalvis, N. glauca, N. langsdorffii, the amphidiploid tumorous hybrid N. glauca × N. langsdorffii, and a nontumorous mutant of it. The effect of deletions of the Ti plasmid varied according to plant genotype. Insertion mutants in iaaM and iaaH suppressed tumor formation in N. langsdorffii, reduced it in N. bigeloviivar quadrivalvis, had no effect in N. glauca and the two amphidiploid hybrids, and promoted tumorigenesis when compared to the wild-type Agrobacterium strain B6S3 in N. bigelovii N. debneyi, and N. knightiana. The same mutations induced shoot formation in N. glauca, increased it in N. debneyi, and suppressed root formation in N. knightiana. On the other hand, an insertion mutation of the isopentenyl transferase gene (ipt-) had no effect in N. bigelovii var quadrivalvis, N. debneyi, the tumorous hybrid, suppressed tumor formation in N. langsdorffii, and inhibited it in N. glauca, the nontumorous hybrid, N. bigelovii var bigelovii, and N. knightiana. Insertion in ipt suppressed shoot formation in the nontumorous hybrid and inhibited it in the nontumorous amphidiploid and N. debneyi, while promoting root formation in N. glauca and N. debneyi.The suggestion of the existence of specific hormone equilibria necessary for the shift to each morphogenetic pattern was supported by experiments with exogenous hormone treatments of three genotypes (N. glauca, N. langsdorffii, and the nontumorous N. glauca × N. langsdorffii).
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    Action of the cubitus interruptus-wallace mutant in Drosophila melanogaster: A study of leg morphology on mosaic and haplo-4 flies (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987), S. 151-163 
    Details
    ISSN: 0192-253X
    Keywords: positional reference ; mitotic activity ; cell identity ; Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: The fourth chromosome mutant cubitus interruptus-Wallace(ciW) produces leg, wing, and body bristle aberrations. The effect on the wing is similar to that produced by cubitus interruptus-dominant (ciD) which also has an influence on larval segmentation indicating that it has a regulatory function. Leg morphology of haplo-4, ciW, and mosaic haplo-4:diplo-4, ci/ci+ flies was examined in an attempt to distinguish between a structural and a regulatory function by ciW. Aberrations recovered include failure of segment elongation, intersegmental gaps, duplication of bristles, and segments that are shorter than normal and of greater than normal diameter. Many of these effects are localized, suggesting that ciW may act to maintain cell positional reference. Increased local cell proliferation appears to be one manifestation of loss of the normal function.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/dvg.1020080304
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    Masthead (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987) 
    Details
    ISSN: 0192-253X
    Keywords: Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/dvg.1020080401
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    Testes of XX ↔ XY chimeric mice develop from fetal ovotestes (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987), S. 207-218 
    Details
    ISSN: 0192-253X
    Keywords: chimeras ; ovotestes ; sex differentiation ; sex mosaics ; hermaphrodites ; Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: The majority of XX ↔ XY chimeric mice develop into fertile males. The sexual differentiation of the gonads in these animals has been examined on days 12-14 postcoitum to determine if their development parallels that of normal testes. It was found that 50% of chimeric fetuses, the proportion predicted to be XX ↔ XY, had neither normal testes nor ovaries. Instead, ovotestes were present, with varying proportions of presumptive ovarian and testicular tissue. On day 12 the ovotestes were organized with testicular tissue in the central region and ovarian tissue at the craniad and/or caudad poles. In the more advanced fetuses there was evidence of regression of the ovarian portion, which would account for the testes found in adults. These results are discussed in light of current theories of sex determination and differentiation and what was previously known about gonads of sex mosaics.
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    Developmental consequences of autosomal aneuploidy in mammals (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987), S. 249-265 
    Details
    ISSN: 0192-253X
    Keywords: trisomy ; trisomy 16 mouse ; trisomy 19 mouse ; Down syndrome ; gene dosage effects ; Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: Autosomal aneuploidy in mammals adversely affects developmental processes. In human beings, for example, trisomy 21 is the most frequent aneuploidy detected among newborns and the most common known genetic cause of mental retardation. In this review, several hypotheses are discussed that have been proposed to explain the mechanisms by which aneuploidy (especially trisomy) disrupts development. These mechanisms included specific gene dosage effects, generalized disruption of genetic homeostasis, and the influence of the parental origin of the duplicated chromosome. The availability of specific chromosomal rearrangements in mice, coupled with selective breeding schemes, permits generation of aneuploidy of specific chromosomes or chromosomal segments on controlled genetic backgrounds, thus enabling the systematic study of the causes and consequences of defined aneuploidy. Phenotypic characteristics associated with a number of specific aneuploidies in the mouse are discussed. Emphasis is placed on the effects of trisomy 16. Genetic homology between mouse chromosome 16 and human chromosome 21 has led investigators to suggest that analogous mechanisms will be responsible for the developmental abnormalities produced in these respective aneuploidies. Analysis of trisomy 16 mice from the organismal to the subcellular level has revealed a number of phenotypic characteristics (particularly neurobiologic ones) shared with human trisomy 21. The dosage effects of shared genes (or their products) may contribute to the development of these features.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/dvg.1020080408
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    Masthead (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987) 
    Details
    ISSN: 0192-253X
    Keywords: Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/dvg.1020080501
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  • 145
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    Structure of the chloroplast psbA gene encoding the QB protein from Oryza sativa L. (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987), S. 339-350 
    Details
    ISSN: 0192-253X
    Keywords: psbA gene ; DNA sequencing ; sequence homologies ; promoter ; Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: The light-regulated chloroplast psbA gene encoding the QB protein has been cloned from rice (Oryza sativa L.), and the nucleotide sequence has been determined. Comparison of nucleotide sequences and derived amino acid sequences between species indicates a high degree of conservation of the primary structure. Comparison of promoter regions from the light-inducible chloroplast psbA, rbcL, and psaA genes indicates conservation of the prokaryotic-like promoter elements in all three genes and of a  - 21 box common only to psbA and rbcL promoter regions. No other putative regulatory signals were found based on nucleotide sequences.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/dvg.1020080505
