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  • 1980-1984  (594)
  • Physical Chemistry  (593)
  • Nuclear reactions
  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 397-405 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A vacuum ultraviolet photolysis of C2H5Br at 147 nm was studied over a pressure range of 0.5-50 torr at 298 K. The effects of additives He and NO were also investigated.The principal reaction products were found to be C2H4 and C2H6, with lesser yields of CH4 and C2H2. With increasing pressure the product quantum yields Φi of C2H4, CH4, and CH2H6 remained constant, while that of C2H2 decreased from 0.03 to almost 0. The effect of He as an additive was found to be extremely small on the quantum yields of the major products. Addition of NO completely suppresses the formation of CH4, C2H2, and C2H6, and reduces partially the production of C2H4. The primary processes appear to involve two electronically excited states. One state mainly yields C2H4 by molecular elimination of HBr and is thought to be due to a Rydberg transition. The other state decomposes to C2H5 and Br radicals by C—Br bond fission. These two competitive reaction modes contribute to the photodecomposition in proportions of 50% and 50%. The extinction coefficient for C2H5Br at 147 nm and at 298 K has been determined as ∊ = (1/PL) In(Io/It) = 712 ± 7 atm-1 · cm-1.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 603-620 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of methyl radicals (Me) with hexafluoroacetone (HFA), generated from ditertiary butyl peroxide (dtBP), was studied over the temperature range of 402-433 K and the pressure range of 38-111 torr. The reaction resulted in the following displacement process taking place: where TFA refers to trifluoroacetone. The trifluoromethyl radicals that were generated abstract a hydrogen atom from the peroxide: such that k6a is given by: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}\,\,k_{6{\rm a}} \left( {M^{ - 1} \cdot {\rm s}^{ - 1} } \right)\,\, = \,\,8.2\, \pm \,0.7\, - \,8.9\, \pm \,{{1.3} \mathord{\left/ {\vphantom {{1.3} \theta }} \right. \kern-\nulldelimiterspace} \theta } $$\end{document} where θ = 2.303RT kcal/mol. The interaction of methyl and trifluoromethyl radicals results in the following steps: Product analysis shows that k17/k151/2k161/2 = 2.0 ± 0.2 such that k17 = 1010.4±0.5M-1 · s-1. The rate constant k5 is given by: \documentclass{article}\pagestyle{empty}\begin{document}$$ {{{\rm log}\,\,k_5 } \mathord{\left/ {\vphantom {{{\rm log}\,\,k_5 } {\left( {M^{ - 1} \cdot {\rm s}^{ - 1} } \right)}}} \right. \kern-\nulldelimiterspace} {\left( {M^{ - 1} \cdot {\rm s}^{ - 1} } \right)}}\,\, = \,\,8.0\, \pm \,1.3\, - \,5.1\, \pm \,{{0.7} \mathord{\left/ {\vphantom {{0.7} \theta }} \right. \kern-\nulldelimiterspace} \theta } $$\end{document} It is concluded that the preexponential factor for the addition of methyl radicals to ketones is lower than that for the addition of methyl radicals to olefins.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 707-724 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of labeled N15NO+ with CO, NO, O2, 18O2, N2, NO2, and N2O have been investigated using a tandem ICR instrument. In each case the total rate coefficient, product distribution, and kinetic energy dependence were measured. The results indicate that very specific reaction mechanisms govern these reactions. This conclusion is suggested by the lack of isotopic scrambling in many cases and by the complete absence of energetically allowed products in almost all of the systems. The kinetic energy studies indicate that most of the reaction channels proceed through an intermediate complex at low energies and via a direct mechanism at higher kinetic energies. Such direct mechanisms include long range charge transfer and atom or ion transfer.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 793-799 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Boiling-temperature measurements have been used to study the kinetics of the decomposition of urea. Values for the rate constants in neutral, acid, and basic media have been obtained and compared with literature data. The effect of the reverse reaction on the value of the experimental rate constants is discussed. The profile of the ebulliometric curves is different for the three media and is correlated with the number of various species present in solution. It is concluded that ebulliometric measurements can be useful for kinetic studies.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 835-847 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chlorocyclopropane has been produced by addition of CH2(1A1) and CH2(3B1) to chloroethene. CH2 was generated by the photolysis of ketene at 313 and 366 nm. Chlorocyclopropane was formed in a chemically activated state, had an energy content between 378 and 427 kJ/mol, and reacted in three parallel channels to 3-chloropropene, cis- and trans-1-chloropropene. As secondary reactions elimination of HCl from the chemically activated primary products occurred to form allene and propyne. The apparent rate constants for the isomerization and elimination reactions are reported. The results of RRKM calculations including distribution functions for the activated chlorocyclopropane and a stepladder model for the deactivation support the proposed reaction scheme.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 801-816 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and mechanism of the thermal decomposition of n-propylsilane have been studied by the single pulse shock tube-comparative rate technique at pressures around 4700 torr between 1095-1240 K. The primary dissociation processes are 1,1 and 1,2 H2 elimination with ø1,1 ⋍ 0.75 and ø1,2 ⋍ 0.25, respectively. Subsequent decompositions of the primary process product, n-propylsilylene, to propylene and ethylene is complete even in the presence of excess butadiene. Possible mechanistic paths for these decompositions are discussed and an activation energy range of 30 ± 4 kcal is established for both processes. Induced decomposition via silylene chains accounts for 36-46% of the overall reaction in the uninhibited decomposition of n-propylsilane. The silylene chains are quenched in excess butadiene, and studies under maximum inhibition give overall decomposition kinetics of, log k(nPrSiD3, s-1) = 15.26-65,300 ± 1950 cal/2.303. Computer modeling results of the overall reaction both in the absence and presence of butadiene are also presented and shown to be in acceptable agreement with the experimental observations.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 817-834 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of hydrogen oxidation near the lower explosion limit in the kinetic region of chain termination has been studied. Major effects, causing deviations of the reaction kinetics from calculations by the linear theory of branched chain processes, are shown to be (1) the inhibition of the reacting mixture by the products of interaction of active centers with vacuum grease or with impurities contained in it and (2) the heterogeneous negative interaction of reaction active centers. The kinetics of hydrogen oxidation in this region has been calculated with consideration of the heterogeneous negative chain interaction. A set of parameters has been obtained that make it possible to determine by the shape of the kinetic curves the sign and the value of nonlinear interaction of chains near the lower explosion limit. It has been shown that the experimental data are in good agreement with the calculations, provided the heterogeneous negative chain interaction is taken into consideration and the inhibiting effect of impurities is eliminated. The rate of heterogeneous generation of chains on a quartz surface treated with hydrofluoric or boric acid has been determined.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 849-866 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An efficient process for converting the energy stored in electronically excited NF(a1Δ) into blue-green BiF (A—X) band emissions has been discovered. Bismuth atoms are converted to BiF and then repeatedly pumped to the (AO+) state in two steps via collisions with NF(a1Δ). A model has been formulated that predicts BiF emission intensities that are in excellent agreement with the observed values. Some of the rate coefficients required for this model are estimated by means of charge-transfer theories. The cyclic nature of this system, along with its other basic properties, suggests that it has a strong potential to be an efficient blue-green laser system.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 867-878 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of OH reactions with furan (k1), thiophene (k2), and tetrahydrothiophene (k3), have been investigated over the temperature range 254-425 K. OH radicals were produced by flash photolysis of water vapor at λ 〉 165 nm and detected by timeresolved resonance fluorescence spectroscopy. The following Arrhenius expressions adequately describe the measured rate constants as a function of temperature (units are cm3 molecule-1 S-1): k1 = (1.33 ± 0.29) × 10-11 exp[(333 ± 67)/T], k2 = (3.20 ± 0.70) × 10-12 exp[(325 ± 71)/T], k3 = (1.13 ± 0.35) × 10-11 exp[(166 ± 97)/T]. The results are compared with previous investigations and their implications regarding reaction mechanisms and atmospheric residence times are discussed.
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  • 11
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 879-886 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate constants for the reactions of hydroxyl radicals with a series of alkyl substituted olefins were measured by competitive reactions between pairs of olefins at 298 ± 2 K and 1 atmospheric pressure. Hydroxyl radicals were produced by the photolysis of H2O2 with 254-nm irradiation. The obtained rate constants were (× 10-11 cm3 molecule-1 s-1): 2.53 ± 0.06, propylene; 5.49 ± 0.17, cis-2-butene; 5.47 ± 0.1, isobutene; 6.46 ± 0.13, 2-methyl-1-butene; 6.37 ± 0.16, cis-2-pentene; 6.23 ± 0.1, 2-methyl-1-pentene; 8.76 ± 0.14, 2-methyl-2-pentene; 6.24 ± 0.08, trans-4-methyl-2-pentene; 10.3 ± 0.1, 2,3-dimethyl-2-butene; 9.94 ± 0.1, 2,3-dimethyl-2-pentene; 5.59 ± 0.07, trans-4,4-dimethyl-2-pentene. A trend in alkyl substituent effect on the rate constant was found, which is useful to predict kOH on the basis of the number of alkyl substituents on the double bond.
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  • 12
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 899-907 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of ground-state S(3PJ) atoms with thiirane, methylthiirane, and trans-2,3-dimethylthiirane have been studied by flash photolysis-VUV kinetic absorption spectroscopy. From the analysis of the S(3PJ) decay plots the following rate constants were determined: (1.4 ± 0.2) × 1013, (2.7 ± 0.3) × 1013 and (4.0 ± 0.2) × 1013 (in cm3 mol-1 s-1 units) for thiirane, methylthiirane and trans-2,3-dimethylthiirane, respectively, showing an upward trend with increasing methylation.
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  • 13
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 887-898 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants have been determined at 296 ± 2 K for the gas phase reaction of NO3 radicals with a series of aromatics using a relative rate technique. The rate constants obtained (in cm3 molecule-1 s-1 units) were: benzene, 〈2.3 × 10-17; toluene, (1.8 ± 1.0) × 10-17; o—xylene, (1.1 ± 0.5) × 10-16; m—xylene, (7.1 ± 3.4) × 10-17; p—xylene, (1.4 ± 0.6) × 10-16; 1,2,3-trimethylbenzene, (5,6 ± 2.6) × 10-16; 1,2,4-trimethylbenzene (5.4 - 2.5) × 10-16; 1,3,5-trimethylbenzene, (2.4 ± 1.1) × 10-16; phenol, (2.1 ± 0.5) × 10-12; methoxybenzene, (5.0 ± 2.8) × 10-17; o-cresol, (1.20 ± 0.34) × 10-11; m-cresol, (9.2 ± 2.4) × 10-12; p-cresol, (1.27 ± 0.36) × 10-11; and benzaldehyde, (1.13 ± 0.25) × 10-15. These kinetic data, together with, in the case of phenol, product data, suggest that these reactions proceed via H-atom abstraction from the substituent groups. The magnitude of the rate constants for the hydroxy-substituted aromatics indicates that the nighttime reaction of NO3 radicals with these aromatics can be an important loss process for both NO3 radicals and these organics, as well as being a possible source of nitric acid, a key component of acid deposition.
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  • 14
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 909-918 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absolute rate constants for reversible addition of the substituted phenylthio radicals to vinylpyridines in solution at 23°C have been determined by flash photolysis method. For each phenylthio radical, the reactivities of vinylpyridines is 3-5 times lower than that of styrene. The relative equilibrium constants estimated with flash photolysis indicate that the stabilities of the adduct carbon-centered radicals generated from vinylpyridines are similar to that from styrene. The Hammett plots suggest that the difference in the reactivities originates in the polar transition state; the nitrogen atom in 4-vinylpyridine withdraws the electrons of vinylic double bond.
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  • 15
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 941-945 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: NO Abstract.
