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  • 1
    Electronic Resource
    Electronic Resource
    Ozone-isoprene reactions: Product formation and aerosol potential (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 955-975 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dark-phase experiments between isoprene and O3 are discussed. UNC outdoor chamber experiments have shown that in high-concentration systems of isoprene and O3 (5 ppm C and 1 ppm) approximately 75% of the reacted carbon can be observed in the product formation of HCHO, CO, methacrolein, methylvinylketone, methylglyoxal, acetaldehyde, and propylene. Mechanisms were developed which gave reasonable fits to dark-phase chamber experiments of MACR, MVK, isoprene, and O3. Experimental data and modeling results were used to generate O3 rates of attack on MVK and MACR. An isoprene-O3 rate of 1.67 × 10-2 ppm-1·min-1 was used and is consistent with other rates reported in the literature. Dark isoprene-O3 systems appear to form homogeneously nucleated aerosol. Most of these particles appear and remain at diameters well below the optical cutoff region (0.3-0.5 μm), as opposed to the particles from similar α-pinene-O3 systems, which also form at smaller sizes but then grow into the optical size range (0.5 μm). Lower concentrations of α-pinene and O3 (0.2 ppm C and 0.12 ppm) still generated substantial aerosol, but by comparison, rapid CN nucleation was not observed during a similar side-by-side system of isoprene and O3.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140902
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  • 2
    Electronic Resource
    Electronic Resource
    The kinetics of the gas-phase reaction between iodine and phenylsilane and the bond dissociation energy D(C6H5SiH2—H) (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 669-677 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reaction has been investigated in the temperature range of 490-573 K. Initial reactant pressures were varied in the range of 0.2-5.2 torr (I2) and 2-20 torr (C6H5SiH3). The rate of iodine consumption, monitored spectrophotometrically, was found to obey \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d[{\rm I}_{\rm 2}]}}{{dt}} = \frac{{k_{3/2} [{\rm I}_{\rm 2}]^{{\raise0.7ex\hbox{$1$} \!\mathord{\left/ {\vphantom {1 2}}\right.\kern-\nulldelimiterspace} \!\lower0.7ex\hbox{$2$}}} [{\rm C}_{\rm 6} {\rm H}_{\rm 5} {\rm SiH}_{\rm 3}]}}{{1 + k'[HI]/[I_2]}}$$\end{document} both by initial rate and integrated equation fitting procedures. The effect of added initial HI conformed to this expression. The data are consistent with a conventional I-atom propagated chain reaction, and for the step \documentclass{article}\pagestyle{empty}\begin{document}$${\rm I}^{\rm .} + {\rm C}_{\rm 6} {\rm H}_{\rm 5} {\rm SiH}_{\rm 3} \to {\rm C}_{\rm 6} {\rm H}_{\rm 5} \mathop {\rm S}\limits^{\rm .} {\rm iH}_{\rm 2} + {\rm HI}$$\end{document} the rate constant is given by \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log}k_1 (dm^3 /mol \cdot s) = (11.52 \pm 0.08) - (76.8 \pm 0.8{\rm kJ/mol})/RT{\rm ln}10$$\end{document} From this is derived the bond dissociation energy value C6H5SiH2—H = 374 kJ/mol(88 kcal/mol). A comparison with other Si—H dissociation energy values indicates that the “silabenzyl” stabilization energy is small, ≈7 kJ/mol.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140609
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  • 3
    Electronic Resource
    Electronic Resource
    Kinetics of the gas-phase reactions of OH radicals with alkyl nitrates at 299 ± 2 K (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 919-926 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate constants for the gas-phase reactions of OH radicals with a series of alkyl nitrates have been determined at 299 ± 2 K, using methyl nitrite photolysis in air as a source of OH radicals. Using a rate constant for the reaction of OH radicals with cyclohexane of 7.57 × 10-12 cm3/molec·s, the rate constants obtained are (× 1012 cm3/molec·s): 2-propyl nitrate, 0.18 ± 0.05; 1-butyl nitrate, 1.42 ± 0.11; 2-butyl nitrate, 0.69 ± 0.10; 2-pentyl nitrate, 1.87 ± 0.12; 3-pentyl nitrate, 1.13 ± 0.20; 2-hexyl nitrate, 3.19 ± 0.16; 3-hexyl nitrate, 2.72 ± 0.22; 3-heptyl nitrate, 3.72 ± 0.43; and 3-octyl nitrate, 3.91 ± 0.80. These rate constants, which are the first reported for the alkyl nitrates, are significantly lower than those for the parent alkanes, and a formula, based on the numbers of the various types of C—H bonds in the alkyl nitrates, is derived for rate constant estimation purposes.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140810
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  • 4
    Electronic Resource
    Electronic Resource