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  • 146
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    Constitutive transcription of a soybean heat-shock gene by a cauliflower mosaic virus promoter in transgenic tobacco plants (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987), S. 365-374 
    Details
    ISSN: 0192-253X
    Keywords: soybean ; heat-shock gene ; CaMV promoter ; plant transformation ; Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: Transcription of heat-shock protein genes in soybean can be induced by high temperature stress leading to a transient expression of heat-shock proteins. We have tested whether the replacement of a native heat-shock promoter by a viral promoter results in constitutive transcript levels of the respective gene in transgenic plants. The 35S-transcript promoter of the cauliflower mosaic virus was linked to the protein-coding region of the genomic heat-shock gene hs6831, encoding a 17.6-kD heat-shock protein of soybean. After transformation of tobacco plants with this chimeric construction using a disarmed Agrobacterium binary vector, abundant mRNA levels were detected in transgenic plants. The steady-state level of this mRNA at 25°C was equal to that generated by the native heat-shock promoter at 40°C; however, it was markedly reduced by heat shock applied to the transgenic plants. These findings suggest a sufficiently high stability of heat-shock mRNA produced at the normal growth temperature to direct constitutive expression of heat-shock proteins. The application of constitutive gene expression for the investigation of thermotolerance is discussed.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/dvg.1020080507
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  • 147
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    Histone genes in higher plants: Organization and expression (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987), S. 461-473 
    Details
    ISSN: 0192-253X
    Keywords: H3 and H4 genes ; plants ; structure ; cloning ; S1 mapping ; Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: The general structure of the plant histone genes has been deduced from the comparison of the nucleotide sequences of ten H3 and H4 genes of maize (3 H3 and 3 H4) and Arabidopsis thaliana (2 H3 and 2 H4). The five H3 and five H4 genes encode the same proteins, respectively. The 5′-flanking regions contain the classical histone gene-specific consensus sequences. In addition, a conserved octanucleotide CGCGGATC was found in all plant histone genes at 200-250 nucleotides before the initiation codon.All six maize H3 and H4 genes are transcribed during early germination as shown by nuclease S1 mapping and reverse transcriptase primer extension experiments. The mRNA 5′-ends are located within the consensus sequence CCAA/CT/C. The 3′-ends lack the classical T-hyphenated dGC-rich palindromic structure and possess long nontranslated sequences.In both plants the multiple copies of the H3 and H4 genes are organized into multigenic families. The genes of each family show a similar proximal environment, suggesting that they originate from the duplication of a common ancestor.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/dvg.1020080512
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  • 148
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    Expression of selected nuclear genes during leaf development in barley (1987)
    Chichester [u.a.] : Wiley-Blackwell
    Developmental Genetics 8 (1987), S. 495-511 
    Details
    ISSN: 0192-253X
    Keywords: barley leaf development ; nuclear genes ; developmental control of transcription ; Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: Groups of cDNA clones encoding abundant leaf proteins or derived from genes (gene families) with other features of interest have been selected from a barley leaf cDNA library. The characteriaztion of nine of the groups is summarized and includes information on the tissue specificity and light dependence of expression of their corresponding genes. Different types of control of gene expression are represented in the collection: leaf-specific expression, both stimulated and inhibited by light, constitutive expression, and expression that is maximal in one case in coleoptiles and in two cases in meristematic tissue. For the light-stimulated genes (gene families) encoding chloroplast proteins (Cab, RbcS, and plastocyanin), relative and absolute levels of messengers were determined as a function of cell age in sections of 7-day-old barley leaves grown under diurnal conditions. Key parameters of cell growth (protein, RNA, and DNA accumulation) were determined in the same leaf sections. The main conclusions of the expression studies are as follows: (1) Light is in no case a requirement for gene expression although it has significant stimulatory effect on some genes; (2) weak expression of some genes coding for chloroplast proteins was detected in the leaf-like, white coleoptiles, whereas expression in roots could not be detected; (3) The cab, rbcS, and plastocyanin genes are expressed very early during leaf cell differentiation, when the plastids morphologically are still in their amyloplast-amoeboid stages; (4) The expression of the cab, rbcS, and plastocyanin genes is not coordinated during leaf cell development.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/dvg.1020080514
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  • 149
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    Masthead (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987) 
    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.550191001
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  • 150
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    Data on the thermochemistry of azoalkanes (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 929-942 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant of the primary decomposition step was determined for four symmetrical and four unsymmetrical azoalkanes. From the experimental activation energies and some literature enthalpy data, the following enthalpies of formation of radicals and group contributions were calculated: ΔHƒ (CH3N2) = 51.5 ± 1.8 kcal mol-1, ΔHƒ (C2H5N2) = 44.8 ± 2.5 kcal mol-1, ΔHƒ (2-C3H7N2) = 37.9 ± 2.2 kcal mol-1, [NA-(C)] = 27.6 ± 3.7 kcal mol-1, [NA-(ṄA) (C)] = 61.2 ± 3.1 kcal mol-1.
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  • 151
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    Masthead (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987) 
    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.550191101
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  • 152
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    Disproportionation reactions between alkyl and fluoroalkyl radicals. IV. Pentafluoroethyl and ethyl radicals (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 963-973 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new determination of the disproportionation/combination ratio for C2F5 and C2H5 radicals gives a value of Δ(C2F5, C2H5) = 0.24 ± 0.02, independent of temperature. The cross-combination ratio for the two radicals was found to increase with temperature and the significance of this is discussed in evaluating Δ.