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  • 16
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 17
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 919-939 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The formation of nitrous acid (HONO) in the dark from initial concentrations of NO2 of 0.1-20 ppm in air, and the concurrent disappearance of NO2, were monitored quantitatively by UV differential optical absorption spectroscopy in two different environmental chambers of ca.4300- and 5800-L volume (both with surface/volume ratios of 3.4 m-1). In these environmental chambers the initial HONO formation rate was first order in the NO2 concentration and increased with the water vapor concentration. However, the HONO formation rate was independent of the NO concentration and relatively insensitive to temperature. The initial pseudo-first-order consumption rate of NO2 was (2.8 ± 1.2) × 10-4 min-1 in the 5800-L Teflon-coated evacuable chamber and (1.6 ± 0.5) × 10-4 min-1 in a 4300-L all-Teflon reaction chamber at ca.300 K and ca.50% RH. The initial HONO yields were ca.40-50% of the NO2 reacted in the evacuable chamber and ca.10-30% in the all-Teflon chamber. Nitric oxide formation was observed during the later stages of the reaction in the evacuable chamber, but ca.50% of the nitrogen could not be accounted for, and gas phase HNO3 was not detected. The implications of these data concerning radical sources in environmental chamber irradiations of NOx- organic-air mixtures, and of HONO formation in polluted atmospheres, are discussed.
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  • 18
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1103-1110 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Results obtained from the photolysis of ketene with acetylene strongly support the formation of C3H3 radicals in the title reaction. Stationary state studies are interpreted in terms of the reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm C}_3 {\rm H}_{\rm 4}^{\rm *} \buildrel3\over\rightarrow{\rm C}_3 {\rm H}_3^ \cdot + {\rm H}^ \cdot$$\end{document} with a rate constant (109.8 s-1) which is compared to RRKM predictions. In pulsed laser induced decomposition experiments, recombination products involving C3H3 have been detected (some for the first time) and their formation modeled using step (3) with the same rate constant.
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  • 19
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1111-1115 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the self- and cross-termination of the isopropylol radical [(CH3)2ĊOH] and its anion [(CH3)2ĊO-] in aqueous solution are determined by kinetic electron spin resonance. Whereas the self-termination of the neutral radical occurs close to the diffusion-controlled limit, the cross- and self-terminations involving the anion are slower and reflect effects of charge repulsion and steric constraints by solvation.
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  • 20
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1151-1160 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absolute rate constant for the OH + HCl reaction has been measured from 240 to 295 K utilizing the techniques of laser/flash photolysis-resonance fluorescence. The HCl concentrations were monitored continuously by ultraviloet and infrared spectrophotometry. The results can be fit to the following Arrhenius expression: \documentclass{article}\pagestyle{empty}\begin{document}$$k_1 = (4.6{\rm } \pm {\rm }0.3){\rm } \times {\rm }10^{ - 12} \exp [- (500{\rm } \pm {\rm }60)/T{\rm cm}^3 /{\rm molecule} \cdot {\rm s}$$\end{document} The rate constant values obtained in this study are 20-30% larger than those recommended previously for modeling of stratospheric chemistry.
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  • 21
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1139-1150 
    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.
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  • 22
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1161-1166 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction \documentclass{article}\pagestyle{empty}\begin{document}${\rm Br} + {\rm CH}_3 {\rm CHO}\buildrel1\over\rightarrow{\rm HBr} + {\rm CH}_3 {\rm CO}$\end{document} has been studied by VLPR at 300 K. We find k1 = 2.1 × 1012 cm3/mol s in excellent agreement with independent measurements from photolysis studies. Combining this value with known thermodynamic data gives k-1 = 1 × 1010 cm3/mol s. Observations of mass 42 expected from ketene suggest a rapid secondary reaction: \documentclass{article}\pagestyle{empty}\begin{document}$${\rm Br} + {\rm CH}_3 {\rm CO}\buildrel2\over\rightarrow[{\rm CH}_3 {\rm COBr}]^* \buildrel3\over\rightarrow{\rm HBr} + {\rm CH}_2 {\rm CO}$$\end{document} in which step 2 is shown to be rate limiting under VLPR conditions and k2 is estimated at 1012.6 cm3/mol s from recent theoretical models for radical recombination. It is also shown that 0 ≤ E1 ≤ 1.4 kcal/mol using theoretical models for calculation of A1 and is probably closer to the lower limit. Reaction -1 is negligible under conditions used.
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  • 23
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 24
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1167-1173 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Potassium persulfate oxidizes triphenylphosphine to triphenylphosphine oxide in 60% aqueous acetonitrile. It has been suggested that the oxygen of the product, triphenylphosphine oxide, might originate from solvent water, following nucleophilic attack on an intermediate phosphonium ion. We have investigated the origin of the oxygen in the oxidation of triphenylphosphine by potassium persulfate in 60% aqueous acetonitrile containing 20% [18O]water. The product was analyzed by using the 18O isotope effect in 31P NMR spectroscopy. The magnitude of the 18O isotope-induced shift was determined by synthesizing triphenylphosphine [18O]oxide and was found to be 0.038 ppm upfield. The product of the oxidation reaction in 20% [18O]water displayed no 18O isotope effect. The origin of the oxygen in the oxidation reaction is the persulfate ion, consistent with an alternative mechanism involving nucleophilic attack by water at the sulfur atom of a phosphonium peroxysulfate intermediate.
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  • 25
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1213-1226 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown how kinetic electron spin resonance spectroscopy with intermittent radical generation can be used to obtain rate constants of various simultaneous reactions in systems containing more than one kind of transient radicals. The technique is applied to reactions of tert-butyl [(CH3)3Ċ] and isopropylol [(CH3)2ĊOH] radicals generated by photolysis of di-tert-butyl ketone and acetone in 2-propanol/acetone mixtures. It yields the rates of generation of the two radicals, the rate constants for their self- and crossterminations and for the reaction of tert-butyl with 2-propanol. The extent of diffusion control of the termination constants is discussed.
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  • 26
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1247-1256 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The extinction coefficients and the decay kinetics of I2-. and (SCN)2-⋅ have been characterized over the 15-90°C-temperature range. The extinction coefficients of I2-⋅ at 385 and 725 nm were determined to be 10,000 and 2560M-1 cm-1, respectively, based on the extinction coefficient of (SCN)2-⋅ at 475 nm being equal to 7600M-1 cm-1. At these three wavelengths, all extinction coefficients were constant over the temperature range studied. The rate of decay of both I2-⋅ and (SCN)2-⋅ was found to be a function of I- and SCN- concentration, respectively, as well as temperature.
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  • 27
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1227-1246 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of O3 with ethylene, allene, 1,3-butadiene, and trans-1,3-pentadiene have been studied in the presence of excess O2 over the temperature range 232 to 298 K. The initial O3 pressure was varied from 4-18 mtorr, and the olefin pressure was varied from 0.1 to 4.5 torr (ethylene), 2.8 to 39.6 torr (allene), 52.7 to 600 mtorr (1,3-butadiene) or 26.2 to 106 mtorr (trans-1,3-pentadiene). The O3 decay was monitored by ultraviolet absorption. The reactions are first order in both O3 and olefin, and the rate coefficients are independent of the O2 pressure. For the O3-ethylene system, various diluent gases (O2, N2, air) were used and the rate coefficients were found to be independent of the nature of the diluent gas. The various rate coefficients fit the Arrhenius expressions (k in cm3 s-1): \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l}{\rm For C}_{\rm 2} {\rm H}_4 :k\{ 232 - 298{\rm K}\} {\rm } = {\rm }(7.72 \pm 0.89){\rm } \times {\rm 10}^{ - 15} \exp [- 5080{\rm } \pm {\rm }60)/RT] \\ {\rm For C}_{\rm 3} {\rm H}_4 :k\{ 252 - 298{\rm K}\} {\rm } = {\rm }(1.54 \pm 0.25){\rm } \times {\rm 10}^{ - 15} \exp [- 5343{\rm } \pm {\rm }87)/RT] \\ {\rm For 1,3 - C}_{\rm 4} {\rm H}_{\rm 6} :k\{ 254 - 299{\rm K}\} {\rm } = {\rm }(2.20 \pm 0.44){\rm } \times {\rm 10}^{ - 14} \exp [- 4828{\rm } \pm {\rm }109)/RT] \\ {\rm For trans - 1,3 - C}_{\rm 5} {\rm H}_{\rm 8} :k\{ 238 - 298{\rm K}\} {\rm } = {\rm }(1.07 \pm 0.25){\rm } \times {\rm 10}^{ - 13} \exp [- 4608{\rm } \pm {\rm }122)/RT] \\ \end{array}$$\end{document} where the reported uncertainties are one standard deviation and R is in cal/mol K.
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  • 28
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1257-1266 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The problem of diethanolamine (DEA) degradation in gas-treating processes was quantified through a detailed kinetic study. This reaction was found to be catalyzed by CO2, and degradation occurs in a successive manner to 3-(2-hydroxyethyl)oxazolidone-2, to N,N,N′-tris(2-hydroxyethyl)ethylenediamine and then to N,N′-bis(2-hydroxyethyl)piperazine. A reaction mechanism consistent with these observations was proposed and tested through kinetic analyses. A satisfactory kinetic model which can be of practical use was derived.
    Additional Material: 4 Ill.
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  • 29
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis kinetics of several ethyl esters with polar substituents at the acyl carbon have been studied in the temperature range of 319.8-400.0°C and pressure range of 50.5-178.0 torr. These eliminations are homogeneous, unimolecular, and follow a first-order rate law. The rate coefficients are given by the Arrhenius equations: for ethyl glycolate, log k1 (s-1) = (12.75 ± 0.30) - (201.4 ± 3.8) kJ/mol/2.303RT; for ethyl cyanoacetate, log k1 (s-1) = (12.19 ± 0.18) - (191.8 ± 2.1) kJ/mol/2.303RT; for ethyl dichloroacetate, log k1 (s-1) = (12.62 ± 0.36) - (193.9 ± 4.3) kJ/mol/2.303RT; for ethyl trichloroacetate, log k1 (s-1) = (12.27 ± 0.09) - (185.1 ± 1.0) kJ/mol/2.303RT. The results of the present work together with those reported recently in the literature give an approximate linear correlation when plotting log k/k0 vs. σ* values (ρ* = 0.315 ± 0.004, r = 0.976, and intercept = 0.032 ± 0.006 at 400°C). This linear relationship indicates that the polar substituents affect the rate of elimination by electronic factors. The greater the electronegative nature of the polar substituent, the faster is the pyrolysis rate. The alkyl substituents yield, within experimental error, similar values in rates which makes difficult an adequate assessment of their real influence.
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  • 30
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By photolyzing azomethane over the temperature range 331-491 K in the presence of trifluoroacetone the kinetics of the addition reaction (1), ĊH3 + CF3COCH3 → CF3C(Ȯ)(CH3)2 have been studied. Detailed analyses have shown that the principal product of the adduct radical, CF3C(Ȯ)(CH3)2, is CH3COCH3 from reaction (-2), CF3C(Ȯ)(CH3)2 → CH3COCH3 + ĊF3. The rate constant of the addition reaction has been determined to be k1(dm3/mol s) = (4.5 ± 1.4) × 107 exp(-(3370 ± 120)/T) over the temperature range 331-491 K, based on the value k3 = 2.2 × 1010 dm3/mol s for the reaction (3), 2ĊH3 → C2H6. The results are discussed in relation to existing data for radical additions to groups.