    Reaction of hydrogen atoms with diethyldisulfide and ethylmethyldisulfide (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 799-815 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: H atoms react with C2H5SSC2H5 to give C2H5SH as the sole retrievable product with φ = 2.32 at 25°C and 2.84 at 145°C. The primary reaction is postulated to be H + C2H5SSC2H5 ← C2H5SH + C2H5S with k1 = (4.73 ± 0.64) × 1013 exp [-(1710 ± 69)/RT] cm3/mol·s relative to the rate constant of the H + C2H4 ← C2H5 reaction. The high value of the entropy of activation suggests the presence of partial hydrogen bonding in diethyldisulfide which is broken in the transition state.Ethylmethyldisulfide reacts similarly: H + C2H5SSCH3 ← C2H5SH + CH3S or CH3SH + C2H5S. The thiyl radicals propagate a chain of radical exchange reactions forming the symmetrical disulfides with exposure-time-dependent quantum yields. The overall kinetics conform to a 16-step mechanism from which the rate constants of the elementary reactions could be established by computer modeling. Thiyl radicals react considerably more slowly with disulfides than H atoms.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130905
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  • 5
    Electronic Resource
    Electronic Resource
    Experimental determination of the energy distribution of activated molecules. Extensive test of hard-collision approximations (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 483-500 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The approximations developed to determine the energy distribution function of molecules activated above energy decomposition threshold, from experimental data, have been tested. The approach involved the theoretical (RRKM) calculations of “pseudoexperimental” data for a variety of activated energy distributions. (Single or double Gaussian representations were used in all cases.) Subsequently the algorithms mentioned were applied in order to recuperate the original (i.e., input) energy distributions from these pseudoexperimental data. The results obtained provide strong evidence in favor of the validity of the algorithms and illustrate the necessary requirements for their applications. A trend toward lower accuracy as the energy distributions move to higher energies has been observed. Evidence of the influence of the distribution width is also reported. The origins of the approximation errors have been studied, and ways for further improvement are suggested.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160414
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  • 6
    Electronic Resource
    Electronic Resource
    Thermal decomposition of methyl nitrite in shock waves studied by laser probing (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1139-1150 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The unimolecular decomposition of methyl nitrite in the temperature range 680-955 K and pressure range 0.64 to 2.0 atm has been studied in shock-tube experiments employing real-time absorption of CW CO laser radiation by the NO product. Computer kinetic modeling using a set of 23 reactions shows that NO product is relatively unreactive. Its initial rate of production can be used to yield directly the unimolecular rate constant, which in the fall-off region, can be represented by the second-order rate coefficient in the Arrhenius form: \documentclass{article}\pagestyle{empty}\begin{document}$$k_1 = 10^{17.90 \pm 0.21} \exp (- 17200 \pm 400/T){\rm cm}^{\rm 3} {\rm mol}^{ - 1} {\rm s}^{ - 1}$$\end{document} A RRKM model calculation, assuming a loose CH3ONO≠ complex with two degrees of free internal rotation, gives good agreement with the experimental rate constants.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160909
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  • 7
    Electronic Resource
    Electronic Resource
    Kinetic and mechanistic studies of oxidation of arginine, histidine, and threonine in alkaline medium by N-chloro-N-sodio-p-toluenesulfonamide (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 1183-1197 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of oxidation of arginine, histidine, and threonine by chloramine-T (CAT) have been investigated in alkaline medium at 35°C. The rates are first order in both [CAT] and [amino acid] and inverse fractional order in [OH-] for arginine and histidine. The rate is independent of [OH-] for threonine. Variation of ionic strength and addition of the reaction product, p-toluenesulfonamide, or Cl- ions had no effect on the rate. A decrease of the dielectric constant of the medium by adding methanol decreased the rate with arginine, while the rates increased with histidine and threonine. The solvent isotope effect was studied using D2O. (kobs)D2O/(kobs)H2O was found to be 0.55 and 0.79 for arginine and histidine, respectively. The reactions were studied at different temperatures, and activation parameters have been computed. The oxidation process in alkaline medium, under conditions employed in the present investigations, has been shown to proceed via two paths, one involving the interaction of RNHCl (formed rapidly from RNCl-), with the amino acid in a slow step to form monochloroamino acid, which subsequently interacts with another molecule of RNHCl in a fast step to give the products, p-toluenesulfonamide (RNH2), and the corresponding nitrile of the amino acid (R'CN). The other path involves the interaction of RNCl- with the amino acid in a similar way to give RNH2 and R'CN. Mechanisms proposed and the derived rate laws are consistent with the observed kinetics. The rate constants predicted using the derived rate laws, as [OH-] varies, are in excellent agreement with the observed rate constants, thus justifying these rate laws and hence the proposed mechanistic schemes.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550141103