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    URL: http://dx.doi.org/10.1002/kin.550191103
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  • 153
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    The gas phase reactions of hydroxyl radicals with a series of aliphatic alcohols over the temperature range 240-440 K (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 1015-1023 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate constants were determined for the gas phase reactions of OH radicals with a series of aliphatic alcohols using the flash photolysis resonance fluorescence technique. Experiments were performed over the temperature range 240-440 K at total pressures (using Ar diluent gas) between 25-50 Torr. The kinetic data for methanol (k1), ethanol (k2), and 2-propanol (k3) were used to derive the Arrhenius expressions \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = (4.8 \pm 1.2) \times 10^{ - 12} \exp [- (480 \pm 70)/T]\,{\rm cm}^3\, {\rm molecule}^{ - 1} {\rm s}^{ - 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_2 = (7.4 \pm 3.2) \times 10^{ - 12} \exp [- (240 \pm 110)/T]{\rm cm}^3 {\rm molecule}^{ - 1} {\rm s}^{ - 1} $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$ k_3 = (5.8 \pm 1.9) \times 10^{ - 12} \exp [- (30 \pm 90)/T]\,{\rm cm}^3\, {\rm molecule}^{ - 1} {\rm s}^{ - 1} $$\end{document} At 296 K, the measured rate constants (in units of 10-13 cm3 molecule-1 s-1) were: k1 = (8.61 ± 0.47), k2 = (33.3 ± 2.3), and k3 = (58.1 ± 3.4). Room temperature rate constants for the OH reactions with several other aliphatic alcohols were also measured. These were (in the above units): 1-propanol, (53.4 ± 2.9); 1-butanol, (83.1 ± 6.3) and 1-pentanol, (108 ± 11). The results are discussed in terms of the mechanisms for these reactions and are compared to previous literature data.
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    URL: http://dx.doi.org/10.1002/kin.550191106
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  • 154
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    Masthead (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987) 
    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.550191201
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  • 155
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    Gas phase thermolysis of cyanomethyl t-butyl sulfide and cyanomethyl t-butyl ether (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 1053-1062 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolyses of cyanomethyl t-butyl sulfide and its oxygen homologue have been studied in a stirred-flow system over the temperature range 490-540°C and pressures between 5 and 14 Torr. In both cases, isobutene is formed as product in over 97% yield. Hydrogen sulfide is obtained in about half the amount of isobutene in the pyrolysis of the sulfide. Hydrogen cyanide is formed in the pyrolysis of the ether. The first-order rate coefficients for the consumption of the reactants followed the Arrhenius equations Cyanomethyl t-butyl sulfide: \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{ - 1}) = 10^{12.63 \pm 0.23} \exp (- 201.7 \pm 3.5)\,{\rm kj}/{\rm mol }\,RT $$\end{document} Cyanomethyl t-butyl ether: \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{ - 1}) = 10^{11.27 \pm 0.30} \exp (- 186 \pm 5)\,{\rm kj}/{\rm mol }\,RT $$\end{document}A molecular mechanism involving polar four-centered cyclic transition states is proposed for both reactions, with the CN group stabilizing the partial negative charge developed at the S and O atoms.
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  • 156
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    Kinetics of the gas-phase reactions of Cl atoms with chloroethenes at 298 ± 2 K and atmospheric pressure (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 1097-1105 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a relative rate technique, rate constants have been determined for the gas-phase reactions of Cl atoms with the cholorethenes and ethane at 298 ± 2 K and 735 torr total pressure of air. Using a rate constant of 1.97 × 10-10 cm3 molecule-1 s-1 for the reaction of Cl atoms with n-butane, the following rate constants (in units of 10-11 cm3 molecule-1 s-1) were obtained: vinyl chloride, 12.7 ± 0.2; 1,1-dichloroethene, 14.0 ± 0.2; cis-1,2-dichloroethene, 9.65 ± 0.10; trans-1,2-dichloroethene, 9.58 ± 0.18; trichloroethene, 8.08 ± 0.10; tetrachloroethene, 4.13 ± 0.23; and ethane, 6.17 ± 0.08 (where the indicated error limits do not include the uncertainties in the rate constant for n-butane). A small amount of cis-trans isomerization was observed for the reactions involving the cis- and trans-1,2-dichloroethenes. These data are compared and discussed with the available literature data.
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  • 157
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    The pyrolysis of acetylene-styrene mixtures between 450 and 550°C (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 659-678 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of acetylene-styrene mixtures has been studied from 450-550°C in a quartz reaction vessel in the absence and presence of O2 or NO. The rates of disappearance of reactants and formation of adducts are first-order in each reactant. The major product is polymer, with the adducts accounting for about 2.5% and 6.2% of the styrene removed at 450 and 550°C, respectively. The acetylene-to-styrene removal ratio is about 27 independent of temperature. The adducts formed are methyl indene and 1,2-dihydronaphthalene. These are about half-suppressed in the presence of O2 or NO. The rate coefficients for reactant removal and adduct formation are: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log \{ k\{ {\rm C}_{\rm 2} {\rm H}_{\rm 2} \},M^{ - 1} {\rm s}^{ - 1} \} = 7.53 \pm 0.10 - (90.6 \pm 1.5)/2.3RT $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \log \{ k\{ {\rm C}_{\rm 8} {\rm H}_{\rm 8} \},M^{ - 1} {\rm s}^{ - 1} \} = 6.63 \pm 0.60 - (98.5 \pm 8.8)/2.3{\rm }\,RT $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \log \{ k\{ {\rm C}_{{\rm 10}} {\rm H}_{{\rm 10}} \},M^{ - 1} {\rm s}^{ - 1} \} = 8.27 \pm 0.66 - (143.3 \pm 9.8)/2.3RT $$\end{document} where the activation energies are in kJ/mol and the uncertainties are one standard deviation. As the reaction proceeds, the methyl indene and 1,2-dihydronaphthalene decompose, and indene and naphthalene are formed. In addition, an unidentified isomer of naphthalene is produced as an initial minor product, and it also decomposes as the reaction proceeds.