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  • 31
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1351-1356 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of some perfluoroalkyl radicals with carbon tetrachloride have been studied using the photolysis of the corresponding perfluoroalkyl iodide as the free radical source. The Arrhenius parameters, based on the value of 2.3 × 1013 cm3 mol-1 s-1 for the self-combination rate constant of all radicals are: TextReactionlog(A/cm3 mol-1 s-1)E/kcal mol-1CF3 + CCl412.811.3C2F5 + CCl412.811.6n-C3F7 + CCl412.912.0
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  • 32
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1337-1350 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of trans-3,4-dimethylcyclopentanone has been studied in the gas phase, principally at 313 nm. However, a few experiments have also been performed using laser sources at 308 and 325 nm. Additionally, experiments were also carried out using the cis isomer. The major products produced by all three wavelengths and in the temperature range 100 to 150°C were propene, 1,2-dimethylcyclobutane, carbon monoxide, and 3,4-dimethylpent-4-en-al. The formation of the cyclobutane was stereospecific and the effects of temperature, pressure, and wavelength on the relative product yields could be rationalized in terms of a mechanism involving the formation of a vibrationally excited triplet state which could yield both hydrocarbons and the aldehyde and a nonexcited triplet yielding only the aldehyde. Some high intensity experiments with an exciplex laser at 308 nm gave results which could be due to the occurrence of some two photon absorption by the cyclopentanone or absorption by an excited intermediate. The results are compared with those previously reported for other substituted cyclopentanones.
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  • 33
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1357-1370 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase reaction of CF3 with HCN has been examined over a wide conversion range using CF3I as a thermal and photolytic source of radicals. Quantitative and qualitative results show a significant increase of the specific rate constant for the hydrogen abstraction reaction relative to CF3 recombination when reaction is carried out under ultraviolet irradiation. This “extra” formation of the reaction product, CF3H, has been assigned to the participation of iodine in this system through the formation of a (I-HCN) intermediate. Arrhenius parameters obtained for the addition mechanism of I to HCN do not seem to conform to a single reaction step, on the contrary, they correspond to a more complex reaction scheme.
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  • 34
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1371-1383 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition kinetics of ethylsilane under shock tube conditions (PT ca. 3100 torr, T ≃ 1080-1245 K), both in the absence and presence of silylene trapping agents (butadiene and acetylene) are reported. Arrhenius parameters under maximum butadiene inhibition are: log k(C2H5SiH3) = 15.14-64,769 ± 1433 cal/2.303 RT; log k(C2H5SiD3) = 15.29-66,206 ± 1414/2.303 RT. The uninhibited reaction is subject to silylene induced decomposition (63% lowest T -- 24% highest T). Major reaction products are ethylene and hydrogen, consistent with two dominant primary dissociation reactions: C2H5SiD3 → C2H5SiD + D2, φ ≃ 0.66; C2H5SiD3 → CH3CH = SiD2 + HD, φ ≃ 0.30. Minor products suggest several other less important primary processes: alkane elimination, φ ≃0.02, and free-radical production via simple bond fission, φ ≃0.02. An upper limit for the activation energy of the decomposition, C2H5SiH → C2H4 + SiH2, of E 〈 30 ± 4 kcal is established, and speculations on the mechanism of this decomposition (concerted or stepwise) with conclusions in favor of the stepwise path are made. Computer modeling studies for the reaction both in the absence and presence of butadiene are shown to be in good agreement with the experimental observations.
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  • 35
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1401-1426 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Small low residence time flow tube reactors made of alumina and used as molecular beam sources are described. In these reactors, gas mixtures are rapidly heated and brought to reaction. The composition of the gas leaving the reactor is analyzed by molecular beam mass spectroscopy. For quantitative simulation of the reacting gas flow, the theory of one-dimensional compressible flow with friction, heat transfer, and chemical reaction is brought into a form suitable for practical computation. The system has been applied to study the thermal decompositions of O3 and N2O. The experimental results on both reactions can be well modeled by homogeneous reaction mechanisms with accepted rate constants. Heterogeneous reaction steps are shown to be unimportant.
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  • 36
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1427-1454 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The use of the KMS method for the evaluation of the exponent by the experimentalist requires that a lag or retardation be chosen. The best choice of lag is discussed quantitatively. Its dependence upon the decade range of the data, the relative magnitude of the background, the level and character of the noise, the number and distribution of the data, and the weighted least-squares method of analysis are all detailed. A table of lags and error factors is given, for various ranges, backgrounds, and kinds of noise. Bias in the extracted rate (k), due to noise and treatment of the data, is also discussed.
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  • 37
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photooxidation of acrylonitrile, methacylonitrile, and allylcyanide in the presence of NO was studied in parts per million concentration using the long-path Fourier transform IR spectroscopic method. The stoichiometry of the OH radical initiated oxidation of methacrylonitrile was established as \documentclass{article}\pagestyle{empty}\begin{document}$ \left( {{\rm OH}} \right) + {\rm CH}_{\rm 2} = {\rm C}\left( {{\rm CH}_{\rm 3} } \right){\rm CN + 2NO + 2O}_{\rm 2} \mathop {\hbox to 20pt{\rightarrowfill}}\limits^{1.0} {\rm HCHO + CH}_{\rm 3} {\rm COCN + 2NO}_{{\rm 2}} + \left( {{\rm OH}} \right) $\end{document}. The yield of HCHO for acrylonitrile and allylcyanide was found to be ca. 100 and 80%, and the stoichiometric reactions were assessed to proceed, \documentclass{article}\pagestyle{empty}\begin{document}$ \left( {{\rm OH}} \right) + {\rm CH}_{\rm 2} = {\rm CHCN + 2NO + 2O}_{\rm 2} \mathop {\hbox to 20pt{\rightarrowfill}}\limits^{1.0} {\rm HCHO + HCOCN + 2NO}_{\rm 2} + \left( {{\rm OH}} \right) $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ \left( {{\rm OH}} \right) + {\rm CH}_{\rm 2} = {\rm CHCH}_{\rm 2} {\rm CN + 2NO + 2O}_{\rm 2} \mathop {\hbox to 20pt{\rightarrowfill}}\limits^{0.8} {\rm HCHO + HCOCH}{\rm 2} {\rm CN + 2NO}_{\rm 2} + \left( {{\rm OH}} \right) $\end{document}, respectively. These results revealed that the reaction mechanism for these unsaturated organic cyanides are analogous to that of olefins.
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  • 38
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 39
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. i 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 40
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1-5 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of the polarity of seven solvents (∊ ≈ 2-60) on the rate of ozone reactions with stilbene and allyl chloride has been studied. The data show that the rate of the reaction is insensitive to the medium polarity. The results of earlier publications are revised and are shown to be in agreement with the present data.
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  • 41
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 7-21 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase decompositions of methylsilane and methylsilane-d3 have been investigated in a single-pulse shock tube at 4700 torr total pressure in the temperature range of 1125-1250 K. For CH3SiD3 at 1200 K three primary steps occur in the homogeneous decomposition with efficiencies in parentheses: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} {\rm SiD}_{\rm 3} \mathop {\longrightarrow} \limits^1 {\rm CH}_{\rm 3} {\rm SiD} + {\rm D}_{\rm 2} \left( {0.71} \right) $$\end{document}, \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} {\rm SiD}_{\rm 3} \mathop {\longrightarrow} \limits^2 {\rm CH}_{\rm 4} + {\rm SiD}_{\rm 2} \left( {0.15} \right) $$\end{document}, and \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} {\rm SiD}_{\rm 3} \mathop {\longrightarrow} \limits^3 {\rm CH}_{\rm 2} \raise1pt\hbox{=\kern-3.45 pt=} {\rm SiD}_{\rm 2} \left( {0.14} \right) $$\end{document}. For CH3SiH3 at 1200 K the primary CH4 elimination efficiency is 0.09 while the total primary H2 elimination efficiency is 0.91. Minor product formations of C2H4, acetylene, dimethylsilane, and SiH4 are discussed.
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  • 42
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 23-30 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The static system pyrolysis of methylsilane (T ∼ 700 K, PT ∼ 150 torr), pure and in the presence of ethylene, propylene, and acetylene, has been investigated. It is proposed that in the uninhibited system, the major products (silane and dimethylsilane) are produced by free radical processes, and that the free radicals are formed at the walls from methylsilylenes. In the presence of olefins, the free radicals are trapped to form methylsilane adducts. In acetylene, trapping of methylsilylenes prevents free radical production and eliminates the free radical produced products of the pure and the olefin inhibited systems. Rates of initiation correlate with rates of reactant loss in acetylene inhibited systems, and with rates of hydrogen formation in olefin inhibited systems. Rough estimates of primary dissociation process yields give for the 1,1-H2 elimination φ1,1 ≅ 0.78, for the 1,2-H elimination φ1,2 ≅ 0.16, and for the methane elimination φCH4 ≅ 0.06 at 700 K. Deuteration lowers initial step kinetics by about 15%.
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  • 43
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 31-39 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The homogeneous gas-phase decomposition kinetics of methylsilane and methylsilane-d3 have been investigated by the comparative-rate-single-pulse shock-tube technique at total pressures of 4700 torr in the 1125-1250 K temperature range. Three primary processes occur: CH3SiH3 → CH3SiH + H2 (1), CH3SiH3 → CH4 + SiH2 (2), and CH3SiH3 → CH2 = SiH2 + H2 (3). The high-pressure rate constants for the primary processes in CH3SiH3 obtained by RRKM calculations are log (k1 + k3) (s-1) = 15.2 - 64,780 Cal/θ and log k2 (s-) = 14.50 - 67,600 → 2800 Cal/θ. For CH3SiD3 these same rate constants are log k1 (s-) = 14.99 - 64,700 cal/θ log k2 (s-) = 14.68 - 66,700 → 2000 cal/θ, and log k3 (s-) = 14.3 - 64,700 cal/θ.
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  • 44
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 45
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cross-disproportionation/combination ratios for CFH2 and CF3 with C2H5 radicals have been determined to be Δ = 0.032 ± 0.012 and δ = 0.098 ± 0.020, respectively, over the temperature range 25-75°C. For the pathway that yields CFH and C2H6, δ = 0.020 ± 0.005 at 25°C.
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  • 46
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 41-55 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absolute rate constants for the reactions of OH + HO2NO2 (1) and OH + HNO3 (2) have been measured with the technique of flash photolysis resonance fluorescence over the temperature ranges of 240-330 K at 760 torr He for reaction (1) and of 240-370 K at 50 and 760 torr He for reaction (2). Reactant concentrations were monitored continuously by ultraviolet and infrared spectrophotometry. The data can be fitted to the following Arrhenius expressions: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = \left( {5.9 \pm 0.4} \right) \times 10^{ - 13} \exp \left[ {{{\left( {650 \pm 30} \right)} \mathord{\left/ {\vphantom {{\left( {650 \pm 30} \right)} T}} \right. \kern-\nulldelimiterspace} T}} \right]{{{\rm cm}^{\rm 3} } \mathord{\left/ {\vphantom {{{\rm cm}^{\rm 3} } {{\rm molecule} \cdot {\rm s}}}} \right. \kern-\nulldelimiterspace} {{\rm molecule} \cdot {\rm s}}} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} {\rm SiD}_{\rm 3} \mathop {\longrightarrow} \limits^3 {\rm CH}_{\rm 2} \raise1pt\hbox{=\kern-3.45 pt=} {\rm SiD}_{\rm 2} \left( {0.14} \right) $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_2 = \left( {8.3 \pm 0.9} \right) \times 10^{ - 15} \exp \left[ {{{\left( {850 \pm 40} \right)} \mathord{\left/ {\vphantom {{\left( {850 \pm 40} \right)} T}} \right. \kern-\nulldelimiterspace} T}} \right]{{{\rm cm}^{\rm 3} } \mathord{\left/ {\vphantom {{{\rm cm}^{\rm 3} } {{\rm molecule} \cdot {\rm s}}}} \right. \kern-\nulldelimiterspace} {{\rm molecule} \cdot {\rm s}}} $$\end{document} These results are in very good agreement with recent studies of reaction (2), and also of reaction (1) at 295 K.