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  • 8
    Electronic Resource
    Electronic Resource
    Laser-induced kinetics: Arrhenius parameters for t-C4H9 + XI → i-C4H9X + I (X = H,D) and the Heat of Formation of the t-butyl radical (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1283-1300 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The metathesis reaction of DI with t-C4H9 generated by 351-nm photolysis of 2,2′-azoisopropane was studied in a low-pressure reactor (VLPφ Knudsen cell) in the temperature range of 302-411 K. The data obeyed the following Arrhenius relation when combined with recent data by Rossi and Golden gathered by the same technique (t-C4H9 by thermal decomposition of 2,2′-azoisobutane): log k2D(M-1s-1) = 9.60 - 1.90/θ, where θ = 2.303RT kcal/mol for 302 K 〈 T 〉 722 K. The metathesis reaction of HI with t-C4H9 was studied at 301 K and resulted in k2H(M-1·s-1) = (3.20 ± 0.62) × 108. An analogous Arrhenius relation was calculated for the protiated system if the small primary isotope effect k2H/k2D was assumed to be √2 at 700 K. It was of the following form: log k2H(M-1·s-1) = 9.73 - 1.68/θ.Preliminary data of Bracey and Walsh indicate that earlier Arrhenius parameters determined for the reverse reaction are somewhat in error. Their value of log k1(M-1·s-1) = 11.5 - 23.8/θ yields 7delta;Hf,3000(t-butyl) = 9.2 kcal/mol and S3000(t-butyl) = 74.2 cal/mol7°K when taken in conjuction with this study.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151204
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  • 9
    Electronic Resource
    Electronic Resource
    The reactions of hydrogen atoms with bis(trifluoromethyl)disulfide (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 741-752 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of hydrogen atoms produced by the mercury-photosensitized decomposition of H2 with bis(trifluoromethyl)disulfide has been studied. The rate coefficient for the primary reaction, H + CF3SSCF3 → CF3SH + CF3S, was determined in competition with the reaction H + C2H4S → SH + C2H4 to have the value k = (3.0 ± 0.18) × 1014 exp[-(4560 ± 140)/RT] cm3 mol-1 S-1. The high A factor can be partially accounted for by assuming free rotation for the two CF3 groups and the SCF3 groups about the S - S bond in the transition state. The relatively high activation energy is attributed to inductive and orbital overlap effects. CH3SH, H2S, and CF3SH all react with CF3SSCF3 to yield solid complexes which were not explored further.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160610
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  • 10
    Electronic Resource
    Electronic Resource
    Kinetics of the reaction of oh radicals with a series of branched alkanes at 297 ± 2 K (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 469-481 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate constants for the reaction of OH radicals with a series of branched alkanes have been determined at 297 ± 2 K, using methyl nitrite photolysis in air as a source of OH radicals. Using a rate constant for the reaction of OH radicals with n-butane of 2.58 × 10-12 cm3/molecule · s, the rate constants obtained are (× 1012 cm3/molecule · s): isobutane, 2.29 ± 0.06; 2-methylbutane, 3.97 ± 0.11; 2,2-dimethylbutane, 2.66 ± 0.08; 2-methylpentane, 5.68 ± 0.24; 3-methylpentane, 5.78 ± 0.11; 2,2,3-trimethylbutane, 4.21 ± 0.08; 2,4-dimethylpentane, 5.26 ± 0.11; methylcyclohexane, 10.6 ± 0.3; 2,2,3,3-tetramethylbutane, 1.06 ± 0.08; and 2,2,4-trimethylpentane, 3.66 ± 0.16. Rate constants for 2,2-dimethylbutane, 2,4-dimethylpentane, and methylclohexane have been determined for the first time, while those for the other branched alkanes are in generally good agreement with the literature data. Primary, secondary, and tertiary group rate constants at room temperature have been derived from these and previous data for alkanes and unstrained cycloalkanes, with the secondary and tertiary group rate constants depending in a systematic manner on the identity of the neighboring groups. The use of these group rate constants, together with a previous determination of the effect of ring strain energy on the OH radical rate constants for a series of cycloalkanes, allows the a priori estimation of OH radical rate constants for alkanes and cycloalkanes at room temperature.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160413
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