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    Masthead (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987) 
    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.550190101
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  • 159
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    Bond dissociation energies and radical heats of formation in CH3Cl, CH2Cl2, CH3Br, CH2Br2, CH2FCl, and CHFCl2 (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 15-24 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An analysis of thermochemical and kinetic data on the bromination of the halomethanes CH4-nXn (X = F, Cl, Br; n = 1-3), the two chlorofluoromethanes, CH2FCl and CHFCl2, and CH4, shows that the recently reported heats of formation of the radicals CH2Cl, CHCl2, CHBr2, and CFCl2, and the C—H bond dissociation energies in the matching halomethanes are not compatible with the activation energies for the corresponding reverse reactions. From the observed trends in CH4 and the other halomethanes, the following revised ΔH°f,298 (R) values have been derived: ΔH°f(CH2Cl) = 29.1 ± 1.0, ΔH°f(CHCl2) = 23.5 ± 1.2, ΔHf(CH2Br) = 40.4 ± 1.0, ΔH°f(CHBr2) = 45.0 ± 2.2, and ΔH°f(CFCl2) = -21.3 ± 2.4 kcal mol-1. The previously unavailable radical heat of formation, ΔH°f(CHFCl) = -14.5 ± 2.4 kcal mol-1 has also been deduced. These values are used with the heats of formation of the parent compounds from the literature to evaluate C—H and C—X bond dissociation energies in CH3Cl, CH2Cl2, CH3Br, CH2Br2, CH2FCl, and CHFCl2.
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    Kinetic studies on the oxidation of carbon monoxide over pure, reduced, and doped indium sesquioxides (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 1-14 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetic studies on the oxidation of carbon monoxide have been carried out between 413 and 473 K at different partial pressures of carbon monoxide and oxygen by means of the static method using vacuum-activated, hydrogen-reduced, and NiO-doped In2O3 semiconductors as catalysts. A strong carbon dioxide inhibiting effect is observed. The experimental data satisfactorily fit an equation derived by assuming the controlling step to be the adsorption of gaseous oxygen on the surface of catalyst. CO and CO2 adsorb on the lattice oxygens (Oo2-), while O2 adsorbs on the oxygen vacancies (Vox) formed by vacuum-activation, H2-reduction, and NiO-doping of In2O3. When CO2 formed during the reaction is removed by means of liquid nitrogen trap, the oxidation is found to be first-order with respect to CO and to be half-order with respect to O2. The concentration of oxygen vacancy in the solid catalyst is shown to be the controlling factor for the oxidation of carbon monoxide. A possible reaction mechanism can be explained by the n-type character of In2O3 and proposed from the experimentally obtained kinetic data and conductivities.
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    Pulse radiolysis study of the reaction of OH radicals with C2H4 over the temperature range 343-1173 KWork performed under the auspices of the Office of Basic Energy Sciences, Division of Chemical Science, US-DOE under contract Number W-31-109-ENG-38. (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 25-34 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of OH and OD radicals with ethylene in the presence of 1 atm argon and 6 Torr water vapor was studied in the temperature range 343-1173 K. The results reveal three kinetically separate temperature regions: (1) 343-563 K, where the disappearance of OH radical is dominated by the addition of OH to the double bond of ethylene; (2) 563-748 K, where concurrent reactions of addition, the reverse reaction of addition and H-atom abstraction is dominant; and (3) 748-1173 K, where H-atom abstraction is likely the main reaction. The rate for hydrogen abstraction is 2.4 × 10-11 exp[(-2104 ± 125)/T] cm3/molec-s (for OD 2.1 × 10-11 exp[(-2130 ± 172)/T] cm3/molec-s). There was no obvious pyrolysis of ethylene below 1073 K. The study of OD radical with ethylene shows a small isotope effect.
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  • 162
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    Sensitivity analysis of the two kinetic states of the Belousov-Zhabotinsky reaction (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 35-48 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A recently published kinetic model of the Belousov-Zhabotinsky reaction was studied by the feature sensitivity analysis of the slow bromide consumption and slow bromide production periods of the relaxing-type oscillatory system. The computed sensitivities allowed us to reveal the kinetic importance of the 17 individual reactions during the two, “kinetically homogeneous” states of the oscillation. Similarities and differences in the relative kinetic importances of the reaction steps were carefully studied when changing the magnitude of the rate constants (high set and low set). Of the 17 reactions examined, the attack of Ce4+ on malonic acid proved to be an essential step of the mechanism. Using the low set, there emerge more reactions which significantly affect the length of the two kinetic states.
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    URL: http://dx.doi.org/10.1002/kin.550190105
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  • 163
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    The photochemistry of methyl cyclobutyl ketone. Part 2. Temperature dependence and the acetyl radical decomposition (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 997-1013 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Following earlier room-temperature studies, gaseous mixtures of methyl cyclobutyl ketone (MCK) diluted in argon have been photolyzed at temperatures up to 205°C. Experiments have been carried out at a variety of pressures (up to ca. 2 atm) at wavelengths of 313 nm (steady state conditions) and 308 nm (pulsed photolysis). The results are consistent with a mechanism dominated by radical-radical reactions involving acetyl, methyl, and cyclobutyl radicals. Acetyl radical processes predominate at lower temperatures while methyl radical reactions are more important at high temperatures.The results are interpreted via kinetic modelling of a mechanism in which a key role is played by the acetyl radical decomposition reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ ({\rm M} +)\,{\rm CH}_{\rm 3} {\rm CO}\mathop {\longrightarrow}\limits^{\rm 3} {\rm CH}_{\rm 3} + {\rm CO\, (+ M)} $$\end{document} Values for k3 have been obtained and its temperature and pressure dependence are fitted by RRKM theory and a weak-collisional activation model to yield \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log(}k_3 ^\infty /{\rm s}^{ - 1}) = 13.3 - 17.5{\rm\, kcal\, mol}^{{\rm - 1}} /RT\ln 10 $$\end{document} This high-pressure limiting Arrhenius equation is consistent with other studies in the same temperature range, but is difficult to reconcile with higher temperature investigations.
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    URL: http://dx.doi.org/10.1002/kin.550191105
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    Kinetics and mechanisms of substitution at paramagnetic metal centers in organometallic complexes (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 1025-1047 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of ligand substitution in 17- and 19-electron organometallic radicals is discussed. These species substitute ligands by an associative process some 106 to 1010 faster than analogous 18-electron complexes. When 17-electron species can be generated by bond homolysis or electron transfer reactions of 18-electron complexes, they can act as intermediates in radical chain reactions of 18-electron complexes. A 17-19 electron rule is proposed to explain transformations of organometallic radicals just as the 16-18 electron rule finds use for closed shell organometallic complexes. The origin of this rule is the favorable two-center three-electron bond that can form when an odd electron in a sterically accessible metal d-orbital interacts with an electron pair on an entering nucleophile. Besides simple substitution, these radicals can disproportionate, dimerize, and undergo insertion or atom abstraction reactions.
