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  • Physical Chemistry  (289)
  • Wiley-Blackwell  (289)
  • American Meteorological Society
  • MDPI Publishing
  • Nature Publishing Group
  • 1970-1974  (289)
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  • Wiley-Blackwell  (289)
  • American Meteorological Society
  • MDPI Publishing
  • Nature Publishing Group
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  • 1
    Electronic Resource
    Electronic Resource
    A flash photolysis-resonance fluorescence kinetics study of the reactions of ground-state sulfur atoms. V. Rate parameters for the reaction of S(3P)with cis-2-butene and tetramethylethylene (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 841-857 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate parameters for the reaction of ground-state atomic sulfur, S(3P), with the olefins cis-2-butene and tetramethylethylene have been determined over a temperature range of ∽280°K. A major finding of this study was that the rate constants for both reactions showed negative temperature dependencies. When k is expressed in the form of an Arrhenius equation, this necessarily leads to negative activation energies: k1 = (4.68 ± 0.70) × 10-12 exp (+0.23 ± 0.09 kcal/mole)/RT (219°-500°K) k2 = (4.68 ± 1.70) × 10-12 exp (+1.29 ± 0.23 kcal/mole)/RT (252°-500°K) Units are cm3 molec-1s-1. When a threshold energy of 0.0 kcal/mole is assumed for reaction (2), the temperature dependence of the preexponential term has a value of T-2. Making the usual simplifying assumptions, neither collision theory nor transition state theory leads to a preexponential factor with a strong enough negative temperature dependence. A comparison of these results with those derived from studies of the reactions of atomic oxygen, O(3P), with the same olefins shows that in both studies simple bimolecular processes were being examined. Also discussed are the possible experimental and theoretical ramifications of these new results.
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    URL: http://dx.doi.org/10.1002/kin.550050511
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  • 2
    Electronic Resource
    Electronic Resource
    Masthead (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050601
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  • 3
    Electronic Resource
    Electronic Resource
    Photolysis of alkyl iodides at 147.0 nm. The reaction H + CnH2n + 1I → HI + CnH2n + 1Work supported in part by the U. S. Atomic Energy Commission. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 893-908 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 147 nm (8.4 eV) photolysis of gaseous C2H5I, n-C3H7I, and sec-C3H7I was investigated in the presence of and absence of HI. The main overall processes are: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{rcll} {{\rm C}_{\rm 2} {\rm H}_{\rm 5} {\rm I} + h\nu} &\to& {{\rm C}_{\rm 2} {\rm H}_{\rm 4} {\rm + H + I}} & {\phi = 0.75} \\{{\rm n{-} C}_{\rm 3} {\rm H}_{\rm 7} {\rm I} + h\nu }&\to& {{\rm C}_{\rm 3} {\rm H}_{\rm 6} {\rm + H + I}} & {\phi = 0.38} \\& \to&{ {\rm CH}_{\rm 3} +{\rm C}_{\rm 2} {\rm H}_{\rm 4} {\rm + I}} & {\phi = 0.47} \\ {\sec - \,{\rm C}_{\rm 3} {\rm H}_{\rm 7} {\rm I}\, + h\nu} &\to &{{\rm C}_{\rm 3} {\rm H}_{\rm 6} {\rm + H + I}} & {\phi = 0.80} \\ &\to&{ {\rm CH}_{\rm 3} +{\rm C}_{\rm 2} {\rm H}_{\rm 4} {\rm + I}} & {\phi = 0.07} \\\end{array} $$\end{document} These dissociative processes occur mainly as a result of initial cleavage of the weak C—I bond, followed by decomposition of the internally excited alkyl radicals. In all cases, approximately 5-10% of the alkyl radicals thus formed do not undergo dissociation at pressures around 3-7 torr. There is also evidence for the elimination of HI as well as C—C cleavage in the primary dissociation. The former is indicated by deuterium labeling experiments and the formation of cyclopropane (Φ = 0.04) as a product in the photolysis of n-C3H7I. Because the processes listed above provide a constant source of H atoms whose quantum yield can be exactly determined, it was feasible to obtain accurate values for ka/kb: For thermally equilibrated H atoms (300 K), ka/kb is 0.44 ± 0.04, 0.57 ± 0.06, 0.95 ± 0.1, and 0.024 ± 0.01 for C2H5I, n-C3H7I, sec-C3H7I, and C2H5Br, respectively.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550050515
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  • 4
    Electronic Resource
    Electronic Resource
    Electronically excited oxygen atoms, O(21D2). A time-resolved study of the collisional quenching by the gases H2, D2, CH4, NO, NO2, N2O, and C3O2 using atomic absorption spectroscopy in the vacuum ultraviolet (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 819-831 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Time-resolved atomic absorption spectroscopy in the vacuum ultraviolet has been employed to monitor electronically excited oxygen atoms, O(21D2), following their genera-tion by the flash photolysis of ozone in the Hartley band region. We report the first values for the absolute second-order rate constants describing the removal of the excited atom on collision with the molecules H2, D2, CH4, NO, NO2, N2O, and C3O2. Where possible, these data are considered within the context of restrictions arising from spin and orbital symmetry and are further discussed in tems of previously reported relative rate data derived from indirect measurements. Consideration is given to the importance of these rate con-stants in discussing processes taking place in the earth's atmosphere and in systems giving rise to chemical laser action.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550050509
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  • 5
    Electronic Resource
    Electronic Resource
    Time-resolved fluorescence studies on the formation and decomposition of the aromatic hydrocarbon-aliphatic amine exciplex in solution (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 833-839 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fluorescence rise and decay processes were measured and rate parameters were determined for the pyrene-tri-n-butylamine and pyrene-N,N-diethylaniline exciplex system in various solvents. An additional activation energy over that for the diffusional motion appears necessary for both exciplex formation and the deactivating quenching processes in the case of the pyrene-tri-n-butylamine system. The rate-determining step for these processes is electron transfer in the encounter collision leading to the nonrelaxed electron transfer state.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550050510
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  • 6
    Electronic Resource
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    Kinetics of the reactions of 2,4,6-tri-t-butylphenoxyl with cumene hydroperoxide, cumylperoxyl radicals, and molecular oxygen (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 869-877 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of 2,4,6-tri-t-butylphenoxyl (TBP) with cumene hydroperoxide (ROOH), cumylperoxyl radicals (RO2), and molecular oxygen in benzene solution have been investigated kinetically by the ESR method. The rate constant of the reaction TBP + ROOH has been estimated in the temperature range 27°-75°C: log10(k-7/M-1sec-1) = (7.1 ± 0.4) - (10.9 ± 0.6 kcal mole-1)/θThe ratio of the rate constants of reactions TBPH + RO2 products has been determined from the experimental dependence of the rate constant of reaction TBP with ROOH on [TBPH]0/[TBP]0. Putting k7 = 4.0 × 103M-1sec-1, we obtain k8 = (2.0 ± 0.2) × 108M-1sec-1 at 30°C. The reaction of TBP with O2 obeys the kinetic law -d[TBP]/dt = k′[O2][TBP]2. This is in accordance with scheme TBP + O2 ← TBP⃛O2 [I]; TBP⃛O2 + TBP · products, log10 (k′/M-2sec-1) = (-14.5 ± 0.9) + (27.2 ± 1.4)/θ at 66°-78°C, where ° = 2.303RT.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050513
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  • 7
    Electronic Resource
    Electronic Resource
    A simple empirical method for the estimation of activation energies in radical molecule metathesis reactions (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 879-892 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several new empirical methods are presented for the prediction of activation energies E of the metathetical transfer reaction of single bonded atoms in radical-molecule reactions of the type A· + BC → AB + C· The methods assign additive contributions to E for the endgroups A· and C·, neglecting the effect of the transferred atom B. Most of the predicted values agree to within l kcal mol-1 with the experimental activation energies (average error = 0.82 and standard deviation = 1.02 kcal mol-1). This is comparable to the best of the more complex schemes available for such estimation.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050514
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  • 8
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    The kinetics reaction of 1-chloro-2,3-epoxypropane with n-butyl and iso-butyl alcohols (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 919-927 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of 1-chloro-2,3-epoxypropane with n-butyl and isobutyl alcohols and their 3-chloro-2-hydroxypropyl ethers, respectively, in the presence of boron fluoride diethyl etherate catalyst are of the first order with regard to 1-chloro-2,3-epoxypropane as well as to the catalyst. In the catalyst concentration range of 1.4 to 47.3 mmol/l., the participation of the catalyst in the reaction is incomplete. The mechanism of the reactions resembles SN2 in regard to changes of activation entropy and influence of dielectric constant of the reaction medium upon the reaction rate. The established values of K (the ratio of propagation to initiation rates) are suitable for calculating the compositions of the adducts obtained. The experimentally obtained yields of 3-chloro-2-hydroxypropyl ethers of lower alcohols are compared with those calculated from the kinetically determined values of K.