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  • 47
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 57-67 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate coefficients for the gas-phase pyrolyses of a series of structurally related secondary acetates have been measured in a static system over the temperature range of 289.1-359.5°C and the pressure range 50.0-203.0 torr. The temperature dependence of the rate coefficients is given by the following Arrhenius equations: for 3-hexyl acetate, log k1 (s-) = (12.12 ± 0.33) - (176.1 ± 3.9)kJ/mol/2.203RT; for 5-methyl-3-hexyl acetate, log k1 (s-) = (13.17 ± 0.20) - (186.2 ± 2.3)kJ/mol/2.303RT; and for 5,5-dimethyl-3-hexyl acetate, log k1 (s-) = (12.70 ± 0.19) - (177.4 ± 2.2)kJ/mol/2.303RT. The direction of elimination of these esters has shown from the invariability of olefin distributions at different temperatures and percentages of decomposition that steric hindrance is a determining factor in the eclipsed cis conformation. Moreover, a more detailed analysis indicates that the greater the alkyl-alkyl interaction, the less favored the elimination tends to be. Otherwise, an increase of alkyl-hydrogen interaction caused steric acceleration to be the determining factor.
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  • 48
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    International Journal of Chemical Kinetics 16 (1984), S. 125-148 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vinylacetylene was pyrolyzed at 300-450°C in a packed and an unpacked static reactor with a pinhole bleed to a quadrupole mass spectrometer. The reactant and C8H8 products were monitored continuously during a reaction by mass spectrometry. In some runs, the products were also analyzed by gas chromatography after the run. In these runs CH4, C2H6, C3H6, and C2H4 were also detected.The reaction for vinylacetylene removal and C8H8 formation is homogeneous, second order in reactant, and independent of the presence of a large excess of N2 or He. However, C8H8 formation is about half-suppressed by the addition of the free-radical scavengers NO or O2. The rate coefficient for total vinylacetylene removal is 1.7 × 106 exp(-79 ± 13 kJ/mol RT) L/mol · s. The major reaction for C4H4 removal is polymerization. In addition four C8H8 isomers, carbon, and small hydrocarbons are formed. The three major C8H8 isomers are styrene, cyclooctatetraene (COT), and 1,5—dihydropentalene (DHP).The C8H8 compounds are formed by both molecular and free-radical processes in a second-order process with an overall k ≃ 3 × 108 exp(-122 kJ/mol RT) L/mol · s (average of packed and unpacked cell results). The molecular process occurs with an overall k = 8.5 × 107 exp (-118 kJ/mol RT) L/mol · s. The COT, DHP, and an unidentified isomer (d), are formed exclusively in molecular processes with respective rate coefficients of 4.4 × 104 exp(-77 kJ/mol RT), 1.7 × 105 exp(-89 kJ/mol RT), and 3.1 × 109 exp(- 148 kJ/mol RT) L/mol · s. The styrene is formed both by a direct free-radical process and by isomerization of COT.
    Additional Material: 16 Ill.
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  • 49
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 117-124 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The static vessel pyrolysis of bicyclo[2.2.2]octa-2,5,7-triene (barrelene) has been studied between 483 and 523 K. The products were acetylene and benzene (in equal quantities) with no other detectable C8H8 isomer (down to less than 1% of total). The time dependence fitted first-order kinetics, and the data are consistent with a homogeneous unimolecular reaction close to, if not at, its high-pressure limit at 0.25 torr. The rate constant was fitted to the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ \log \left( {{k \mathord{\left/ {\vphantom {k {s^{ - 1} }}} \right. \kern-\nulldelimiterspace} {s^{ - 1} }}} \right)\, = \,\left( {14.27\, \pm \,0.18} \right)\, - \,{{\left( {41.71\, \pm \,0.41\,{{{\rm kcal}} \mathord{\left/ {\vphantom {{{\rm kcal}} {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}}} \right)} \mathord{\left/ {\vphantom {{\left( {41.71\, \pm \,0.41\,{{{\rm kcal}} \mathord{\left/ {\vphantom {{{\rm kcal}} {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}}} \right)} {RT}}} \right. \kern-\nulldelimiterspace} {RT}}\,\ln \,10 $$\end{document} These Arrhenius parameters are shown to imply a concerted single-step process. Alternative mechanisms are discussed and a comparison is made with the retro-Diels - Alder reactions of other bicyclo[2.2.2]octa-olefin systems.
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  • 50
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 103-115 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the thermal reaction between CF3OF and C3F6 have been investigated between 20 and 75°C. It is a homogeneous chain reaction of moderate length where the main product is a mixture of the two isomers 1-C3F7OCF3 (68%) and 2-C3F7OCF3 (32%). Equimolecular amounts of CF3OOF3 and C6F14 are formed in much smaller quantities. Inert gases and the reaction products have no influence on the reaction, whereas only small amounts of oxygen change the course of reaction and larger amounts produce explosions.The rate of reaction can be represented by eq. (I): The following mechanism explains the experimental results: Reaction (5) can be replaced by reactions (5a) and (5b), without changing the result: Reaction (4) is possibly a two-step reaction: \documentclass{article}\pagestyle{empty}\begin{document}$$ E_1 = 15.90 \pm 0.45{\rm kcal}\,{\rm mol}^{ - 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = \left( {7.60 \pm 0.68} \right)10^8 {\rm exp}\left( { - 15,900\,\, \pm \,\,450\,\,{{{\rm cal}} \mathord{\left/ {\vphantom {{{\rm cal}} {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \right)M^{ - 1} \cdot s^{ - 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ E^ * \, = \,12.30\, \pm \,0.25\,{\rm kcal}\,{\rm mol}^{ - 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k^ * \, = \,\left( {6.11\, \pm \,0342} \right)10^7 \,{\rm exp}\left( { - 12,300\, \pm \,250\,{{{\rm cal}} \mathord{\left/ {\vphantom {{{\rm cal}} {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \right)M^{ - 1} \, \cdot \,{\rm s}^{ - 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {E^ * \, - \frac{1}{2}E_1 \, = \,4.35\,{\rm kcal}\, = \,E_3 \, - \,\frac{1}{2}E_4 ;} & {E_3 \,} \\ \end{array} 〉 \,4.35\,{\rm kcal} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \nu \,\left( {{\rm chain}\,{\rm length}} \right)\, = \,1 + \,\frac{{k_3 }}{{k_1 ^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} \left( {2k_4 } \right)^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} }}\left( {\frac{{\left| {{\rm CR}_{\rm 3} {\rm OF}} \right|}}{{\left| {{\rm C}_{\rm 3} {\rm F}_{\rm 6} } \right|}}} \right)^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} $$\end{document} For ∣CF3 = ∣C3F6∣, ν20°C = 36.8, ν50°C = 24.0, and ν70°C = 14.2.
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  • 51
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 93-102 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions where Y = CH3 (M), C2H5 (E), i—C3H7 (I), and t—C4H9 (T) have been studied between 488 and 606 K. The pressures of CHD ranged from 16 to 124 torr and those of YE from 57 to 625 torr. These reactions are homogeneous and first order with respect to each reagent. The rate constants (in L/mol·s) are given by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} k_{{\rm NMBO}} = - {{\left( {26530 \pm 80} \right)} \mathord{\left/ {\vphantom {{\left( {26530 \pm 80} \right)} {4.576T + \left( {6.05 \pm 0.03} \right)}}} \right. \kern-\nulldelimiterspace} {4.576T + \left( {6.05 \pm 0.03} \right)}} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} k_{{\rm XMBO}} = - {{\left( {28910 \pm 130} \right)} \mathord{\left/ {\vphantom {{\left( {28910 \pm 130} \right)} {4.576T + \left( {6.32 \pm 0.05} \right)}}} \right. \kern-\nulldelimiterspace} {4.576T + \left( {6.32 \pm 0.05} \right)}} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} k_{{\rm NEBO}} = - {{\left( {26150 \pm 120} \right)} \mathord{\left/ {\vphantom {{\left( {26150 \pm 120} \right)} {4.576T + \left( {5.85 \pm 0.05} \right)}}} \right. \kern-\nulldelimiterspace} {4.576T + \left( {5.85 \pm 0.05} \right)}} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} k_{{\rm XEBO}} = - {{\left( {28560 \pm 120} \right)} \mathord{\left/ {\vphantom {{\left( {28560 \pm 120} \right)} {4.576T + \left( {6.07 \pm 0.05} \right)}}} \right. \kern-\nulldelimiterspace} {4.576T + \left( {6.07 \pm 0.05} \right)}} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} k_{{\rm NIBO}} = - {{\left( {26560 \pm 80} \right)} \mathord{\left/ {\vphantom {{\left( {26560 \pm 80} \right)} {4.576T + \left( {5.57 \pm 0.03} \right)}}} \right. \kern-\nulldelimiterspace} {4.576T + \left( {5.57 \pm 0.03} \right)}} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} k_{{\rm XIBO}} = - {{\left( {28350 \pm 100} \right)} \mathord{\left/ {\vphantom {{\left( {28350 \pm 100} \right)} {4.576T + \left( {5.47 \pm 0.04} \right)}}} \right. \kern-\nulldelimiterspace} {4.576T + \left( {5.47 \pm 0.04} \right)}} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} k_{{\rm NTBO}} = - {{\left( {28920 \pm 50} \right)} \mathord{\left/ {\vphantom {{\left( {28920 \pm 50} \right)} {4.576T + \left( {5.86 \pm 0.02} \right)}}} \right. \kern-\nulldelimiterspace} {4.576T + \left( {5.86 \pm 0.02} \right)}} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} k_{{\rm XTBO}} = - {{\left( {32890 \pm 120} \right)} \mathord{\left/ {\vphantom {{\left( {32890 \pm 120} \right)} {4.576T + \left( {6.19 \pm 0.05} \right)}}} \right. \kern-\nulldelimiterspace} {4.576T + \left( {6.19 \pm 0.05} \right)}} $$\end{document} The Arrhenius parameters are used as a test for a biradical mechanism and to discuss the endo selectivity of the reactions.
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  • 52
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 53
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 149-157 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction between ozone and carbon monoxide was reinvestigated in the range of 80-160°C. The previously reported rate law -d[O3]/dt = ka[O3][CO] + kb[O3]2 was confirmed and simulated using a mechanism based on an impurity-initiated chain reaction. When the CO was sufficiently purified, kb tended to zero and ka reduced to the value expected for the thermal decomposition of O3. Subsequent reactions of O atoms with CO produced chemiluminescence which was used to measure k3 for \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm O}\,\, + \,\,{\rm CO}\,\,\mathop {\longrightarrow}\limits^{\rm 3} \,\,{\rm CO}_{\rm 2} \left( {^3 B_2 } \right) $$\end{document} as 10-14.0±0.3 exp[-(1630 ± 325)/T] cm3 molecule-1 s-1. The implications of this are discussed.
    Additional Material: 3 Ill.
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  • 54
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 159-193 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new reaction mechanism describing the atmospheric photochemical oxidation of toluene is formulated and tested against environmental chamber data from the University of California, Riverside, Statewide Air Pollution Research Center (SAPRC). On simulations of toluene - NOx and toluene - benzaldehyde - NOx irradiations, the average predicted O3 and PAN maxima are within 3% of the experimental values. Simulations performed with the new mechanism are used to investigate various mechanistic paths, and to gain insight into areas where our understanding is not complete. Specific areas that are investigated include benzaldehyde photolysis, organic nitrate formation, alternate ring fragmentation pathways, and conjugated γ-dicarbonyl condensation to the aerosol phase.
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  • 55
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 195-204 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the oxidation of cyclopentanol, cyclohexanol, 2—methylcyclohexanol, and cycloheptanol by hexacyanoferrate(III) ions in mild alkaline medium has been studied in the presence of traces of ruthenium(VI) ≈ 10-7M at constant ionic strength (0.26M). The results suggest that the oxidation of the studied cyclic alcohols proceeds via the formation of a complex between Ru(VI) and the substrate which slowly decomposes, giving the reduced form of ruthenium which was reoxidized to Ru(VI) in a fast step by alkaline hexacyanoferrate(III) ions. The product study shows the production of the corresponding ketone.