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    URL: http://dx.doi.org/10.1002/kin.550191107
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  • 165
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    Rate constant for the reaction of OH radicals with dimethyl sulfide (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 1073-1082 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constants of the gas phase reaction of OH radicals with dimethyl sulfide (CH3SCH3) over the temperature range 260-393 K have been studied using the discharge flow-resonance fluorescence technique. The rate constants were fitted by the Arrhenius equation k = (11.8 ± 2.2) × 10-12 exp[-(236 ± 150)/T] cm3 molecule-1 s-1 with k = (5.5 ± 1.0) × 10-12 cm3 molecule-1 s-1 at 298 K. Our results are in good agreement with the lower range of values reported previously. The observation of a small positive activation energy agrees well with that reported by Hynes et al. The rate constant was not affected by the total pressure variation (0.8-3.0 torr) or by the addition of oxygen (up to 1 torr) in the flow tube.
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  • 166
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    Erratum (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 1107-1107 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Br atoms produced in a microwave discharge react abnormally rapidly with isobutane to produce HBr + t-Butyl. A VLPR study of the system at high Br atom concentration (Br ˜ 1013/cc) between 298 and 363 K permits one to separate the effects of excited atoms, Br* (2P1/2) from ground state atoms, Br (2P3/2). Rate constants for the latter agree well with bromination measurements and permit fixing ΔHƒ2980(tBu) at 9.5 ± 0.5kcal/mol in agreement with earlier work.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550191207
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  • 167
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    Investigation of the gas phase reaction of dinitrogen pentoxide with water vapor (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 191-205 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase reaction of N2O5 with water vapor was investigated in a 17.3-m3 Teflon lined chamber. Temporal concentration profiles for ozone, total nitrogen oxides, and nitrogen dioxide were measured. Concentration profiles for N2O5 and HNO3 were calculated from a combination of measurements of nitrogenous species. A kinetic mechanism with an adjustable value for the rate constant of N2O5 + H2O was used to model the experiments. From this analysis an upper limit value of k ≤ 4 × 10-7 ppm-1 min-1 for the gas phase reaction N2O5 + H2O → 2HNO3 was derived.
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    URL: http://dx.doi.org/10.1002/kin.550190304
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  • 168
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    Bimolecular QRRK analysis of methyl radical reactions (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 207-228 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions which proceed through energized adducts, including radical recombinations, insertions, and addition to unsaturates, frequently exhibit unusual kinetic behavior. The branching ratios among various product channels are often complex functions of both temperature and pressure. Four such reactions involving methyl radicals are analyzed by combining chemical activation distribution functions with QRRK methods to predict rate constants for each channel. These include three oxidation paths, CH3 + O, CH3 + O2, CH3 + OH, and the addition reaction CH3 + C2H2. These predictions are compared to experiments wherever possible; generally, the agreement is quite satisfactory. Analysis of the energetics of the various reaction channels, using parameters which are readily available, provides a convenient framework for prediction. Suggested rate constants for the various channels for the four reactions are given at three pressures, 20, 760, and 7600 Torr, for the temperature range 300-2500 K. The approach used here can easily be applied to other reactions.
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  • 169
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    Direct and sensitized photolysis of bicyclo[4.2.0]octa-2,4-diene in the gas phase (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 229-242 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The direct photolysis of bicyclo[4.2.0]octa-2,4-diene in the gas phase at 280-300 nm produces mainly 1,3,5-cyclooctatriene and benzene plus ethylene. The yield of the former product is enhanced by added gases, and it is proposed that it is formed in a vibrationally excited state which can revert to bicyclooctadiene unless the excess energy is removed in collisions. Computer modelling of the direct photolysis yielded quantitative agreement with the experimental results, but only when large, arbitrary adjustments were made to the calculated rate constants for the interconversion of cyclooctratriene and bicyclooctadiene. The Hg(63P1) sensitized reaction of bicyclooctadiene produces mainly benzene plus ethylene, a process which is also enhanced by added gases.
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    URL: http://dx.doi.org/10.1002/kin.550190306
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  • 170
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    Kinetics of the reactions of the hydroxyl radical with dimethyl ether and diethyl ether (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 251-259 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate coefficients for the reactions of the hydroxyl radical with dimethyl ether (k1) and diethyl ether (k2) were measured over the temperature range 295-442 K. The rate coefficient data, in the units cm3 molecule-1 s-1, were fitted to the Arrhenius equations k1 (T) = (1.04 ± 0.10) × 10-11 exp[-(739 ± 67 cal mol-1)/RT] and k2(T) = (9.13 ± 0.35) × 10-12 exp[+(228 ± 27 kcal mol-1)/RT], respectively, in which the stated error limits are 2σ values. Our results are compared with those of previous studies of hydrogen-atom abstraction from saturated hydrocarbons by OH. Correlations between measured reaction-rate coefficients and C—H bond-dissociation energies are discussed.
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    URL: http://dx.doi.org/10.1002/kin.550190308
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  • 171
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    Cross-reaction and cross-combination ratios (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 261-268 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simple collision theory model for reaction between two different radicals shows that the cross-reaction ratio, φ*, is 2 only if the masses and collision diameters of the radicals are identical; for all other combinations of mass and size, φ* is greater than 2. The value of φ* is shown to depend simply on the ratios of the masses and diameters of the two radicals: which of the two is the heavier or larger is unimportant.Calculated and experimental values of φ* are compared for several systems involving small alkyl and fluoroalkyl radicals, and the relationship between φ* and φ, the cross-combination ratio, is discussed.