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    URL: http://dx.doi.org/10.1002/kin.550050603
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  • 9
    Electronic Resource
    Electronic Resource
    A method for computer analysis of kinetics of competing first- and second-order reactions (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 977-989 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Competing first- and second-order reactions of transient molecular species (e.g., triplet states and free radicals) are a common occurrence in kinetic studies such as flash photolysis and pulse radiolysis. We have developed a method for analyzing the decay kinetics of any species (Y) whose disappearance is described by -dY/dt = k1Y + k2Y2. The computer program (written in time-sharing BASIC) employs an iterative technique to obtain the least-squares estimates of the three parameters in the integrated rate equation.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050607
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  • 10
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    Low-pressure thermal decomposition of ONBr and ONCl in shock waves (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 1023-1037 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the low-pressure unimolecular decomposition of ONBr and ONCl in an argon bath have been determined at temperatures in the vicinity of 1000°K. Both molecules exhibit the usual depression of the observed activation energy below the bond dissociation energy. The Arrhenius expressions obtained are (units of cc mole-1 sec-1): \documentclass{article}\pagestyle{empty}\begin{document}$$ ONBr - Ar:\log k = (15.06 \pm 0.27) - (25.06 \pm 1.13)kcalmole^{ - 1} /\theta $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ ONCl - Ar:\log k = (15.95 \pm 0.52) - (43.79 \pm 2.04)kcalmole^{ - 1} /\theta $$\end{document} Treatment of the data by the classical RRK theory yields s ≅ 2.7 ± 1 for ONCl and 3.0 ± 0.6 for ONBr. Coupling the shock tube results for ONCl with lower-temperature data from Ashmore and Burnett [3], one obtains s ≅ 2.5 ± 0.5 and λ ≍ 1. If it is assumed that s is also 2.5 for ONBr, then one finds the surprising (but tentative) result that λONCl—Ar/λONBr—Ar ≍ 3 to 4.
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  • 11
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    Absolute rate constants for reactions of free radicals in the high-temperature photolysis of formamide vapor. II. Amino radicals (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 1039-1046 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rotating-sector method has been applied to the photoinitiated radical-chain decomposition of formamide at 300°C to measure the rate constant for the bimolecular disappearance of NH2 radicals. The decomposition is propagated by the reactions (1) \documentclass{article}\pagestyle{empty}\begin{document}$$ NH_2 + NH_2 CHO \to NH_3 + NH_2 CO $$\end{document} (2) \documentclass{article}\pagestyle{empty}\begin{document}$$ NH_2 CHO \to N_2 + CO $$\end{document} Conditions were chosen so that reaction (1) was rate controlling and NH2 the terminating radical. A flow system was employed with C2F6 as a carrier gas at a pressure of 300 Tort, and the chain reaction was initiated by the photolysis of either formamide or NH3. A value of 4.7(±2.0) × 1010 (M ·sec)-1 was estimated for the termination reaction (3) \documentclass{article}\pagestyle{empty}\begin{document}$$ 2NH_2 \to N_2 H_4 $$\end{document} and a value of 8.4 × 106 (M ·sec)-1 for reaction (1) in the same system, both at 300°C.
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    URL: http://dx.doi.org/10.1002/kin.550050612
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  • 12
    Electronic Resource
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    Masthead (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550060101
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  • 13
    Electronic Resource
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    Masthead (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550060201
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  • 14
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    Mechanism of the acid hydrolysis of aromatic o-carboxyamides and relative imides (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 245-256 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of N-phenylphthalamic acid and of N-phenylphthalimide hydrolysis in aqueous solutions of sulfuric acid has been studied. A reaction mechanism is proposed implying that unreactive forms of the reactant appear by protonization of the amide bond at the carbonyl oxygen and by dissociation of the o-carboxyl group (N-phenylphthalamic acid). Attack of the nonprotonized amide bond by the hydroxonium ion is suggested to be the rate-limiting step.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550060204
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  • 15
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    A study of the collisional quenching of O(21D2) by the noble gases employing time-resolved attenuation of atomic resonance radiation in the vacuum ultraviolet (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 77-87 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electronically excited oxygen atoms O(21D2) have been generated by the pulsed irradiation of ozone in the Hartley-band continuum and monitored photoelectrically in absorption by time-resolved attenuation of atomic resonance radiation at λ = 115.2 nm [O(31D2°) → O(21D2)]. Collisional quenching of the excited atom has been investigated for all the noble gases, and the first absolute values for the second-order deactivation rate constants are reported. The resulting rate data are discussed in terms of a curve-crossing mechanism based on existing spectroscopic data for the noble gas oxides. The absolute rate constants are compared with previous relative rate data for the deactivation of O(21D2) by the noble gases.
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    URL: http://dx.doi.org/10.1002/kin.550060108
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  • 16
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    Masthead (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550060301
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  • 17
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    Reaction of excited iodine atoms with methyl iodide: Rate constant determinations (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 297-308 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant for the reaction I(2P1/2) + CH3I → I2 + CH3 has been reevaluated taking into account both collisional deactivation of excited iodine atoms and loss of I2 by I2 + CH3 → I + CH3I. The reevaluation is based upon data obtained (R. T. Meyer), J. Chem. Phys., 46, 4146 (1967) from the flash photolysis of CH3I using time-resolved mass spectrometry to measure the rate of I2 formation. Computer simulations of the complete kinetic system and a closed-form solution of a simplified set of the differential equations yielded a value of 6(± 4) × 106 1./mole-sec for the excited iodine atom reaction in the temperature region of 316 to 447 K. A slight temperature dependence was observed, but an activation energy could not be evaluated quantitatively due to the small temperature range studied. An upper limit for the collisional deactivation of I(2P1/2) with CH3I was also determined (2.4 × 107 1./mole-sec).
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  • 18
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    Rates and mechanism of alkyne ozonationThis paper presents the results of one phase of research carried out at the Jet Propulsion Laboratory, California Institute of Technology, under Contract No. NAS 7-100, sponsored by the National Aeronautics and Space Administration. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 161-173 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates and products of the reactions of ozone with acetylene, methylacetylene, dimethylacetylene, and ethylacetylene have been studied in a long-path infrared cell at 21 ± 1°C. The gas phase reaction gives products formed by cleavage of the carbon-carbon triple bond. A mechanism is proposed that involves formation of a short-lived acid anhydride intermediate, which is energized by virtue of the reaction exothermicity and undergoes unimolecular decomposition. Formation of an α-dicarbonyl was observed in every case, but there is evidence that a side reaction on the walls accounted for that product. The general relationship between alkyne and alkene ozonation is discussed. The rate measurements showed that, unlike the alkenes, the rate of alkyne ozonation is not greatly affected by substitution with simple alkyl groups. The rate constant for C2H2 agrees with earlier work and thus provides additional support for the previously derived high A-factor for acetylene ozonation relative to alkenes.