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  • 56
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 205-211 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constants for the quenching of O2(1Δg) with carbon disulfide, dimethyl sulfide, dimethyl disulfide, diallyl disulfide, ethyl mercaptan, and thiophene have been determined in a discharge flow system in the absence of oxygen atoms. The rate constants are found to be (6.5 ± 0.6) × 104, (1.8 ± 0.2) × 104, and (3.5 ± 0.6) × 103 L/mol · s for dimethyl sulfide, ethyl mercaptan, and thiophene, respectively. The other compounds have rate constants 〈9.9 × 102 L/mol · s. In the case of dimethyl sulfide, even when NO2 concentration is more than what is required to remove oxygen atoms completely, the rate constants are found to vary with different amounts of NO2. No correlation is found to exist between the logarithm of the rate constants and the ionization potentials of the compounds.
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  • 57
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    International Journal of Chemical Kinetics 16 (1984), S. 213-220 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Energetic H atoms produced by photolysis of gaseous HI react with CD3Br by D abstraction (1) and Br abstraction (2) and possibly also by the substitution reactions (4) and (5). Yields of HD and CD3H have been determined for several defined initial translational energies of H*. The phenomenological threshold energy of reaction (1) is 53 ± 5 kJ/mol. Over the range of initial energies of 76-109 kJ mol the integral probability of reaction (1) increases substantially, but the sum of the integral probabilities of reactions (2) and (5) shows little change. The ratio of the sum of the integral yields of reactions (2) and (5) to the integral yield of reaction (1), when normalized to equal numbers of Br and D atoms, is 69 ± 33 at an initial energy of 76 kJ/mol and 31 ± 6 at 109 kJ/mol.
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  • 58
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 221-230 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reactions of iron(III) with diglycolic, tartaric, and citric acids have been studied in aqueous acid solutions by the temperature-jump method at 25.0°C and at ionic strengths 1.0 (for tartaric and citric acids) and 0.50 mol/dm3 (for diglycolic acid). The experimental data indicate that iron(III) monochelate formation occurs by the same reaction mechanism for all three ligands examined and that only pathways involving the FeOH2+ ion contribute to the chelation process. The reacting species for citric acid is the undissociated ligand. For tartaric and diglycolic acids both the neutral ligands and the corresponding monoanions react significantly under the experimental conditions used. Kinetic evidence for the contribution of intermediate steps to the limiting rate in the overall chelate-formation process has been obtained and discussed.
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  • 59
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 231-250 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mixtures of cyanogen and nitrous oxide diluted in argon were shock-heated to measure the rate constants of A broad-band mercury lamp was used to measure CN in absorption at 388 nm [B2Σ+(v = 0) ← X2Σ+(v = 0)], and the spectral coincidence of a CO infrared absorption line [v(2 ← 1), J(37 ← 38)] with a CO laser line [v(6 → 5), J(15 → 16)] was exploited to monitor CO in absorption. The CO measurement established that reaction (3) produces CO in excited vibrational states. A computer fit of the experiments near 2000 K led to \documentclass{article}\pagestyle{empty}\begin{document}$$ k_2 \, = \,10^{11.70\left( { + 0.25, - 0.19} \right)} \,{{{\rm cm}^3 } \mathord{\left/ {\vphantom {{{\rm cm}^3 } {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}}\, \cdot \,{\rm s} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_3 \, = \,10^{13.26 \pm 0.26} \,{{{\rm cm}^3 } \mathord{\left/ {\vphantom {{{\rm cm}^3 } {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}}\, \cdot \,{\rm s} $$\end{document} An additional measurement of NO via infrared absorption led to an estimate of the ratio k5/k6: with k5/k6 ≃ 103.36±0.27 at 2150 K. Mixtures of cyanogen and oxygen diluted in argon were shock heated to measure the rate constant of and the ratio k5/k6 by monitoring CN in absorption. We found near 2400 K: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_4 \, = \,10^{12.68\left( { + 0.27, - 0.19} \right)} \,{{{\rm cm}^3 } \mathord{\left/ {\vphantom {{{\rm cm}^3 } {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}}\, \cdot \,{\rm s} $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$ {{k_5 } \mathord{\left/ {\vphantom {{k_5 } {k_6 }}} \right. \kern-\nulldelimiterspace} {k_6 }}\, = \,10^{2.68 \pm 0.28} $$\end{document} The combined measurements of k5/k6 lead to k5/k6 ≃ 10-3.07 exp(+31,800/T) (±60%) for 2150 ≤ T ≤ 2400 K.
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  • 60
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 251-258 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of the reaction of aqueous sulfite with the N-chloropeptide N-chloroalanylalanylalanine has been studied as a function of pH, temperature, and ionic strength. The results of this work suggest that the mechanism of the reaction involves the interaction of the neutral chloramine with the three ionic forms of sulfite, SO3-2, HSO3-, and H2SO3, with the rate of reaction increasing rapidly with increasing protonation. The estimated second-order rate constants for each ionic species as a function of temperature are \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm H}_{\rm 2} {\rm SO}_{\rm 3} } \hfill & {k_1 \, = \,2.00\, \times \,10^8 \,{\rm exp}\left( {{{ - 1544} \mathord{\left/ {\vphantom {{ - 1544} {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \right){\rm min}^{ - 1} } \hfill \\ {{\rm HSO}_{\rm 3}^ - } \hfill & {k_2 \, = \,4.35\, \times \,10^4 \,{\rm exp}\left( {{{ - 1170} \mathord{\left/ {\vphantom {{ - 1170} {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \right){\rm min}^{ - 1} } \hfill \\ {\,\,{\rm SO}_{\rm 3}^{ - 2} } \hfill & {k_3 \, = 1.58\, \times \,10^{12} \,{\rm exp}\left( {{{ - 12,660} \mathord{\left/ {\vphantom {{ - 12,660} {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \right){\rm min}^{ - 1} } \hfill \\ \end{array} $$\end{document} where the activation energies are in units of cal/mol.
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  • 61
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 259-268 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the reactions of O3 and OH radicals with acetylene, propyne, and 1-butyne have been determined at room temperature. The rate constants obtained at 294 ± 2 K for the reactions of O3 with acetylene, propyne, and 1-butyne were (7.8 ± 1.2) × 10-21 cm3/molecule · s, (1.43 ± 0.15) × 10-20 cm3/molecule · s, and (1.97 ± 0.26) × 10-20 cm3/molecule · s, respectively. The rate constants at 298 ± 2 K and atmospheric pressure for the reactions with the OH radical, relative to a rate constant for the reaction of OH radicals with cyclohexane of 7.57 × 10-12 cm3/molecule · s, were determined to be (8.8 ± 1.4) × 10-13 cm3/molecule · s, (6.21 ± 0.31) × 10-12 cm3/molecule · s, and (8.25 ± 0.23) × 10-12 cm3/molecule · s for acetylene, propyne, and 1-butyne, respectively. These data are discussed and compared with the available literature rate constants.
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  • 62
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    International Journal of Chemical Kinetics 16 (1984), S. 269-276 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of the perchloric acid hydrolysis of aqueous ethyl and butyl vinyl ethers at 25.0°C, in the presence of micellar aggregates [anionic, sodium dodecyl sulfate (SDS); cationic, cetyl trymethyl ammonium bromide (CTAB); and nonionic, polyoxyethylen—23—dodecanol, (Brij 35)], has been studied. Negligible effects were observed in the cases of cationic and nonionic micelles. Anionic micelles produce an enhancement in the reaction velocity, and the rate constants go through maxima with increasing SDS concentration. These maxima disappear in the presence of excess sodium perchlorate. All these facts are interpreted quantitatively by means of the pseudo-phase ion-exchange model.
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  • 63
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 64
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    International Journal of Chemical Kinetics 16 (1984), S. 277-287 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The recent experiments on the chloride-assisted dealkylation of alkylcobalamins by a variety of oxidants (IrCl62-, AuCl4-, Fe(H2O)5Cl2+, and PtCl62-), which are scattered in several previous publications, and their general kinetic characteristics are summarized. The kinetic studies are also extended to include the dealkylations of (methylaquo)-3,5,6-trimethylbenzimidazolylcobamide and protonated base-off ethylcobalamin by IrCl62- (1.0M Cl-) and by Fe(III) ions at 0.1M Cl-, and the demethylation of (methylaquo)-3,5,6-trimethylbenzimidazolylcobamide by AuCl4- (1.0M Cl-). This extension is in an effort to substantiate the general mechanism which has been previously proposed for these oxidative dealkylations. The general kinetic characteristics are described in terms of a preassociation of the reactants, followed by a rate-determining electron-transfer process to yield the R-B12+ radical, which then undergoes further reactions to produce the products observed. The overall reactions are discussed within the framework of chlorine-bridging inner sphere electron-transfer reactions.
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  • 65
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    International Journal of Chemical Kinetics 16 (1984), S. 289-305 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The shock-induced thermal decompositions of vinylsilane and vinylsilane-d3 (0.2% on argon) have been studied in the temperature range of 1085-1275 K, and at total pressures of about 3100 torr. In systems without silylene traps, some induced decomposition occurs which is attributed to the silylene chain sequence VSiH → C2H2 + SiH2, S̈iH2 + VSiH3 ⇄ VSiH2SiH3 → VSiH2S̈iH + H2, VSiH2S̈iH → VSiH + S̈iH2. In the presence of silylene traps (butadiene and acetylene), the overall decomposition kinetics are log k(VSiH3, s-1) = 14.95 - 63,268 cal/2.303RT and log k(VSiD3, s-1) = 15.14 - 64,815 cal/2.303RT. Three primary processes contribute to the decomposition: 1,1-H2 elimination, 1,2-H2 elimination, and ethylene elimination. Two mechanisms are proposed, one for exclusive primary process formation of C2H4, and the other for both primary and secondary formation routes. Modeling studies are reported which show that both mechanisms can be made compatible with the rate and product yield data within experimental errors.
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  • 66
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    International Journal of Chemical Kinetics 16 (1984), S. 345-352 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photochlorination of tetrachloroethylene has been studied in a homogeneous liquid system. Kinetic parameters such as reaction orders for chlorine, tetracholoroethylene and light intensity, preexponential factor, and activation energy were evaluated from experimental data. The following kinetic equation was obtained by parameter estimation following the Marquardt procedure: \documentclass{article}\pagestyle{empty}\begin{document}$$ r = \left( {4.02 \pm 0.46} \right)10^{ - 5} \exp \left( { - \frac{{54,700 \pm 200}}{{RT}}} \right)I^{0.489 \pm 0.003} C_{Cl_2 }^{0.889 \pm 0.160} C_{C_2 Cl_4 }^{1.040 \pm 0.042} $$\end{document}
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  • 67
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    International Journal of Chemical Kinetics 16 (1984), S. 335-344 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydrogen abstration from H2S by CF3 radicals, generated by the photolysis of both CF3COCF3 and CF3I, has been studied in the temperature range 314-434 K. The rate constant, based on the value of 1013.36 cm3/mol · s for the recombination of CF3 radicals, is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log }\,k_2 \, = \,\left( {12.20\, \pm \,0.05} \right)\, - \,{{\left( {19,220\, \pm \,360} \right)} \mathord{\left/ {\vphantom {{\left( {19,220\, \pm \,360} \right)} {19.145T}}} \right. \kern-\nulldelimiterspace} {19.145T}} $$\end{document} with CF3COCF3 as the radical source, and \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log }\,k_2 \, = \,\left( {12.00\, \pm \,0.07} \right)\, - \,{{\left( {18,270\, \pm \,470} \right)} \mathord{\left/ {\vphantom {{\left( {18,270\, \pm \,470} \right)} {19.145T}}} \right. \kern-\nulldelimiterspace} {19.145T}} $$\end{document} with CF3I as the radical source, where k2 is in cm3/mol · s and E is in J/mol. These results resolve a previously existing controversy concerning the values of the rate constants for this reaction. They show that CF3 radicals are less reactive than CH3 radicals in attacking H2S, and this behavior indicates that polar effects play a significant role in the hydrogen transfer reactions of CF3 radicals.