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  • 172
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    A study of the reaction NO3 + NO2 + M → N2O5 + M(M = N2, O2) (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 243-249 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase reaction of the NO3 radical with NO2 was investigated, using a flash photolysis-visible absorption technique, over the total pressure range 25-400 Torr of nitrogen or oxygen diluent at 298 ± 2 K. The absolute rate constants determined (in units of 10-13 cm3 molecule-1 s-1) at 25, 100, and 400 Torr total pressure were, respectively, (4.0 ± 0.5), (7.0 ± 0.7), and (10 ± 2) for M = N2 and (4.5 ± 0.5), (8.0 ± 0.4), and (8.8 ± 2.0) for M = O2. These data show that the third-body efficiencies of N2 and O2 are identical, within the error limits, and that previous evaluations for M = N2 are applicable to the atmosphere. In addition, upper limits were determined for the rate constants of the reactions of the NO3 radical with methanol, ethanol, and propan-2-ol of ≤6 × 10-16, ≤9 × 10-16, and ≤2.3 × 10-15 cm3 molecule-1 s-1, respectively, at 298 ± 2 K.
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    URL: http://dx.doi.org/10.1002/kin.550190307
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  • 173
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    Measurement of absolute rate data for the reaction of ground state atomic silicon, Si(33PJ), with halogenated olefinic and aromatic compounds by time-resolved atomic resonance absorption spectroscopy (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 1083-1096 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present a kinetic study of the reaction of ground state silicon atoms with halogenated unsaturated organic compounds (R). Si(33PJ) was generated by the repetitive pulsed irradiation of SiCl4 in the presence of excess helium buffer gas and the reactant R in a slow flow system, kinetically equivalent to a static system. The ground state atom was monitored by time-resolved atomic resonance absorption spectroscopy at λ = 252 nm [Si(43PJ) ← Si(33PJ)] on time scales by which the optically metastable tates,Si(31D2) and Si(31S0) had relaxed to the 3P state, using signal averaging methods. Computerized fitting of the resulting atomic decay traces in the presence of the various reactants, R, yielded the following new body of absolute second-order rate constants (kR, T = 300 K, errors = 2sigma;): TextRkR/cm3 molecule-1 s-1C2F41.6 ± 0.2 × 10-10C2Cl49.9 ± 1.7 × 10-10CH2CF24.0 ± 0.6 × 10-10CHClCCl27.0 ± 1.1 × 10-10CF3CH—CH24.6 ± 0.5 × 10-10C6H64.4 ± 1.0 times; 10-10C6F64.4 ± 0.6 × 10-10C6HF54.6 ± 1.3 × 10-10C6H2F43.9 ± 0.8 × 10-10C6F5 - CF35.1 ± 0.6 × 10-10These data are compared, where appropriate, with analogous data for unsaturated hydrocarbon organic compounds. They are also discussed within the general context of nuclear recoil measurements involving 31Si.
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    URL: http://dx.doi.org/10.1002/kin.550191205
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    Masthead (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987) 
    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.550190601
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  • 175
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    FTIR study of the DMS/NO2/I2/N2 photolysis system: The reaction of IO radicals with DMS (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 489-501 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A steady-state system involving the photolysis of NO2 in an excess of I2 as a source of IO radicals has been used to study the reaction IO + DMS in 760 Torr N2 at 296 K. IO radicals were found to react rapidly with DMS, one molecule of DMSO being produced for each molecule of DMS consumed. Numerical analysis of the experimental results yielded a rate constant of (3.0 ± 1.5) × 10-11 cm3 s-1 for the reaction IO + DMS → DMSO + I.
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    URL: http://dx.doi.org/10.1002/kin.550190602
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  • 176
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    Micellar catalysis by perfluorooctanoic acidAbstracted in part from the M.A. Thesis of M.E.A., Western Michigan University, 1986. (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 513-518 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rates of acidic hydrolysis of hexano-, octano-, and decanohydroxamic acids and of 4-bromophenylaceto- and phenylacetohydroxamic acids have been determined in aqueous perfluorooctanoic acid - a reactive counterion surfactant system. Typical micellar catalysis was observed for the hydrolyses of the n-alkyl hydroxamic acids but not for the arylacetohydroxamic acids. The Arrhenius activation energy for hydrolysis of octano-hydroxamic acid is smaller above the cmc of the surfactant than it is below the cmc.
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    URL: http://dx.doi.org/10.1002/kin.550190604
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  • 177
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    Kinetics of methylchlorosilane formation on Zn-promoted Cu3Si (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 519-537 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the direct synthesis reaction (Si + 2CH3Cl → (CH3)2SiCl2) were measured on a Cu3Si alloy containing 1.2 atom % Zn. Reaction was carried out in a differential reactor (520-595 K, 1 atm) attached to an ultrahigh vacuum (UHV) system. Auger spectroscopy was used to characterize the surface before and after reaction. Zinc does not significantly change the overall rate of reaction, but it changes selectivity to dimethyldichlorosilane (the desired product), surface composition, activation energies, and induction times. The rate of silicon diffusion to the surface is not limiting in the presence of zinc. Zinc is found to be a promoter for improved selectivity only in low concentrations, and only a fraction of the surface appears to be active for reaction. The kinetics appear relatively insensitive to the surface composition or the form of surface carbon. A Cu3Si surface with Zn is shown to be a good model catalyst for the direct synthesis reaction.
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  • 178
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    Approximation techniques in complex reaction kinetics (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 553-570 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We examine the kinetic model D. The differential equations describing this reaction scheme are cast in a nondimensional form and analyzed in four basic approximation regimes: a ‘pseudo-first order’ approximation valid for small values of the ratio of the initial concentrations of the reactants; an asymptotic solution valid for large values of k3; the standard steady state (Bodenstein) approximation; and an approximation to a second order system without intermediate. Interconnecting relationships between the various approximations derived are examined, and the approximations are compared to numerical solutions to the full equations. The results are assessed from the standpoint of the experimental kineticist, and it is suggested that the reaction studied, and consequently many other more complex reactions, may under certain circumstances be subject to non-unique interpretation.