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    URL: http://dx.doi.org/10.1002/kin.550030208
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  • 19
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    Masthead (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/kin.550030301
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  • 20
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    The pyrolysis of neopentane at small extents of reaction (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 197-213 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of neopentane, at small extents of reaction, was studied by gas chromatography, in Pyrex reaction vessels between 450° and 530°C and in the initial pressure range 25-200 mm Hg. At initial time, this thermal decomposition can be essentially represented by a homogeneous long-chain radical mechanism. The rate constant of the unimolecular initiation process is approximately given by the expression \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm 0} \simeq 10^{13} {\rm exp}\left({\frac{{50,000}}{{RT}}} \right){\rm mole}^{- {\rm 1/2}} {\rm .ml}^{- {\rm 1/2}} {\rm .s}^{- {\rm 1}}$$\end{document} The initial rate constant of the global reaction (order 3/2) is nearly equal to \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm 1} + 10^{16.8} {\rm exp}\left({\frac{{82,000}}{{RT}}} \right){\rm s}^{- {\rm 1}}$$\end{document} This reaction is strongly inhibited by propene or isobutene and self-inhibited by the isobutene formed; an interpretation of all these inhibition phenomena of the neopentane pyrolysis is proposed. Our observations and conclusions, which have been summarized in communications during 1968 and 1969, are compared to those of other authors, particularly to the recent ones of Purnell and colleagues [13] and of Taylor and colleagues [14], [15].
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  • 21
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    Arrhenius parameters for reactions of oxygen atoms with the fluorinated ethylenesThis paper was presented at the Seventh International Symposium on Fluorine Chemistry at Santa Cruz, California, July 1973. (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 443-452 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Competitive studies of the reactions of ground-state oxygen atoms, generated by mercury-photosensitized decomposition of nitrous oxide, have been carried out with ethylene and all the fluoroethylenes using 2-(trifluoromethyl)-propene as reference compound. From measurements at 25°C and 150°C relative rate constants have been determined and used to calculate the Arrhenius parameters shown in the following table: TextOlefin\documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{A_{{\rm olefin}} }}{{A_{{\rm 2TFMP}} }}$$\end{document}ΔERef\documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{A_{{\rm olefin}} }}{{A_{{\rm C}_{\rm 2} {\rm H}_{\rm 4} } }}$$\end{document}ΔEC2H4CH2—CH21.10-1.18(1.0)(0)CH2—CHF1.030.840.942.02CH2—CF20.711.490.652.67CHF—CHF (cis-)1.231.921.123.10CHF—CHF (trans-)1.400.791.271.97CF2—CHF1.060.000.961.22CF2—CF20.86-3.220.78-2.04ΔERef = Eolefin - E2TFMP and ΔEC2H4 = Eolefin - EC2H4. Units are kJ/mole.The results are compared with corresponding data for other atoms and radicals, and discussed in terms of the electronic changes produced in the double bond by fluorine substitution, and in relation to the nature of the transition state.
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    The kinetics of nucleophilic substitution processes in the alkyl halides. Part B - analysis of experimental data (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 467-479 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nucleophilic substitution reactions in the alkyl halides, RX + Y- → RY + X-, proceeding in polar media are considered on the basis of the theory presented in Part A. It is shown that the solvent reorganization energy is the main part of the activation energy for this processes. According to calculations performed, the values of the solvent reorganization energy equal ∼2.5-3 eV for H2O and ∼ 1.8-2.3 eV for acetone. From experimental data on the kinetic isotope effect, an estimate for the splitting of nonadiabatic terms and for the slope of the potential curve v′ of the intermolecular interaction between halide ion and methyl halide near transition configuration is made. Further, the parameter v′ is used for calculating the activation entropy of substitution reactions in the methyl halides. Theoretical activation energies and activation entropies agree with experimental values. In the framework of theory presented an interpretation of change of Ea and the preexponential factor with the type of alkyl halide is given.
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    Thermochemical kinetics of nitrogen compounds. V. The unimolecular thermal decomposition of diallylamine in the gas phase (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 371-382 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the thermal decomposition of diallylamine to propylene and prop-2-enaldimine have been studied in the gas phase in presence of an excess of methylamine over the temperature range of 532.7 to 615.6°K, using a static reaction system. Methylamine reacted with the unstable primary product prop-2-enaldimine, forming the thermally stable N-methyl prop-2-enaldimine.First-order rate constants, based on the internal standard technique, fit the Arrhenius relationship log k(s-1) = (11.04 ± 0.13) - (37.11 ± 0.33 kcal/mole)/2.303 RT. They were independent on the initial total pressure (46-340 torr), the initial pressure of diallylamine (9.2-65 torr), or methylamine as well as the conversion attained. Despite an apparent surface sensitivity, the reaction is essentially homogeneous in nature as demonstrated by experiments carried out in a packed reaction vessel.The observed activation parameters for the title reaction together with those observed earlier for triallylamine and allylcyclohexylamine are consistent with the proposed concerted reaction mechanism involving a cyclic 6-center transition state. The observed substituent effects suggest a nonsynchronous mode of bond breaking and bond formation.
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    Masthead (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 25
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    The kinetics of nucleophilic substitution processes in the alkyl halides. Part A - theory (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 457-466 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Activation energies for substitution reactions of the type AC + B → A + CB, occurring in polar media and characterized by an abrupt change of the term along two coordinates have been calculated within the framework of the quantum-mechanical theory of chemical reactions. In the case of nonadiabatic processes, the transmission coefficient and activation energy for these reactions are expressed in terms of characteristic parameters of the medium (reorganization energy, effective frequency of solvent fluctuation polarization) and the potential energy curves for intermolecular interactions between the reactants (AC and B) and between the products (A and BC).
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    The thermochemical kinetics of retro- “ene” reactions of molecules with the general structure (allyl) XYH in the gas phase. IX. The thermal unimolecular decomposition of ethyallylether in the gas phasePart 8; P. Vitins and K. W. Egger, J . Chem. Sac. Faraday I, Vol. 70, submitted. (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 429-435 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of ethylallylether (EAE) has been studied in the gas phase over the temperature range of 560-648°K. Propylene and acetaldehyde are the only reaction products observed. The reaction is apparently homogeneous in nature and independent of the pressure of EAE and of added foreign gases. The experimetally determined first-order rate constants, using the internal standard technique, fit the Arrhenius relationship log k(s-1) = 11.84 ± 0.29 - (43.57 ± 0.77 kcal/mole)/2.303RT. Independently the same rate constants are obtained, based on the amounts of products formed. The observed activation parameters are in general agreement with expectations based on the concept of a 6-center 1,5-H-shift retro-“ene” reaction mechanism, and they agree with previous results obtained for the similar reactions involving alkylallylamines and olefins.
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  • 27
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    Rate constants for the bimolecular self-reactions of ethyl, isopropyl, and tert-butyl radicals in solution. A direct comparison (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 453-456 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A competitive method involving the direct measurement of radical concentrations by EPR spectroscopy has been used to show that in solution at 25°C the rate constants for the bimolecular self-reactions of ethyl, isopropyl, tert-butyl, cyclopentyl, and trichloromethyl are all approximately equal, as had been indicated previously by direct measurement of the rate constants for decay of these radicals.
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    The ferric ion catalyzed decomposition of hydrogen peroxide in perchloric acid solution (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 507-516 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Predictions of the “redox” and “complex” schemes for the Fe3+ catalyzed decomposition of H2O2 have been compared with published and new experimental data by numerical integratior of the appropriate complete sets of differential equations. Apparent discrepancies for the redox scheme at high Fe3+/H2O2 ratios are shown to disappear in the complete treatment, and inconsistencies of the complex scheme with both kinetic data and spectroscopic measurements are pointed out.