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  • 68
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    International Journal of Chemical Kinetics 16 (1984), S. 353-369 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction chemistry of C2N2—Ar and C2N2—NO—Ar mixtures has been investigated behind incident shock waves. Progress of the reaction was monitored by observing the cyano radical (CN) in absorption at 388.3 nm. A quantitative spectroscopic model was used to determine concentration histories of CN. From initial slopes of CN concentration during cyanogen pyrolysis, the rate constant for C2N2 + M → 2CN + M (1) was determined to be k1 = (4.11 ± 1.8) × 1016 exp(-47,070 ± 1400/T) cm3/mol · s. A reaction sequence for the C2N2—NO system was developed, and CN profiles were computed. By comparison with experimental CN profiles the rate constant for the reaction CN + NO → NCO + N (3) was determined to be k3 = 10(14.0 ± 0.3) exp(-21,190 ± 1500/T) cm3/mol · s. In addition, the rate of the four-centered reaction CN + NO → N2 + CO (2) was estimated to be approximately three orders of magnitude below collision frequency.
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  • 69
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    International Journal of Chemical Kinetics 16 (1984), S. 469-481 
    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.
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  • 70
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    International Journal of Chemical Kinetics 16 (1984), S. 503-511 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The product quantum yields in the photolysis of 2,2,4,4-tetramethyl-3-pentanone have been measured in homogeneous solvents of different viscosities, in micellar solutions of cetyltrimethylammonium chloride and sodium dodecyl sulfate, and in dioctadecyl ammonium chloride vesicles.The product quantum yield in n-heptane was found to be 1. This value decreases to 0.5 in paraffin oil as a consequence of geminate recombination. In the presence of free radical scavengers, the extent of geminate disproportionation can be evaluated from the yields of isobutene and 2,2-dimethyl propionaldehyde. From these yields and the geminate recombination yields the total amount of geminate processes and the disproportionation-to-combination ratio for caged radicals are estimated. It is found that micelles provide the most efficient cages. In these media only about 10% of the radicals avoid cage processes. The disproportionation-to-combination ratio of tert-butyl and pivaloyl radicals was found to be extremely media dependent. The measured values ranged from about 0.2 in paraffin oil to 0.8 in cetyltrimethylammonium chloride micelles.
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  • 71
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    International Journal of Chemical Kinetics 16 (1984), S. 513-524 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The autooxidation of retinyl acetate and methyl retinoate was investigated in chlorobenzene at 45°C. The rates of thermal initiation in the retinyl acetate solutions were measured, and a value was determined of the rate constant for the reaction of oxygen with retinyl acetate (RH + O2 → R· + HO2·): kio = (1.3 ± 0.2) × 10-5 L/mol · s. The number of moles of oxygen absorbed per mole of polyene depends on the substrate concentration. A kinetic scheme for the methyl retinoate autooxidation was proposed which takes into account the isomerization of primary peroxy radicals, and the rate constants for different elementary reactions were estimated. The partial rate constant for “allylic” hydrogen abstraction from retinyl acetate was estimated to be ≥ 1.65 × 103 L/mol · s. A probable propagation sequence was proposed for the autooxidation of retinyl acetate.
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  • 72
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    International Journal of Chemical Kinetics 16 (1984), S. 543-558 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Cl}\,\, + \,\,{\rm RI} \to {\rm ICI}\,\, + \,\,{\rm R} $$\end{document} (R = CF3, C2F5, and i,-C3F7) have been studied competitively in the gas phase over the range of 27-231°C. The following Arrhenius parameters were obtained: Textlog A,(cm3/mol · s)E,(kJ/mol)R = CF313.99 ± 0.2117.1 ± 2.0R = C2F513.97 ± 0.2011.5 ± 2.0R = i,-C3F714.18 ± 0.2010.2 ± 2.0The above data lead to bond dissociation energies D(R-I) which are compared with previous published results. The following values are recommended: D,(CF3-I) = 224, D,(C2F5-I) = 219, and D,(i,-C3F7-I) = 215 kJ/mol.
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  • 73
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    International Journal of Chemical Kinetics 16 (1984) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 74
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    International Journal of Chemical Kinetics 16 (1984), S. 591-602 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of CCl3 with O(3P) and O2 and those of CCl3O2 with NO have been studied at 295 K using discharge flow methods with helium as the bath gas. The rate coefficient for the reaction of CCl3 with O was found to be (4.2 ± 0.6) × 10-11 cm3/s and that for CCl3O2 with NO was (18.6 ± 2.8) × 10-12 cm3/s with both coefficients independent of [He]. For reaction between CCl3 and O2 the rate coefficient was found to increase from 1.51 7times; 10-14 cm3/s to 7.88 × 10-14 cm3/s as the [He] increased from 3.5 × 1016 cm-3 to 2.7 × 1017 cm-3. There was no evidence for a direct two-body reaction, and it is concluded that the only product of this reaction is CCl3O2. Examination of these results for CCl3 + O2 in terms of current simplified falloff treatment suggests that the high-pressure limit for this reaction is ∼ 2.5 × 10-12 cm3/s, which may be compared with a direct measurement of the high-pressure limit of 5 × 10-12 cm3/s. A value of (5.8 ± 0.6) × 10-31 cm6/s has been obtained for k0, the coefficient in the low-pressure region. This value is compared with corresponding values found earlier for the (CH3, O2) and (CF3, O2) systems and with estimates based on unimolecular rate theory.
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  • 75
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    International Journal of Chemical Kinetics 16 (1984), S. 621-631 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The abstraction of hydrogen/deuterium from CH3CH2Cl, CH3CHDCl, and CH3CD2Cl by photochemically generated ground-state chlorine atoms has been investigated over the temperature range of 8-94°C using methane as a competitor. Rate constant data for the following reactions have been obtained:The temperature dependence of the relative rate constants ki/kj was found to conform to the Arrhenius rate law, where the stated error limits are one standard deviation:\documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 /k_2 = (1.099 \pm 0.015)\exp [(429 \pm 2)/T] $$ $$ k_1 /k_r = (1.422 \pm 0.026)\exp [(1113 \pm 3)/T] $$ $$ k_2 /k_r = (1.295 \pm 0.029)\exp [(684 \pm 3)/T] $$ $$ k_3 /k_r = (1.177 \pm 0.025)\exp [(717 \pm 4)/T] $$ $$ k_4 /k_r = (1.115 \pm 0.023)\exp [(732 \pm 2)/T] $$ $$ k_5 /k_r = (0.978 \pm 0.020)\exp [(985 \pm 2)/T] $$\end{document} and kr is the rate constant for the reference reaction (CH4 + Cl → CH3 + HCl). The β secondary kinetic isotope effects (k2/k3/k4) are close to unity and show a slight inverse temperature dependence. Both preexponential factors and activation energies decrease as a result of deuterium substitution in the adjacent chloromethyl group. The trends are well outside the limits of experimental error.
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  • 76
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    International Journal of Chemical Kinetics 16 (1984), S. 655-668 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of particle size, type of crucible, and heating rate on the thermal curves obtained simultaneously for CuSO4 · 5H2O were discussed. The dissociation steps were confirmed. Thermogravimetric techniques for determining the rate-controlling processes and kinetic parameters were applied for the dehydration steps and the calcination of CuSO4 and CuSO4 · CuO. For the dehydration of the monohydrate one mechanism operates but the activation energy and preexponential factor vary over wide ranges. Differentiating between various mechanisms using the same technique was sometimes difficult giving completely different values for the kinetic parameters. In view of such difficulties the various methods were assessed, the best techniques to treat similar results were recommended and the operating mechanisms and kinetic parameters for the various steps were thus established.
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  • 77
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    International Journal of Chemical Kinetics 16 (1984), S. 633-653 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report laser absorption measurements of NH3 decay within the flame front region of rich, atmospheric pressure ammonia flames. These data are combined with earlier OH, NH, and NH2 measurements to obtain new estimates for the oscillator strength of NH2. This value, fi = 6.4 × 10-5 for the PQ1,7 line in the (0,9,0) ← (0,0.0) vibrational band of the A2A1 ← X2B1 transition, suggests ΔH°f(NH) ≅ 87 kcal/mol. The ammonia profiles were also combined with previous data on NO, NH, NH2, and OH to provide an extensive database at fuel equivalence ratios (ø) of 1.28, 1.50, and 1.81 for comparison to our kinetic model predictions. This modeling used a one-dimensional flame code which explicitly accounts for the diffusional component in our flame experiments. Modeling results using a conventional mechanism predicted concentration profiles which deviated markedly from our observations. It was possible to obtain much more satisfactory fits by postulating reactions between various NHi (i = 1, 2) species to form N - N bonds. The N2Hj (j = 1-3) species could then lose H atoms via dissociation to ultimately form N2. Inclusion of these reactions in the mechanism allowed us to predict concentration - distance profiles for five different species at three different equivalence ratios that are in good agreement with experiment. The most important component of this mechanism is the recognition that the NHi + NHi reactions dominate the kinetics in rich flames. A most satisfying aspect of these calculations is that the key rate constants in the NHi + NHi sequence were estimated using simple RRK theory.
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  • 78
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    International Journal of Chemical Kinetics 16 (1984), S. 679-695 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of 1 and 2% ethane in krypton has been studied in shock waves by the laser-schlieren technique over 1700-4800 K. For 2400-2800 K an effective zero density gradient is seen following the rapid dissociation of the ethane. Through simulation with various mechanisms it is evident that the high rates for the dissociative recombination reactions of methyl radicals\documentclass{article}\pagestyle{empty}\begin{document}$$ 2{\rm CH}_3 \to {\rm C}_2 {\rm H}_4 + {\rm H}_2 $$ $$ 2{\rm CH}_3 \to {\rm C}_2 {\rm H}_5 + {\rm H} $$\end{document}obtained in recent shock-tube studies, are incompatible with this observation; these rates must be reduced at least an order of magnitude. On the basis of theory and previous low-temperature (T) measurements, k = 7.8 × 1011 (-6562/T) (cm3/mol s) is recommended for the second of these reactions.
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  • 79
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    International Journal of Chemical Kinetics 16 (1984), S. 697-706 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas phase reactions of NO2 with a series of organics have been studied at 295 ± 2 K. It was observed that only 2,3-dimethyl-2-butene and the conjugated dialkenes studied reacted at observable rates, with rate constants which ranged from 1.5 × 10-20 cm3 molecule-1 s-1 for 2,3-dimethyl-2-butene to 1.3 × 10-17 cm3 molecule-1 s-1 for α-phellandrene. These rate constants are compared with the available literature data and the mechanisms of these reactions are discussed.
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  • 80
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    International Journal of Chemical Kinetics 16 (1984), S. 741-752 
    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.