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    URL: http://dx.doi.org/10.1002/kin.550190607
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  • 179
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    A reinvestigation of the rate constants for the reactions of ozone with cyclopentene and cyclohexene under atmospheric conditions (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 609-614 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates of decay of ozone in a large excess of the cycloalkene have been re-measured by an improved experimental procedure, and the following second-order rate constants (cm3 molecule-1 s-1) have been determined in synthetic air at atmospheric pressure: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm O}_3 + {\rm cyclopentene} \longrightarrow {\rm products,}} & {k = (4.97 \pm 0.30) \times 10^{ - 16} {\rm at}} \\ \end{array}291.5{\rm K} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm O}_3 + {\rm cyclohexene} \longrightarrow {\rm products,}} & {k = (1.51 \pm 0.10) \times 10^{ - 16} {\rm at}} \\ \end{array}295{\rm K} $$\end{document} The results are discussed in relation to existing literature data on the kinetics of ozonecycloalkene reactions.
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  • 180
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    Differential energy distributions in nonthermal systems: Model calculations and applications to 18F-for-F nuclear recoil substitutions in CH3CF3 (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 583-608 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general method has been developed for the determination of the differential energy distribution in nonthermally activated reacting systems. A series of known distributions and kinetic models has been used to test this method and to determine its efficacy. Application was then made to the kinetic data of energetic CH3CF2 18F formed by the substitution of F by 18F produced by nuclear recoil. The distribution obtained for this activated CH3CF2 18F is seen to be highly energetic with a median energy of 137.6 kcal mol-1 and with 33.1% of the molecules possessing energy in excess of 171 kcal mol-1. The shape of the calculated distribution suggests that there are two mechanisms for the formation of CH3CF2 18F from CH3CF3 and 18F, as well as that 62 kcal mol-1 is a lower limit to the kinetic energy needed by the 18F atom for this substitution to take place.
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    URL: http://dx.doi.org/10.1002/kin.550190702
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  • 181
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    Masthead (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987) 
    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.550190801
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  • 182
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    Analysis of flow dynamics in a new, very low pressure reactor. Application to the reaction: Cl + CH4⇌ HCl + CH3 (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 691-708 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new, improved variant of the very low pressure reactor (VLPR) system with interchangeable discharge orifices was used for studying the compatibility of the chemical and physical processes occurring simultaneously. It is shown that the ratio of calculated and effective escape rate constants is a complex function of the reactor cell geometry for reactions of non-spherical symmetry.The test reaction of atomic chlorine with methane proved to be a pure chemical process free of side reactions and was used to calibrate the system. The measured rate constant is k1 = (0.993 ± 0.013) × 10-13 cm3/molec-s at 25°C. A new procedure is outlined for measuring the equilibrium constant by changing the concentrations of all three components resulting in a remarkable accuracy of K1 = 1.406 ± 0.034 for the test reaction at 25°C.
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  • 183
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    Kinetics of the gas phase reaction of hydroxyl radicals with ethane, benzene, and a series of halogenated benzenes over the temperature range 234-438 K (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 725-739 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate constants for the gas phase reactions of OH radicals with ethane (k1), benzene (k2), fluorobenzene (k3), chlorobenzene (k4), bromobenzene (k5), iodobenzene (k6), and hexafluorobenzene (k7) have been measured over the temperature range 234-438 K using the flash photolysis resonance fluorescence technique. The rate constants measured at room temperature (296 K), at total pressures of argon diluent between 25 and 50 Torr, were (in units of 10-13 cm3 molecule-1 s-1): k1 = (2.30 ± 0.26), k2 = (12.9 ± 1.4), k3 = (6.31 ± 0.81), k4 = (7.41 ± 0.94), k5 = (9.15 ± 0.97), k6 = (13.2 ± 1.6), and k7 = (1.61 ± 0.24), respectively. The indicated errors are our estimate of 95% confidence limits and include two standard deviations from the least-squares analysis together with an allowance for any possible systematic errors in the measurements. At elevated temperatures and under pseudo-first-order reaction conditions, non-exponential hydroxyl radical decays were observed for benzene and the monosubstituted halo-aromatics. For ethane and hexafluorobenzene, exponential decays were observed over the complete temperature range and the data were fit by the Arrhenius expressions: k1 = (8.4 ± 3.1) × 10-12 exp[(-1050 ± 100)/T] and k7 = (1.3 ± 0.3) × 10-12 exp[(-610 ± 80)/T], respectively. The results are compared with previous literature data and the mechanistic implications are discussed.