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    The correction of rate data for the effects of internal temperature change (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 531-543 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of reactant self-heating or cooling upon rate data is considered, and three approaches to the problem of obtaining valid kinetic parameters are described in detail. A comparison of these approaches emphasises the need to assess and allow for thermal effects during the initial planning of kinetic experiments if satisfactory results are to be acquired. An integrated rate expression is given for use with nonisothermal data, and is used to provide correction factors for rate constants which have been derived without allowance for thermal effects.
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    The reaction of O(3P) with C2HCl3 (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 553-565 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of O(3P), prepared from the Hg photosensitization of N2O, with C2HCl3 was studied at 25°C. The products of the reaction in the absence of O2 were CO, CHCl3, and polymer (as well as N2 from the N2O). The quantum yields of CO and CHCl3 were 0.23 ± 0.01 and 0.14 ± 0.05, is respectively independent of reaction conditions. The reaction mechanism is with k14a/k14 = 0.23, where k14a + k14b. Most of the HCl and CCl2 combine to form CHCl3, but some other products must also be formed to account for the difference in the CO and CHCl3 quantum yields. The C2HCl3O* adduct polymerizes without involving additional C2HCl3 molecules, since the quantum yield of C2HCl3 disappearance, —Φ{C2HCl3}, was about 1.0 at high values of [N2O]/[C2HCl3]. The rate coefficient for the reaction of O(3P) with C2HCl3 is 0.10 that for the reaction of O(3P) with C2F4.In the presence of O2 the free radical chain oxidation occurs because of the reaction The main product is CHCl2CCl(O) with smaller amounts of CO and CCl2O, and some CO2. The chain lengths were long and values of — Φ {C2HCl3} up to 90 were observed.
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    Rate of the reaction of hydroxyl radical with acetylene (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 587-595 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the decay of hydroxyl radicals in the presence of excess acetylene were studied at pressures in the vicinity of 1 torr and at ambient temperature in a tubular discharge-flow reactor. Hydroxyl radicals were produced by the reaction of atomic hydrogen with nitrogen dioxide, H + NO2 → OH + NO. The concentration of hydroxyl was followed by line absorption photometry at 308.939 nm and 308.328 nm. Second-order rate coeffcients were determined in two sets of experiments. The initial concentration ratio [C2H2]0/[OH]0 was in the range of 2.3 to 13.2 in the first set, and 14 to 125 (owing to greater hydroxyl detection sensitivity) in the second set. Values of the second-order rate coefficient obtained were nk5 = (2.9 ± 0.3) × 10-13 cm3/molec-sec in the first set, and nk5 = (2.1 ± 0.6) × 10-13 cm3/molec-sec in the second set, where n is the stoichiometric coefficient of OH. A value of the bimolecular rate constant k5 = (2.0 ± 0.6) × 10-13 cm/molec-sec is consistent with both sets of data, as well as an earlier determination.
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    Masthead (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974) 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Very low-pressure pyrolysis (VLPP) of t-butylmethyl ether (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 631-641 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of t-butylmethyl ether has been studied using the VLPP technique. The recommended Arrhenius parameters for the molecular elimination, reaction (1), are A(800°K) = 101 3, 9 sec-1 and Ea (800°K) = 59.0 ± 1.0 kcal/mole. No radical reactions occur under the conditions used. These parameters are in good agreement with earlier experimental work and with theoretical estimates of both A and E.
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    A kinetic study of the chemistry of the SO2 (3B1) reactions with cis- and trans-2-butene (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 829-848 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chemical reactions of SO2(3B1) molecules with cis- and trans-2-butene have been studied in gaseous mixtures at 25°C by excitation of SO2 within the SO2(3B1) → SO2(+, 1A1) ‘forbidden’ band using 3500-4100-Å light. The initial quatum yields of olefin isomerization were determined as a function of the [SO2]/[2-butene] ratio and added gases, He and O2. The kinetic treatment of these data suggests that there is formed in the SO2(3B1) quenching step with either cis- or trans-2-butene, some common intermediate, probably a triplet addition complex between SO- and olefin. It decomposes very rapidly to form the 2-butene isomers in the ratio [trans-2-butene]/[cis-2-butene] = 1.8. In another series of experiments SO2 was excited using a 3630 ± 1-Å laser pulse of short duration, and the SO2(3B1) quenching rate constants with the 2-butenes were determined from the SO2(3B1) lifetime measurements. The rate constants at 21°C are (1.29 ± 0.18) × 1011 and (1.22 ± 0.15) × 1011 l/mole·sec with cis-2-butene and trans-2-butene, respectively, as the quencher molecule. Within the experimental error these quenching constants equal those derived from the quantum yield data. Thus the rate-determining step in the isomerization reaction is suggested to be the quenching reaction, presumably the formation of the triplet SO2-2-butene addition complex. In a third series of experiments using light scattering measurements, it was found that the aerosol formation probably originates largely from SO3 and H2SO4 mist formed following the reaction SO2(3B1) + SO2 → SO3 + SO(3Σ-). Aerosol formation from photochemically excited SO2-olefin interaction is probably unimportant in these systems and must be unimportant in the atmosphere.
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    Yet another direct measurement of the rate constant for the recombination of methyl radicals (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 887-891 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decaying absorption of CH3 radicals at 216.4 nm has been followed over more than three half-lives using a photoelectric split-beam kinetic spectrometer. The rate constant for recombination kr was found to be (5.60 ± 0.76) × 10-11 cm3/molecule·s.
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    Isomerization of chemically activated bicyclo[3.1.0]hex-2-ene and related C6H8 isomers (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 899-920 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Singlet methylene was reacted with cyclopentadiene to give chemically activated bicyclo[3.1.0]hex-2-ene (BCH). The rate of isomerization of BCH to 1,4-cyclohexadiene, 1,3-cyclohexadiene, cis-1,3,5-hexatriene, and l-methylcyclopentadiene is compared with calculated rate constants using the RRKM theory and measured or estimated thermal Arrhenius parameters. Subsequent isomerizations of the C6H8 products are also measured and calculated. These include 1,4-cyclohexadiene to benzene and the reversible reactions between 1,3-cyclohexadiene, cis-1,3,5-hexatriene, and trans-1,3,5-hexatriene. The results provide new data for several of these reactions which have not been observed in thermal studies. Agreement between the observed and calculated rates using the strong collision assumption is satisfactory except for the trans-1,3,5-hexatriene to cis-1,3,5-hexatriene reaction.
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    The pyrolysis of 2-nitrosoisobutane and the bond dissociation energies of nitroso compounds (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 813-828 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Study of the reaction by very-low-pressure pyrolysis (VLPP) in the temperature range of 550-850°K yields for the high-pressure Arrhenius parameters \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }\,k_{\rm 1} = (15.6 \pm 0.5) - (36.0 \pm 1.0)/\theta {\rm \,(sec}^{{\rm - 1}})$$\end{document} where θ = 2.303RT in kcal/mole. These in turn yield for the high-pressure second-order recombination of tBu + NO, k-1 = (3.5 ± 1.7) × 109 1./mole·sec at 600°K. For the competing reaction l./mole·sec and E4 ≥ 4.2 kcal/mole. The bond dissociation energy DHo (tBu-NO) was determined to be (39.5 ± 1.5) kcal/mole, both from the equilibrium constant and from the activation energy of reaction (1), obtained from RRKM calculations. A ‘free-volume’ model for the transition state for dissociation is consistent with the data. A limited study of the system at 8-200 torr showed an extremely rapid inhibition by products and a very complex set of products.