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  • 81
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    International Journal of Chemical Kinetics 16 (1984), S. 753-766 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of azoethane (AE) was studied by detailed product analysis in the temperature and pressure intervals 508-598 K and 2.7-13.3 kPa. Besides the hydrocarbon products, three characteristic and quantitatively important nitrogen-containing compounds were also determined: ethyl-2-butyldiimide, ethanal-diethylhydrazone, and tetraethyl-hydrazine. Apart from the predominant termination reactions of the ethyl radical with itself and with the μ2 radical, the decomposition is characterized by a very short chain reaction. The measurements led to determination of the following rate constants and rate constant ratios:\documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{rcl} {\rm log}(k_1 /S^{ - 1} ) &=& (16.0 \pm 0.2) - (207.6 \pm 2.0){\rm kJ mol}^{ - 1} /2.3RT\\ log(k_4 /k_3^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} {\rm dm}^{{3 \mathord{\left/ {\vphantom {3 2}} \right. \kern-\nulldelimiterspace} 2}} {\rm mol}^{{{ - 1} \mathord{\left/ {\vphantom {{ - 1} 2}} \right. \kern-\nulldelimiterspace} 2}} s^{{{ - 1} \mathord{\left/ {\vphantom {{ - 1} 2}} \right. \kern-\nulldelimiterspace} 2}} ) &=& (3.3 \pm 0.1) - (54.3 \pm 1.3){\rm kJ mol}^{ - 1} /2.3RT \\ \log (k_5 /k_3^{1/2} {\rm dm}^{{3 \mathord{\left/ {\vphantom {3 2}} \right. \kern-\nulldelimiterspace} 2}} {\rm mol}^{{{ - 1} \mathord{\left/ {\vphantom {{ - 1} 2}} \right. \kern-\nulldelimiterspace} 2}} {\rm s}^{{{ - 1} \mathord{\left/ {\vphantom {{ - 1} 2}} \right. \kern-\nulldelimiterspace} 2}} ) &=& (3.0 \pm 0.1) - (33.7 \pm 1.4){\rm kJ mol}^{ - 1} /2.3RT \\ k_{11} /k_{12} &=& 1.3 \pm 0.1 \end{array} $$\end{document} for the following reactions:
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  • 82
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    International Journal of Chemical Kinetics 16 (1984), S. 767-779 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of azoisopropane (AIP) was studied by detailed product analysis in the temperature and pressure intervals 498-563 K and 0.67-5.33 kPa. Besides the predominant termination and hydrogen-abstraction reaction of the 2-propyl radical, the decomposition is characterized by a very short chain process. The following rate constants were determined from the measurements\documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{rcl} \log (k_1 {\rm /s}^{ - 1} ) &=& (16.3 \pm 0.2) - (199.9 \pm 1.6){\rm kJ mol}^{ - 1} /2.3RT \\ \log (k_4 /k_3^{1/2} {\rm dm}^{{3 \mathord{\left/ {\vphantom {3 2}} \right. \kern-\nulldelimiterspace} 2}} {\rm mol}^{{{ - 1} \mathord{\left/ {\vphantom {{ - 1} 2}} \right. \kern-\nulldelimiterspace} 2}} {\rm s}^{{{ - 1} \mathord{\left/ {\vphantom {{ - 1} 2}} \right. \kern-\nulldelimiterspace} 2}} ) &=& (4.1 \pm 0.3) - (52.5 \pm 3.0){\rm kJ mol}^{ - 1} /2.3RT \\ \log (k_5 /k_3^{1/2} {\rm dm}^{{3 \mathord{\left/ {\vphantom {3 2}} \right. \kern-\nulldelimiterspace} 2}} {\rm mol}^{{{ - 1} \mathord{\left/ {\vphantom {{ - 1} 2}} \right. \kern-\nulldelimiterspace} 2}} {\rm s}^{{{ - 1} \mathord{\left/ {\vphantom {{ - 1} 2}} \right. \kern-\nulldelimiterspace} 2}} ) &=& (2.4 \pm 0.1) - (27.6 \pm 1.3){\rm kJ mol}^{ - 1} /2.3RT \\ k_2 /k_3 &=& 0.51 \pm 0.02 \end{array}$$\end{document} for the following reactions:
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  • 83
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    International Journal of Chemical Kinetics 16 (1984), S. 781-792 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of azoisopropane (AIP) was studied in the presence of various quantities of propylene in the temperature and pressure intervals 498-553 K and 3.33-5.33 kPa. The inhibition functions relating to formation of the products were determined; these proved a good basis for interpretation of the formation of the secondary decompositon products of AIP. The experimental data support the conception that the βμ radical - radical reactionoccurs. The product of this is not stable; its decomposition is one of the sources of the secondary products. The ratio of the rate constants was determined for the following reactions:
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  • 84
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    International Journal of Chemical Kinetics 16 (1984), S. 961-966 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An examination of the results of measurements of the forward and reverse rate constants for the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm H} + {\rm C}_{\rm 2} {\rm H}_{\rm 6} \mathbin{\lower.3ex\hbox{$\buildrel\textstyle\rightarrow\over {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}}$}} {\rm H}_{\rm 2} + {\rm C}_{\rm 2} {\rm H}_{\rm 5} $$\end{document} shows that agreement between the kinetics and the thermochemistry is achieved only through use of a value of ΔHf(C2H5) = 28 kcal mol-1. This system therefore provides further support for the recent measurement of this quantity.
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  • 85
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    International Journal of Chemical Kinetics 16 (1984), S. 1129-1137 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A readily applicable empirical formula is obtained for the collisional efficiency for energy transfer between a highly vibrationally excited reactant and a seasoned (usually quartz) wall, in terms of the molecular weight, potential well depth and dipole moment of the reactant. This expression is used to examine corrections due to nonunit wall collision efficiency in the high-pressure rate parameters obtained from very low-pressure pyrolysis experiments. It is found that these corrections are up to ca. ±5 kJ/mol in the high-pressure activation energy and a factor of ca. 2 in the high-pressure frequency factor, for molecules with molecular weight less than ca. 100 and where experiments are carried out at temperatures exceeding 1000 K.
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  • 86
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    International Journal of Chemical Kinetics 16 (1984) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 87
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    International Journal of Chemical Kinetics 16 (1984), S. 1455-1470 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The average downward collisional energy transfer (〈ΔEdown〉) is obtained for highly vibrationally excited tert-butyl chloride, both undeuterated and per-deuterated, with Kr, N2, CO2, and C2H4 bath gases, at ca. 760 K. Data are obtained using the technique of pressure-dependent very low-pressure pyrolysis. Reactant internal energies to which the data are sensitive are in the range 200-250 kJ mol-1. For C4H9Cl, the 〈ΔEdown〉 values (cm-1) are 255 (Kr), 265 (N2), 440 (CO2), and 585 (C2H4), and for C4D9Cl, 245 (N2), 370 (CO2), and 540 (C2H4). The uncertainties in these values are ca. 20% (40% for Kr); the uncertainties in the deuteration ratios are 10-15%. The value for Kr is in agreement with theoretical predictions of a biased random walk model for internal energy change in monatomic/substrate collisions. The effect of deuteration of 〈ΔEdown〉 is also in accord with that predicted by a modification of the theory. Extrapolated highpressure rate coefficients for the thermal decomposition of reactant are 1013.6 exp(-187 kJ mol-1/RT) s-1 (C4H9Cl) and 1014.2 exp(-196 kJ mol-1/RT) s-1 (C4D9Cl), in accord with other studies and the expected isotope effect.
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  • 88
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    International Journal of Chemical Kinetics 16 (1984), S. 1471-1479 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal curves obtained simultaneously at constant heating rates were used to study calcination of ZnCO3 in air. Carroll and Manche's technique, Reich's equation, and Kissinger's method gave an average value for the activation energy of 23 kcal/mol. On the other hand, Coats and Redfern's technique showed the activation energy and preexponential factor to vary over wide ranges. They increase to a maximum and decrease again on increasing the temperature. Their values decrease as the heating rate was increased. One-dimensional diffusion mechanism, obeying parabolic law, may control the entire calcination process.
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  • 89
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    International Journal of Chemical Kinetics 16 (1984), S. 1495-1503 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The yield of benzene in the reaction of 1,4- and 1,3-cyclohexadiene with OH radicals in the presence of oxygen was determined using H2O2 and CH3ONO as OH radical sources. Both in the H2O2 and the CH3ONO systems, the yield of benzene from 1,4-cyclohexadiene was 15.3% and the yield from 1,3-cyclohexadiene was 8.9%. On the basis of the obtained yields, the rate constant for allylic hydrogen abstraction per C—H in cyclohexadiene was determined to be 3.8 × 10-12 cm3 molecule-1 s-1. The branching ratio of the hydrogen abstraction to overall reaction for 1-butene and 1-pentene was estimated to be (25-14)% by applying the obtained rate constants. The result was in good agreement with the branching ratio determined directly by use of the discharge flow photoionization mass spectrometer by Biermann, Harris, and Pitts [4].
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  • 90
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    International Journal of Chemical Kinetics 16 (1984), S. 307-333 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of CH4 + Cl2 produces predominantly CH3Cl + HCl, which above 1200 K goes to olefins, aromatics, and HCl. Results obtained in laboratory experiments and detailed modeling of the chlorine-catalyzed polymerization of methane at 1260 and 1310 K are presented. The reaction can be separated into two stages, the chlorination of methane and pyrolysis of methylchloride. The pyrolysis of CH3Cl formed C2H4 and C2H2 in increasing yields as the degree of conversion decreased and the excess of methane increased. Changes of temperature, pressure, or additions of HCl had little effect. In the absence of CH4 C2H4 and C2H2 are formed by the recombination of ĊH3 and ĊH2Cl radicals. With added CH4 recombination of ĊH3 forms C2H6, which dehydrogenates to C2H4 + H2. C2H4 in turn dehydrogenates to C2H2 + H2. While HCl, C, CH4, and H2 are the ultimate stable products, C2H4, C2H2, and C6H6 are produced as intermediates and appear to approach stationary concentrations in the system. Their secondary reactions can be described by radical reactions, which can lead to soot formation. ĊH3 - initiated polymerization of ethylene is negligible relative to the Ċ2H3 formation through H abstraction by Cl. The fastest reaction of Ċ2H3 is its decomposition to C2H2. About 20% of the consumption of C2H2 can be accounted for by the addition of Ċ2H3 to it with formation of the butadienyl radical. The addition of the latter to C2H2 is slow relative to its decomposition to vinylacetylene. Successive H abstraction by Cl from C4H4 leading to diacetylene has rates compatible with the experimental values. About 10% of Ċ4H5 abstracts H from HCl and forms butadiene. Successive additions of Ċ2H3 to butadiene and the products of addition can account for the formation of benzene, styrene, naphthalene, and higher polyaromatics. The following rate parameters have been derived on the basis of the experimentally measured reaction rates, the estimated frequency factors, and the currently available heat of formation of the Ċ2H3 radical (69 kcal/mol): \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {\mathop {{\rm C}_{\rm 2} }\limits^. {\rm H}_{\rm 3} \mathop {\longrightarrow}\limits_{\left( {\rm M} \right)}^{39} {\rm H}\,\, + \,\,{\rm C}_{\rm 2} {\rm H}_{\rm 2} } & {\log k\left( {1\,{\rm atm,}\,{\rm 1300}\,{\rm K}} \right)\, = \,5.2\, + \,0.3\,s^{ - 1} } \\ \end{array} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm C}_{\rm 2} {\rm H}_{\rm 4} \, + \,\mathop {{\rm C}_{\rm 2} }\limits^. \,\mathop {\longrightarrow}\limits^{17} \,\mathop {{\rm C}_{\rm 4} }\limits^. {\rm H}_{\rm 7} } \hfill & {E\, \ge \,2\, \pm \,2\,{{{\rm kcal}} \mathord{\left/ {\vphantom {{{\rm kcal}} {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}}\,} \hfill \\ {\mathop {{\rm C}_{\rm 2} }\limits^. {\rm H}_{\rm 5} \, + \,{\rm C}_{\rm 6} {\rm H}_{\rm 6} \,\mathop {\longrightarrow}\limits^{40} \,\mathop {{\rm C}_{{\rm 12}} }\limits^. {\rm H}_{{\rm 11}} } \hfill & {E\, = \,11\, \pm \,2\,{{{\rm kcal}} \mathord{\left/ {\vphantom {{{\rm kcal}} {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}}} \hfill \\ \end{array} $$\end{document}
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  • 91
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    International Journal of Chemical Kinetics 16 (1984), S. 371-377 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of tert-butoxyl radicals with amines, leading to the formation of α-aminoalkyl radicals, and the reactions of these with the electron acceptor methyl viologen have been examined using laser flash photolysis techniques. For example, the radicals CH3ĊHNEt2 and HOCH2ĊH N(CH2CH2OH)2 react with methyl viologen with rate constants equal to (1.3 ± 0.1) × 109 and (2.1 ± 0.4) × 109M-1 · s-1, respectively, in wet acetonitrile at 300 K.