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    URL: http://dx.doi.org/10.1002/kin.550190806
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    Kinetics and mechanism of transesterification of phenyl salicylate (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 757-776 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The first-order rate constants, k1, obtained for methanolysis and ethanolysis of phenyl salicylate (PSH) in aqueous mixed solvents, fit to a relationship: k1 = A1 · [ROH]T/(1 + A2[ROH]T) where A1 and A2 are the unknown parameters and [ROH]T is the total concentration of alkanol. It is proposed that the alkanolysis of PSH involves the preequilibrium formation of monomeric ROH from polymeric (ROH)n, followed by an intramolecular general base-catalysed nucleophilic attack by monomeric ROH on the carbonyl carbon of the ester. In the mixed solvents containing alkanol and MeCN, the k1 - [ROH]T profiles obtained in the presence of K+ ions are different from those obtained in the presence of Na+ ions which could be attributed to the cation-induced changes in the alkanol structure. Negative KCl salt effect has been observed on methanolysis of PSH, while it is essentially unaffected by the presence of tetraalkylammonium iodide salts (R4NI). The rates of ethanolysis of PSH have been found to increase with increase in [R4NI] and this increase becomes more pronounced with increasing hydrophobic surface area of R4NI. The rate constants for methanolysis of PSH in aqueous mixed solvents containing 80% MeOH (v/v) are independent of [ŌH] within the [ŌH] range of 0.01 to 0.15 M. The rate of methanolysis could not be detected within ca. 47 h in mixed solvents containing 96% HeOH (3.8% MeCN and 0.2% H2O), 80% MeOH (19.8% MeCN and 0.2% H2O), and 0.022 M HCl. It is concluded that for efficient transesterification, PSH should exist in ionized form. The reaction of PSH with MeOH is ca. 400 times faster than that with t-BuOH which could be ascribed to the most likely steric effect. The values of ΔH* and ΔS* obtained for methanolysis and ethanolysis are essentially independent of [ROH] within the ROH content of 20% to 96% for MeOH and 50% to 96% for EtOH. The effect of organic co-solvent on rate of hydrolysis of PSH could be explained in terms of organic co-solvent-induced water polarization.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550190808
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  • 185
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    Systematic characterization of transition states for radical decompositions (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 869-879 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A one-parameter analytical potential energy function for β-bonds in free radicals is described, which accounts quantitatively for their observed stretching frequencies and the position and size of the activation barriers for their fission. It is shown that such a function can be used to characterize a priori the corresponding transition states by assuming that the structural and spectroscopic changes taking place along the minimum energy path track the development of pi bonding rather than following a simple exponential dependence on the reaction coordinate. This procedure, tested by comparing predicted A-factors and isotope effects with experimental data for alkyl radicals and ab-initio calculations on C2H5, fully encodes the basic features of radical decomposition reactions and provides a simple, realistic, and self-consistent technique for the estimation of their kinetic parameters.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550190907
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  • 186
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    Kinetics and mechanism of the thermal reactions of endo- and exo-5-cyanobicyclo[2.2.2]oct-2-ene and methyl-substituted derivatives in the gas phase (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 885-894 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal reactions of endo- and exo-5-cyanobicyclo-[2.2.2]oct-2-ene and their trans- and cis-6-methyl-substituted derivatives have been investigated in the gas phase between 518 and 630 K. Each product decomposes by two parallel first-order retro-Diels-Alder reactions, a main one with formation of cyclohexa-1,3-diene and a minor one with elimination of ethene. Slight isomerizations are also observed. The kinetic results can be explained in terms of a biradical mechanism. The rate-determining step is shown to depend on the amount of resonance energy in the biradical. Heats of formation and entropies of the bicyclo[2.2.2]oct-2-enes studied are estimated.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550191002
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  • 187
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    Large inefficiencies of unweighted least-squares treatment of logarithmically transformed A exp(-kt) data (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 923-927 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The standard deviations (σ) of the parameters of a single exponential function can vary strongly with the range of the data, the character of the underlying error structure and also with the inclusion or omission of the appropriate relative weights. These effects are studied quantitatively, for least squares analysis of uniformly spaced, ln-linearized simulated data. The parameters, k and A, extracted are less precise when weighting is omitted, increasingly so as the range of the data increases, particularly for the case of equal amplitude errors for each A exp(-kti) datum. The results, expressed as efficiencies (σ2[using weights]/σ2[omitting weights]), show 〈 1% efficiency in some cases. This is tantamount to ignoring 〉 99% of the data and treating the remainder with proper relative weighting.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550191004
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  • 188
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    Electronic Resource
    Rate constants for hydrogen abstraction by resonance stabilized radicals in high temperature liquids (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 943-957 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Benzylic H-atom abstraction rates by diphenylmethyl radicals from a series of donors were determined in nonpolar liquids at elevated temperatures. Relative rates were converted to absolute rates via available equilibrium constant data for the dimerization of diphenylmethyl radicals. Abstraction by diphenylmethyl from 1, 2, 3, 4-tetrahydronaphthalene (tetralin) was studied over the temperature range 489-573 K. Its Arrhenius expression is 109.9±0.3 exp{-(10183 ± 373)/T} M-1 s-1. Abstraction from other donors was studied at 548 K. Rate constant values ranged from a low of 3.6 M-1 s-1 for toluene to a high of 3000 M-1 s-1 for 9, 10-dihydroanthracene. Similar reactions with the fluorenyl radical were also studied. In this case, relative rates were converted to absolute rates with an equilibrium constant for fluorenyl dimerization determined from the observed homolysis rate of the dimer and an assumed recombination rate. In addition, forward and reverse rate measurements yielded the equilibrium constant for hydrogen transfer between fluorenyl and diphenylmethyl. At 548 K, fluorenyl is favored by a factor of 13 over diphenylmethyl.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550191006
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  • 189
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    Editorial (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 961-961 
    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.550191102
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  • 190
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    Pyrolysis of acetylene behind reflected shock waves (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 975-996 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of acetylene has been studied in the temperature and pressure regimes of 1900-2500 K and 0.3-0.55 atm using a shock tube coupled to a time-of-flight mass spectrometer. A series of mixtures varying from 1.0-6.2% C2H2 diluted in a Ne-Ar mixture yielded a carbon atom density range of 0.24-2.0 × 1017 atoms cm-3 in the reflected shock zone. Concentration profiles for C2H2, C4H2, and C6H2 were constructed during typical observation times of 750 μs. C8H2 and trace amounts of C4H3 were found in relatively low concentrations at the high-temperature end of this study. A mechanism for acetylene pyrolysis is proposed, which successfully models this work and the results obtained by several other groups employing a variety of analytical techniques. Two values of the heat of formation for C2H(134 ± 2 and 127 ± 1 kcal/mol) were employed in the modeling process; superior fits to the data were attained using the latter value. The initial step of acetylene decomposition involves competition between two channels. In mixtures (〈200 ppm) where the acetylene concentrations are less than 2.18 × 10-9 mol cm-3, the decay is predominantly first order with respect to C2H2; in mixtures 〉200 ppm, the dominant initial step is second order. The rate constant for the second-order reaction is described by the equation \documentclass{article}\pagestyle{empty}\begin{document}$$ k = 2 \times 10^{13} \exp\, {\rm }(- 44.5{\rm\, kcal/}RT){\rm cm}^{\rm 3}\, {\rm mol}^{{\rm - 1}} {\rm s}^{{\rm - 1}} $$\end{document}Benzene concentrations predicted by the model are below the TOF detectability limit. C4H3 was observed in the 6.2% C2H2 mixture in accordance with the proposed mechanism.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550191104
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