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    A computer program for the Kassel integral (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 875-876 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    The thermal unimolecular isomerization of 1,1-divinylcyclopropane (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 893-897 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal isomerization of 1,1-divinylcyclopropane has been investigated in the gas phase in the temperature range of 238 to 288°C and for pressures in the range of 4 to 12 torr. The isomerization to 1-vinylcyclopentene is homogeneous and kinetically first order and almost certainly unimolecular. The rate constants yield the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k({\rm s}^{ - 1} {\rm)} = 13.53 \pm 0.13 - (42.45 \pm 0.33{\rm \,kcal/mole})/RT\,{\rm In 10}$$\end{document} or \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k({\rm s}^{ - 1} {\rm)} = 13.53 \pm 0.13 - (117.6 \pm 1.4{\rm \,kJ/mole})/RT\,{\rm In 10}$$\end{document} The assumption of a similar transition state for this isomerization with that of l-methyl-l-vinylcyclopropane leads to a value for an alkylpentadienyl radical stabilisation energy of 19.2 ± 1.6 kcal/mole (80.4 ± 6.7 kJ/mole), and this value is compared with other estimates.
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    Multistage reactions, equilibrium, and detailed balancing: A linear algebra approach (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 491-499 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methods of linear algebra are applied to (a) the problem of determining whether detailed balancing for some or all stages of a chemical process is implicit from the existence of steady state for some or all of the chemical species involved, and (b) the formulation of general concentration-type equilibrium relationships solely from kinetic considerations and the assumption of full detailed balancing.
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    The reactions of O(1D) with ozone and nitrous oxide (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 501-508 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ozone was photolyzed at room temperature in the presence of N2O at 2537 Å and 2288 Å to produce O(1D) atoms. These atoms can react with either O3 or N2O via From the quantum yield of N2, the relative rate constants k6a/k6 and k2/k6 could be obtained, where k6 + k6a + k6b. The former rate constant ratio was found to be 0.37 ± 0.03 at 2537 Å and 0.33 ± 0.03 at 2288 Å, in good agreement with an earlier report from our laboratory. The ratio k2/k6 was found to be 2.6 at 2537 Å, but 4.1 at 2288 Å. The difference in the two numbers, if real, may reflect differences in reactivity due to different amounts of excess translational energy in the O(1D) atom at the two wavelengths.
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    Second international symposium on gas kinetics, July 5-9, 1971, University College of Swansea, United Kingdom (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 553-554 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Disproportionation-combination ratios of small alkyl radicals formed by the mercury-photosensitized hydrogenation of olefins in the gas phase (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 523-534 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Disproportionation-combination ratios have been obtained for small alkyl radicals produced in the mercury-photosensitized hydrogenation of ethylene, propylene, butene-1, butene-2, and isobutene. For conditions favoring thermalized radicals, kd/kc (ethyl, ethyl) = 0.14, kd/kc (isopropyl, isopropyl) = 0.69, kd/kc (isopropyl, n-propyl) = 0.41, kd/kc (2-butyl, 2-butyl) = 0.77, kd/kc (2-butyl, n-butyl) = 0.45, and kd/kc (t-butyl, t-butyl) = 3.1. The results are consistent with kd/kc (n-propyl, n-propyl) = 0.15 and kd/kc (n-butyl, n-butyl) = 0.14. The general agreement between these disproportionation-combination ratios and those obtained where photolytic radical sources have been used indicates that under appropriate conditions, H atom addition to olefins is a suitable source for the study of thermalized alkyl radicals and may be especially useful for larger alkyl radicals for which clean photolytic precursors are not available.
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    Disproportionation-combination ratios of large branched alkyl radicalsThis work was supported by the Office of Naval Research. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 535-551 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The disproportionation-combination reactions of radicals 4,4-dimethylpentyl-2 and 2,4-dimethylpentyl-2, produced by collisional stabilization of the respective chemically activated species, have been studied at 298°K, with and without getter radicals. Use of getters t-C4H9 and C2H5 with 4,4-dimethylpentyl-2, and of iso-C3H7 with 2,4-dimethylpentyl-2 yielded disproportionation-combination ratios ω for parent-getter and t-C4H9-C2H5 cross reactions, and for the mutual reaction of t-C4H9 radicals. The unstabilized hot radicals decompose, and these experiments also yielded values for the high-pressure rate constant ka∞ of 1.70 × 108sec-1 and 2.11 × 107sec-1 for 4,4-dimethylpentyl-2 and 2,4-dimethylpentyl-2, respectively. The results, compared to those for other large alkyl radical systems obtained earlier, suggest that steric effects influence the accessibility of H atoms for transfer.
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    Kinetics of the gas phase reaction of methyl benzoate with bromine and iodine: The methoxyl C—H bond strength of methyl estersThis work supported in part by Grant No. 00353-06 from the Environmental Protection Agency, Air Pollution Control Administration. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 509-522 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase reactions of PhCOOCH3 with I2 and Br2 were studied spectrophotometrically in a static system over the temperature ranges 344-359° and 246-303°, respectively. For each system the initial rate was first order in PhCOOCH3 and half order in halogen as the concentration of PhCOOCH3 was varied from 1.4 to 15.2 torr, that of I2 from 6.2 to 26.4 torr, and that of Br2 from 3.0 to 13.6 torr. The rate-determining step is the extraction of a methoxyl hydrogen atom: Empirical assignment of A-factors for k1 lead to \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log(k}_{\rm 1} {\rm /M}^{- {\rm 1}} {\rm sec}^{- {\rm 1}} {\rm) = (11}{\rm .5} \pm {\rm 0}{\rm .3)} - (29.9 \pm 0.8)/\theta $$\end{document} for the I2 system, and to \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log(k}_{\rm 1} {\rm /M}^{- {\rm 1}} {\rm sec}^{- {\rm 1}} {\rm)} = {\rm (11}{\rm .3} \pm {\rm 0}{\rm .3)} - (14.6 \pm 0.8)/\theta $$\end{document}for the Br2 system, where φ = 2.303RT in kcal/mole. Combined with the assumption that E-1 = 1 ± 1 kcal/mole and 2 ± 1 kcal/mole for HI and HBr, respectively, DH2980 (PhCOOCH2—H) calculated from the two systems shows excellent agreement at 100.2 ± 1.3 kcal/mole and 100.1 ± 1.3 kcal/mole. Using a value of δHf,2980 (PhCOOMe) = -65.6 ± 1.5 kcal/mole obtained from group additivity estimates, δHf,2980 (PhCOOCH2) is calculated to be -16.7 ± 2.0 kcal/mole. Unimolecular decomposition of the Ph(CO)O°CH2 radical was also observed: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Ph}\left( {{\rm CO}} \right){\rm O\dot CH}_{\rm 2} \mathop {\hbox to 20pt{\rightarrowfill}}\limits^3 {\rm Ph\dot CO} + {\rm H}_{\rm 2} {\rm CO} $$\end{document} with a rate constant equal to \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log(}k_{\rm 3} {\rm /sec}^{- {\rm 1}} {\rm)} = {\rm (15} \pm {\rm 0}{\rm .5)} - (26 \pm 3)/\theta $$\end{document} The abnormally high methoxyl C—H bond strength is discussed in relation to the bonding in ethers, alkanes, and esters.
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    Masthead (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972) 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Iron (II) and iron (III) isotope exchange in water-dimethyl sulfoxide mixturesAbstracted in part from the Ph.D. Thesis of Marian S. Henry, University of Minnesota, December 1970. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 37-48 
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The rate of the isotope exchange reaction between iron(II) and iron(III) perchlorates has been measured in a solvent mixture containing a 3:2 mole ratio of water to dimethyl sulfoxide over the temperature range from 25° to -98°C. In this temperature range, the reactants can diffuse together faster than they can undergo isotope exchange. The activation enthalpy and entropy for the acid-independent reaction were 6.0 ± 1.2 kcal/mole and -38 ± 17 cal/deg mole, respectively. Below -22°C, the acid-dependent exchange reaction did not contribute significantly to the exchange. In liquid media at -112° and -117°C and in a solid glass at -136°C, no isotope exchange was observed over the period of a calculated half-life for the reaction. At these temperatures, the rate at which the reactants diffuse together is slower than the calculated rate of isotope exchange. In a solid glass at -196°C, no isotope exchange was observed over the period of one week.