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  • 92
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    International Journal of Chemical Kinetics 16 (1984), S. 379-396 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of fast elementary recombination of neutral ketyl radicals of benzophenone and its four derivatives (BPH⋅), the dismutation of benzophenone radical anions, the disproportionation between BPH⋅ and stable nitroxyl radicals, (), and the electron transfer have been investigated in both individual solvents and binary mixtures of different viscosities. Reaction (1) for unsubstituted BPH in water, water glycerol, and n-hexane is controlled by diffusion with 2k1 ≃ kdiff. In aliphatic alcohols and toluene, which form solvation complexes with BPH⋅, reaction (1) is diffusion-enhanced and activation-controlled, respectively, with 2k1 〈 kdiff. In a viscous solvent such as 1-propanol-glycerol mixture (100 ≲ η ≲ 450 cP) reaction (1) is diffusion-controlled. Reaction (2) in alkaline 1-propanol and alkaline 1-propanol-glycerol mixture is activation controlled. The rates of reactions (3) and (4) for benzophenone radicals and nitroxyl radicals of the imidazoline series decrease as the viscosity of the water-glycerol and 1-propanol-glycerol mixtures is increased. The reactions are molecular mobility limited; nevertheless, the numerical values of k3 (k4) are 2-6 times as small as the corresponding kdiff values due to the low steric factor of the reactions (therefore called pseudodiffusion-controlled reactions). The theoretical estimates of k3 (k4) are in good agreement with the experimental results. The elimination of spin forbiddance in the process of radical recombination in viscous solvents is discussed.
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  • 93
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    International Journal of Chemical Kinetics 16 (1984), S. 669-677 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The technique of laser photolysis of alkyl and perfluoroalkyl iodides at 266 nm followed by time-resolved detection of the 1.3-μm emission from I*(2P1/2) has been used to measure the rate constants for deactivation of I* by CH3I, C2H5I, CF3I, and CH4. The recommended values are (2.76± 0.22) × 10-13, (2.85 ± 0.40) × 10-13, (3.5 ± 0.5) × 10-17, and (7.52 ± 0.12) × 10-14, respectively, in units of cm3 molecule-1 S-1.
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  • 94
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    International Journal of Chemical Kinetics 16 (1984), S. 725-739 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mixtures of NH3 and N2O dilute in Ar were heated behind incident shock waves in the temperature range 1750-2060 K. A cw ring dye laser, tuned to the center of an OH absorption line in the ultraviolet, was used to monitor OH concentration profiles by absorption spectroscopy. Infrared emission was used to follow N2O (at 4.5 μm) and NH3 (at 10.5 μm) concentration - time histories. The early-time NH3 and OH concentration profiles were sensitive to the rate constants of the reactionsleading to the following best-fit expressions for k2 and k3:k2 = 1013.34±0.3 exp(-4470/T) and k3 = 1013.91±0.2 exp(-4230/T) cm3 mol-1 s-1. The results of this study combined with previous low-temperature data suggest a significant non-Arrhenius behavior for both k2 and k3.
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  • 95
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    International Journal of Chemical Kinetics 16 (1984), S. 949-960 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and equilibria of the reaction: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Br} + {\rm CH}_{\rm 3} {\rm CH}_{\rm 2} {\rm OCH}_{\rm 2} {\rm CH}_{\rm 3} {\rm}\mathop {{\rm \rightleftharpoons}}\limits^{\rm 1} {\rm HBr} + {\rm CH}_{\rm 3} {\rm CHOCH}_{\rm 2} {\rm CH}_{\rm 3} $$\end{document} have been studied in the temperature range 298-333 K by using the very low pressure reactor (VLPR) technique. Combining the estimated entropy change of reaction (1), ΔS°1 = 8.1 ± 1.0 eu, with the measured ΔG°1, we find ΔH°1 = 4.2 ± 0.4 kcal/mol; ΔH°f(CH3CHOC2H5) = -20.2 kcal/mol, and DH° [Et OCH(Me)-H] = 91.7 ± 0.4 kcal/mol. We find: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_1 (1/{\rm mol s)} = 10.8(\pm 0.7) - (3.9 \pm 4.0)/\theta $$\end{document} where θ = 2.3 RT in kcal/mol. It has been shown that the reaction proceeds via a loose transition state and the “contact TS” model calculation gives a very good agreement with the observed value.
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  • 96
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    International Journal of Chemical Kinetics 16 (1984), S. 977-993 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chemiluminescence from the a1Δ and b1Σ+ excited electronic states of nitrogen halide diatomics is observed when HN3 is allowed to react with mixtures of halogen atoms in a discharge-flow apparatus. Excited NF (a1Δ) is produced by the F + HN3 reaction, and NCl (a1Δ, b1Σ+) and NBr (a1Δ, b1Σ+) are produced by the F, Cl, + HN3 and F, Br + HN3 reactions, respectively. In the low-density limit, the yield of NF(a1Δ) was found to be near unity. The yields of the b1Σ+ states of NCl and NBr were determined to have a lower limit of ca. 10%. A number of results from these experiments, including direct observation of N3 radicals in the flow, support a hypothetical mechanism in which N3 acts as an intermediate. A second possible mechanism proceeding via an HNF intermediate cannot be ruled out.
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  • 97
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    International Journal of Chemical Kinetics 16 (1984), S. 967-976 
    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 O3 and OH radicals with 1,3-cycloheptadiene, 1,3,5-cycloheptatriene, and cis- and trans-1,3,5-hexatriene and also of O3 with cis-2,trans-4-hexadiene and trans -2,trans -4-hexadiene have been determined at 294 ± 2 K. The rate constants determined for reaction with O3 were (in cm3 molecule-1s-1 units): 1,3-cycloheptadiene, (1.56 ± 0.21) × 10-16; 1,3,5-cycloheptatriene, (5.39 ± 0.78) × 10-17; 1,3,5-hexatriene, (2.62 ± 0.34) × 10-17; cis-2,trans-4-hexadiene, (3.14 ± 0.34) × 10-16; and trans -2, trans -4-hexadiene, (3.74 ± 0.61) × 10-16; with the cis- and trans-1,3,5-hexatriene isomers reacting with essentially identical rate constants. The rate constants determined for reaction with OH radicals were (in cm3 molecule-1 s-1 units): 1,3-cycloheptadiene, (1.31 ± 0.04) × 10-10; 1,3,5-cycloheptatriene, (9.12 × 0.23) × 10-11; cis-1,3,5-hexatriene, (1.04 ± 0.07) × 10-10; and trans 1,3,5-hexatriene, (1.04 ± 0.17) × 10-10. These data, which are the first reported values for these di- and tri-alkenes, are discussed in the context of previously determined O3 and OH radical rate constants for alkenes and cycloalkenes.
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  • 98
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    International Journal of Chemical Kinetics 16 (1984), S. 995-1008 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The very low pressure reactor (VLPR) technique has been used to measure the bimolecular rate constant of the title reaction at 300 K. The rate constant is given by log k1 (1/mol s) = (11.6 ± 0.4) - (5.9 ± 0.6)/θ the equilibrium constant has also been measured at the same temperature and is given by K1 = (5.6 ± 1) × 10-3 and hence log k-1 (1/mol s) = 9.5 ± 0.1. The results show that the reaction Br + t—C4H9 → HBr + i—C4H8 is unimportant under the present experimental conditions. Assigning the entropy of t-butyl radical to be 74 ± 2 eu which is in the possible range, the value of K1 gives ΔH°f (t-butyl) = 9.1 ± 0.6 kcal/mol-1. This yields for the bond dissociation, DH° (t-butyl-H) = 93.4 ± 0.6 kcal/mol. Both of these values are found to be in good agreement with recent VLPP studies.
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  • 99
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    International Journal of Chemical Kinetics 16 (1984), S. 1085-1101 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The yields of C5 and C6 alkyl nitrates from neopentane, 2-methylbutane, 2-methylpentane, 3-methylpentane, and cyclohexane have been measured in irradiated CH3ONONO-alkane-air mixtures at 298 ± 2 K and 735-torr total pressure. Additionally, OH radical rate constants for neopentyl nitrate, 3-nitro-2-methylbutane, 2-nitro-2-methylpentane, 2-nitro-3-methylpentane, and cyclohexyl nitrate, relative to that for n-butane, have been determined at 298 ± 2 K. Using a rate constant for the reaction of OH radicals with n-butane of 2.58 × 10-12 cm3 molecule-1 s-1, these OH radical rate constants are (in units of 10-12 cm3 molecule-1 s-1): neopentyl nitrate, 0.87 ± 0.21; cyclohexyl nitrate, 3.35 ± 0.36; 3-nitro-2-methylbutane, 1.75 ± 0.06; 2-nitro-2-methylpentane, 1.75 ± 0.22; and 2-nitro-3-methylpentane, 3.07 ± 0.08. After accounting for consumption of the alkyl nitrates by OH radical reaction and for the yields of the individual alkyl peroxy radicals formed in the reaction of OH radicals with the alkanes studied, the alkyl nitrate yields (which reflect the fraction of the individual RO2 radicals reacting with NO to form RONO2) determined were: neopentyl nitrate, 0.0513 ± 0.0053; cyclohexyl nitrate, 0.160 ± 0.015; 3-nitro-2-methylbutane, 0.109 ± 0.003; 2-nitro-2methylbutane, 0.0533 ± 0.0022; 2-nitro-2-methylpentane, 0.0350 ± 0.0096; 3- + 4-nitro-2-methylpentane, 0.165 ± 0.016; and 2-nitro-3-methylpentane, 0.140 ± 0.014. These results are discussed and compared with previous literature values for the alkyl nitrates formed from primary and secondary alkyl peroxy radicals generated from a series of n-alkanes.
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  • 100
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    International Journal of Chemical Kinetics 16 (1984), S. 1117-1128 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constants for reactions (4) and (5) were determined at room temperature by pulsed laser photolysis and time resolved mass spectrometry. A description of the experimental setup is given. CFCl2O2 radicals were generated by photolysis of CFCl3 at 193 nm in the presence of an excess of oxygen, using an excimer laser. The rate constant for reaction (4), determined under different experimental conditions is: \documentclass{article}\pagestyle{empty}\begin{document}$$k_4 = 1.6{\rm }(\pm 0.2) \times 10^{ - 11} {\rm cm}^{\rm 3} \cdot {\rm molecule}^{ - 1} \cdot {\rm s}^{ - 1}$$\end{document} The rate constant of reaction (5) was determined in the pressure range of 1-12 torr, using oxygen as the buffer gas. The reaction is in its fall-off region and the parameters determined by using the semiempirical method of Troe, taking Fc = 0.6 are: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} k(0) = 3.5{\rm }(\pm 0.5) \times 10^{ - 29} {\rm cm}^{\rm 6} \cdot {\rm molecule}^{ - 2} \cdot {\rm s}^{ - 1} \\ k(\infty) = 6.0{\rm }(\pm 1.0) \times 10^{ - 12} {\rm cm}^{\rm 3} \cdot {\rm molecule}^{ - 1} \cdot {\rm s}^{ - 1} \\ \end{array}$$\end{document} The value of k(∞) is obtained from the low-pressure measurements and therefore the uncertainty on the actual high-pressure limit is higher than the error limits quoted above. The results are compared with those reported for similar reactions.
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