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    Reaction of H and D atoms with deuterated propylenes (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 307-314 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Effects of deuterium substitution in propylene on the relative rates of H(D) atom abstraction from and addition to the olefin, and on the orientation of H(D) atom addition, have been studied in the gas phase at room temperature. Effects of isotopic substitution of the olefinic hydrogen atoms on abstraction could not be observed, but abstraction is reduced five- to tenfold by deuteration of the methyl group. Deuteration of either olefinic position enhances the rate of addition to the substituted carbon atom. Disproportionation-combination ratios for deuterium-substituted propyl radicals are not greatly different from those for unsubstituted radicals, the largest effect being for C3D7 radicals, for which the overall kd/kc is reduced 10-15%.
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    Abstraction by hydrogen atoms from ethylene, propylene, butene-1, and cis- and trans-butene-2 (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 315-324 
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The position of abstraction by H atoms from ethylene, propylene, butene-1, and cis- and trans-butene-2 and the rates of abstraction relative to addition have been measured at 25°C. Only allylic abstraction was observed. From ethylene, abstraction relative to addition was ≤3×10-4. For propylene, butene-1, cis-butene-2, and trans-butene-2, abstraction occurred on 0.2%, 1.6%, 1.5%, and 0.9% of the reactive encounters, if dis-proprotionation-combination ratios for allyl and alkyl radicals are similar to those for alkyl-alkyl pairs.
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    Vibrational excitation of deuterium fluoride and hydrogen fluoride by atomic and diatomic species (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 293-306 
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The vibrational excitation of HF and DF and the energy transfer efficiencies for various collision partners were investigated over the temperature and pressure ranges of 1400°K to 4100°K and 0.1 to 0.3 atm, respectively. The extent of excitation was determined as a function of time by continuously monitoring the infrared emission intensity at the center of the 1-0 vibration-rotation band of the molecule. Collisional efficiencies of HF, N2, O2, F, Cl, and DF in relaxing HF and of DF, HF, and N2 in relaxing DF are reported. A comparison with relaxation data for pure HF taken at lower temperature suggests that long-range attractive forces are mechanistically of major importance in the relaxation process. The relatively high efficiency of atomic chlorine in relaxing HF, i.e., (τP)HF-HF/(τP)HF-C1 ≥ 5 at 3000°K is discussed in terms of our previous result for atomic fluorine, i.e., (τP)HF-HF/(τP)HF-F = 18.
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    Secondary hydrogen isotope effect for the transition from olefin to free radical (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 325-330 
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Secondary kinetic isotope effects occur in radical additions to deuterated olefins. Substitution of a deuterium at a carbon undergoing an sp2 to sp3 hybridization-change during reaction, Cβ in eq. (1), leads to an inverse isotope effect of 3-5% (kH/kD = 0.95-0.97). The effect at a carbon going from an olefinic to a radical center, Cα in eq. (1), generally has been assumed to be negligible, since a nominal sp2 hybridization is maintained throughout reaction. Using new, sensitive instrumentation for radioactivity determination and a recently developed quench correction technique, we now find that there is a small, normal isotope effect (kH/kT 1) associated with a change from olefin to radical. Specifically, when R· is the polystyryl radical, X is phenyl, and the α-C bears a tritium, kH/kT = 1.04. This result is discussed in relation to recent data on cycloaddition reactions.
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    Radical reactions of highly polar molecules. Chlorination of halopropanes (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 331-338 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In polychloro-2,2-difluoropropanes, where a large inductive effect results in relatively low reactivity to chlorination, the presence of additional chlorine causes an increased reactivity of the hydrogens geminal to the chlorine and a reduced reactivity of the remote (third carbon) hydrogens. The ways in which resonance, inductive effect, and steric crowding interact in the rates of chlorination of polar molecules are discussed.
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    Carbon-nitrogen bond dissociation energy values in C-nitrosocompounds (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 339-343 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Measurements of the D(R—NO) bond strength in some C-nitrosocompounds have been made using an electron impact method. The appearance potential of the radical ion (R+) has been determined, the D(R—NO) bond energy being obtained from the relation \documentclass{article}\pagestyle{empty}\begin{document}$$D{\rm (R} - {\rm NO) = }AP{\rm (R}^{\rm + } {\rm)} - IP({\rm R}.)$$\end{document} The values obtained are: D(C6H5—NO) = 41 kcal/mole, D(t-C4H9—NO) = 34 kcal/mole, D(t-C5H11—NO) = 36 kcal/mole and D(i-C3H7—NO) = 36.5 kcal/mole. These values are in good agreement with the numerous estimations of Benson and coworkers and confirm that the C—N bond strength in C-nitrosocompounds is very much less than in nitrocompounds or in amines.
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    Computational modeling of the mechanisms of the free radical-chain reaction of alkanes with oxygen. The oxidation of isobutane, n-butane, and isopentane (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 345-362 
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general computational method for obtaining complete solutions of time-dependent kinetic equations has been developed and applied to free radical-initiated reactions of alkanes with oxygen. The method has been applied to the low-temperature, peroxide-initiated oxidations of isobutane and isopentane. Using available independently measured and estimated values for the rate constants and activation parameters for each of the 20 proposed reaction steps for the oxidation of isobutane, the rates and products have been calculated for both the liquid phase and gas phase in the range of 100°-155°C. The calculated rates and products of oxidation agree with published experimental values. The oxidation of isopentane was examined by a 32-reaction model. The rate constants were estimated using values for the appropriate rate steps in the oxidation of n-butane and isobutane. The calculation of the oxidation rate and products agree with our experiments.
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    The alpha effect. A review (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 1-26 
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Instances of high reactivity (as signaled by a positive Brönsted deviation) by nucleophiles bearing one or more unshared pairs of electrons on an atom adjacent to the nucleophilic center (the alpha effect) are surveyed in the context of possible explanations for this phenomenon. No single cause appears to account satisfactorily for all the data. However, four factors (ground-state destabilization of the nucleophile, transition-state stabilization, solvent effect differences for alpha and nonalpha nucleophiles, and product stability) may be involved in contributory roles. The response to proton basicity of a substrate is probably not related to its susceptibility to the alpha effect. Carbon electrophiles seem to be receptive to the alpha effect in the order digonal 〉 trigonal 〉 tetrahedral. The inconsistent behavior of alpha nucleophiles makes the prediction of alpha effects rather risky and confirms the complicated nature of nucleophilic substitutions.
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    Very low-pressure pyrolysis. VIII. The decomposition of Di-t-amyl peroxideThis work was supported in part by Contract No. F44620-71-C-0103 with the Air Force Office of Scientific Research. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 55-65 
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The very low-pressure pyrolysis (VLPP) technique has been applied to the pyrolysis of di-t-amyl peroxide (DTAP) over the temperature range 523-633°K. VLPP yields a low-pressure rate constant, kuni The conversion of kuni to k∞ which must be made to calculate the Arrhenius parameters, is accomplished via the RRKM theory. The transition state model used in the RRKM calculations was based on a transition state model which accurately reproduced the VLPP data for di-t-butyl peroxide for which the Arrhenius parameters are well known. For the decomposition of DTAP it was found that log k∞(300°K) = 15.8 - 36.4/θ, where θ = 2.303RT, in kcal/mole, and the units of k∞, are sec-1.
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    The dissociation of 3-chloro-1-butene and the resonance energy of the chloro-allyl radical (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 67-75 
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Methane is a primary product of pyrolysis of 3-chloro-l-butene at temperatures in the range 776-835°K, and from its rate of formation values have been obtained for the limiting high-pressure rate constant of the reaction These may be represented by the expression log [(k1)∞/sec-1] = (16.7 ± 0.3) - (71.5 ± 1.5)/θ, where θ = 2.303RT kcal/mole. Assuming a zero activation energy for the reverse reaction and that over the experimental temperature range the rates at which a methyl radical adds on to chlorobutene are comparable to those at which it abstracts hydrogen, the activation energy for the dissociation reaction leads to a value of 83.2 ± 1.9 ckal/mole for D(H—CHClCH:CH2) at 298°K. Taking D(H—CHClCH2CH 3) = 95.2 ± 1.0 kcal/mole a value of 12.0 ± 2.1 kcal/mole is obtained for the resonance energy of the chloroallyl radical. This value in conjunction with resonance energies obtained in earlier work indicates that substitution of a hydrogen atom on the carbon atom adjacent to the double bond in the allyl radical leads to no significant variation in the allylic resonance energy.
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    The homogeneous gas phase H2—D2 metathesis at room temperature: Reaction induced by specific vibrational excitation (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 93-106 
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have demonstrated that reactions for which substantial activation energies are needed can be induced to occur at room temperature via specific vibrational excitation. Indeed, the indications are that the atom-switching reactions for which Ea 〉 25 kcal take place with high probability only when the activation energy is localized in the vibrational mode. In this preliminary report on the utilization of the stimulated Raman effect to generate substantial populations in the critical vibrational states required for the homogeneous atom exchange between H2 and D2, we first summarized the historical development of the concept. The experimental arrangement is then described and the analytical results tabulated; the observed dependence on relative concentrations is semiquantitatively rationalized on the basis of a model proposed in 1964. Independent shock tube and molecular beam investigations were similarly accounted for. Attention is called to the discrepancy between the generally concordant experimental results and the ab initio quantum mechanical calculations of the potential energy surface for 4H atoms.
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    Kinetics of chemically activated ethane (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 77-92 
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chemically activated ethane, with an excitation energy of 114.9 ± 2 kcal/mole, was formed by reaction with methane of excited singlet methylene radicals produced by the 4358 Å photolysis of diazomethane. A decomposition rate constant of (4.6 ± 1.2) × 109 sec-1 was measured for the chemically activated ethane. This result agrees, via RRKM theory, with most other chemically activated ethane data, and the result predicts, via RRKM and absolute rate theory for E0 = 85.8 kcal/mole, E* = 114.9 kcal/mole, and kE = 4.6 × 101 sec-1, a thermal A-factor at 600°K of 1016.6±0.2 sec-1, in approximate agreement with the more recent experimental values. Combining 2 kcal/mole uncertainties in E0 and E* with the uncertainty in our rate constant yields an A-factor range of 1016.6±0.7 sec-1. It is emphasized that this large uncertainty in the A-factor results from an improbable combination of uncertainty limits for the various parameters. These decomposition results predict, via absolute rate theory (with E0(recombination) = 0) and statistical thermodynamic equilibrium constants, methyl radical recombination rates at 25°C of between 4.4 × 108 to 3.1 × 109 l.-mole-1-sec-1, which are 60 to 8 times lower, respectively, than the apparently quite reliable experimental value. A value of E0(recombination) greater than zero offers no improvement, and a value less than zero would be quite unusual. Activated complexes consistent with the experimental recombination rate and E0(recombination) = 0 greatly overestimate the experimental chemical activation and high pressure thermal decomposition rate data. Absolute rate theory as it is applied here in a straightforward way has failed in this case, or a significant amount of internally consistent data are in serious error. Some corrections to our previous calculations for higher alkanes are discussed in Appendix II.
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    A study of the bimolecular intersystem crossing reaction induced in the first excited singlet of SO2 by collisions with O2 and other atmospheric gases (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 107-117 
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relative intensities of phosphorescence of SO2(3B1) molecules have been determined following the optical excitation of SO2(1B1) molecules by a 2662 Å laser pulse. From a kinetic treatment of these measurements, the intersystem crossing ratio, k2b/(k1b + k2b), was determined; SO2(1B1) + M → SO2(3B1) + M (2b); SO2(1B1) + M → SO2 + M (1b). With M = O2, N2, Ar, CO2, and CO, k2b/(k1b + k2b) = 0.030 ± 0.013, 0.034 ± 0.029, 0.025 ± 0.005, 0.052 ± 0.014, and 0.045 ± 0.028, respectively. These data allow a new, more quantitative evaluation of the extent of involvement of the “excess” triplet SO2 in the 3130 Å-irradiated mixtures of SO2 and CO at high pressures [5, 6]. The new data are also of direct interest in the determination of the theoretical maximum rates of photooxidation of SO2 in the sunlight-irratiated atmosphere of the earth.
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    Masthead (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973) 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Kinetics of the I2-catalyzed isomerization of allyl chloride to cis- and trans-1-chloro-1-propene. The stabilization energy of the chloroallyl radicalThis work was supported in part by Grant No. 00353-07 of the Environmental Protection Agency, Air Pollution Control Administration. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 155-167 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The I2-catalyzed isomerization of allyl chloride to cis- and trans- l-chloro-l-propene was measured in a static system in the temperature range 225-329°C. Propylene was found as a side product, mainly at the lower temperatures. The rate constant for an abstraction of a hydrogen atom from allyl chloride by an iodine atom was found to obey the equation log [k,/M-1 sec-1] = (10.5 ± 0.2) -; (18.3 ± 10.4)/θ, where θ is 2.303RT in kcal/mole. Using this activation energy together with 1 ± 1 kcal/mole for the activation energy for the reaction of HI with alkyl radicals gives DH0 (CH2CHCHCl—H) = 88.6 ± 1.1 kcal/mole, and 7.4 ± 1.5 kcal/mole as the stabilization energy (SE) of the chloroallyl radical. Using the results of Abell and Adolf on allyl fluoride and allyl bromide, we conclude DH0 (CH2CHCHF—H) = 88.6 ± 1.1 and DH0 (CH2CHCHBr—H) = 89.4 ± 1.1 kcal/ mole; the SE of the corresponding radicals are 7.4 ± 2.2 and 7.8 ± 1.5 kcal/mole. The bond dissociation energies of the C—H bonds in the allyl halides are similar to that of propene, while the SE values are about 2 kcal/mole less than in the allyl radical, resulting perhaps more from the stabilization of alkyl radicals by α-halogen atoms than from differences in the unsaturated systems.
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    Chemical lasers produced from O(3P) atom reactions. I. Observation of CO and HF laser emissions from several O atom reactions (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 173-176 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    The pyrolysis of hexachloroethane (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 187-195 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of hexachloroethane in the presence of chlorine has been studied over the temperature range 340-400°C and a pressure range of 0.5°2.5 atm. The rate of the unimolecular C—C bond spliting reaction can be described by the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$\log k_1 = 1707 - \frac{{68,300}}{{2.3RT}}$$\end{document} Comparison of these rate data with thermodynamic data suggests a combination rate for CCl3 radicals which is consistent with earlier measurements.
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    Kinetics of the thermal decomposition of CF3CHCL2 in a single-pulse shock tubeWork supported by the National Research Council of Canada. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 363-373 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of 2,2-dichloro-1,1,1-trifluoroethane was studied over the temperature range of 1120-1260°K at total reflected shock pressures from ∼2800 to 3100 torr. Below 1260°K, the decomposition leads to three reaction products which were identified as CF2CFCl, CF2CFH, and CF3CCl3. The results are interpreted in terms of a parallel C—Cl bond rupture process which becomes competitive with the molecular HCI elimination. The rate constant for the α,α-elimination process \documentclass{article}\pagestyle{empty}\begin{document}$$ CF_3 CHCl_2 \to CF_2 CFCl + HCL $$\end{document} has been deduced to be \documentclass{article}\pagestyle{empty}\begin{document}$$ \log \left( {K_1 ^\infty /\sec ^{ - 1} } \right) = \left( {13.4 \pm 0.7} \right) - \left( {63.1 \pm 3.8kcal} \right)/2.303RT $$\end{document} It was also possible to obtain the overall rate constant for the formation of CF2CFH, which is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ \log \left( {K^{''} /\sec ^{ - 1} } \right) = \left( {11.5 \pm 0.8} \right) - \left( {54.1 \pm 3.8kcal} \right)/2.303RT $$\end{document} Some evidence for hydrogen fluoride elimination was found at temperatures above 1260°K. However, at these higher temperatures C—C bond scission also occurs and the kinetics of the system become untractable.
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    Reactions of unsymmetrically substituted allyl radicals with methyl radicals (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 513-522 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Hg(63P1) photosensitized decompositions of 3-methyl-1-butene, 2-methyl-2-butene, 3,3-dimethyl-1-butene, and 2,3-dimethyl-1-butene have been used to generate 1-methylallyl, 1,2-dimethylallyl, 1,1-dimethylallyl, and 1,1,2-trimethylallyl radicals in the gas phase at 24 ± 1°C. From a study of the relative yields of the CH3 combination products, the relative reactivities of the reaction centers in each of these unsymmetrically substituted ambident radicals have been determined. The more substituted centers are found to be the less reactive, and this is ascribed primarily to greater steric interaction at these centers during reaction. Measurement of the ratio of trans- to cis-2-pentene formed from the 1-methylallyl radical, combined with published values for this ratio at higher temperatures, enabled the differences in entropy and heat of formation of the trans- and cis-forms of this radical to be calculated as 0.62 ± 0.85 J mol-1 K-1 and - 0.63 ± 0.25 kJ mol-1, respectively, at 298K. Approximate values of the disproportionation/combination ratios for reaction of CH3 with 1,1-dimethylallyl and 1-methylallyl have been estimated and used to compute rate constants for the recombinations of tert-butyl and isopropyl radicals that are in agreement with recently published data.
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    The pyrolysis of trimethylene sulfide. A unimolecular decomposition (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 545-551 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of decomposition of trimethylene sulfide to ethylene and thioformaldehyde was investigated in a single-pulse shock tube using the «relative rate» technique. The extent of reaction was measured in the reflected shock regime from 860° to 1170°K, but experimental difficulties limited the useful data to the temperature range of 980°-1040°K. The first-order rate constant was found to be k = 1013.0 exp (-48,200/RT) sec-1. This result sets an upper limit of 50 kcal/mole for the standard enthalpy of formation of CH2S, with 35 kcal/mole as a more likely value. The isomerization of cyclopropane to propene was used for the reference reaction; in turn, this was checked, in a relative rate experiment, against the pyrolysis of cyclohexene.
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    Investigation of the rate coefficient for O(3p) + NO2 → O2 + NOThis work was supported by Contract DAHC04-70-c-0034 with the Army Research Office, Durham, North Carolina. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 615-620 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Measurements of the rate coefficient of the reaction (O3P) + NO2 → O2 + NO have been made at 296°K and 240°K, using the technique of NO2* chemiluminescent decay. Values of 9.3 × 10-12 cm3 molec-1 sec-1 at 296°K and 10.5 × 10-12 cm3 molec-1 sec-1 at 240°K were obtained, in excellent agreement with the recent results of Davis, Herron, and Huie [1]. The earlier lower values may have resulted from loss of NO2 on surfaces.
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    A classical trajectory study of the effect of reaction barrier height on the vibrational energy transfer efficiency in the Cl + HCl systemThis work was sponsored by the McDonnell Douglas Independent Research and Development Program (IRAD). (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 629-642 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of reaction barrier height and initial rotational excitation of the reactants on the overall rate of H atom exchange between atomic chlorine and HCl (v = 0) and on the 0 → 1 vibrational excitation of HCl via reactive and nonreactive collisions have been investigated using quasiclassical trajectory techniques. Two empirical LEPS potential energy surfaces were employed in the calculations having reaction barrier heights of 9.84 and 7.05 kcal mol-1. Trajectory studies of planar collisions were carried out on each surface over a range of relative translational energies with the ground-state HCI collision partner given initial rotational excitation corresponding J = 0, 3, and 7. Initial molecular rotation was found to be relatively inefficient in promoting the H atom exchange; the computed rate coefficient for H atom exchange between Cl + HCl (v = 0, J = 7) was only 4 times larger than that for CI + HCI (v = 0, J = 0). The vibrational excitation rate coefficient exhibited a stronger dependence on initial molecular rotational excitation. The observed increase in the vibrational excitation rate coefficient with increasing initial molecular rotational excitation was due primarily to nonreactive intermolecular R → V energy transfer. The vibrational excitation rate coefficients increase with decreasing reaction barrier height.
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    The thermal decomposition of azomethane. III. Kinetics of the noninhibited reaction (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 691-714 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of azomethane (A) has been studied in a static system at temperatures between 250° and 320°C and at pressures between 5 and 402 torr, with particular attention to identification of products. Major products, in decreasing order of importance, were nitrogen, methane, ethane, methylethyldiimide, dimethylhydrazone, propane, tetramethylhydrazine, ethylene, methylpropyldiimide, and methylethylhydrazone. Carbon balance at the lowest pressure and highest temperature was 92%, but decreased with increasing pressure and decreasing temperature owing to the formation of a polymer. A fairly simple mechanism accounts reasonably well for a short chain in the decomposition, propagated by the radical CH3N2CH2 (B), and for the five most abundant products, except ethane. It turns out that there is a second source of ethane, arising by C2H5 + A → C2H6 + B; this explains an anomalously high apparent activation energy for the reaction CH3 + A → CH4 + B. Ethyl radicals are also shown to be responsible for the formation of propane, ethylene, methylethylhydrazone, and methylpropyldiimide. The radical B decomposes to CH3 + CH2 + N2, and the methylene radical (probably both singlet and triplet) is shown to yield C2H5 at low pressure and high temperature, and mostly polymer at high pressure and low temperature.
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    Methyl-radical association studied by time-resolved mass spectroscopy (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 721-732 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Time-resolved mass spectroscopy has been utilized to study the kinetics of methylradical association. The rate coefficient for the association process was determined by following the time dependence of ethane formation after flash photolysis of CH3I in the presence of N2. The net rate coefficient for the process 2CH3 (+M) → C2H6(+M) has a high-pressure limit of (4.0 ± 0.3) × 10-11 cm3 molecule-1 sec-1 at 313°K. This rate coefficient has found to be insensitive to the third-body number densities for pressures ranging from 13 Torr down to below 0.5 Torr, indicating that the lifetime for dissociation of the intermediate C2H6* species is greater than 2 × 10-7 sec at 313°K for a gas pressure of 0.5 Torr.
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    Kinetics of diffusion-controlled reaction between chemically asymmetric molecules. II. Approximate steady-state solution (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 733-752 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The previously published equation for the rate of a diffusion-limited bimolecular reaction between chemically asymmetric molecules is studied numerically for the case that one of the reactant molecules is uniform. The results are reproduced quite well by a simple approximate chemical-kinetic steady-state scheme and, in principle, allow estimates of the size of the reactive region and of the activation-controlled rate to be made from the observed dependence of rate on solvent viscosity. The simple scheme is easily generalized to the case of two nonuniform reactants. In general, restriction of reactivity to some fraction of the molecular surface (i.e., a steric factor) must reduce the observable reaction rate, but to an extent which is moderated by the rotational diffusion of the reactant molecules.
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    Vibrational energy transfer in near resonance due to dipole-dipole interactions (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 753-768 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The contribution of long-range forces to the observed rates of V → V energy transfer processes has been studied. The theoretical model uses the first order perturbation approximation to generate a probability function, with the dipole-dipole perturbing potential as given by Margenau: Vif = [(1/6)1/2μ1 · μ2]R-3. The probability function derived is shown to be a strong function of the energy mismatch between the IR bands of the colliding molecules. The calculation emphasizes the importance of rotational state population effects, the most important J states being those which minimize the energy mismatch. A complete analysis of energy transfer between CO(v) and COS(000) where v = 1,2, ⃛ 13 is presented. The calculation reveals the importance of combination bands in the energy transfer mechanism of polyatomics. The temperature dependence for near-resonant processes is also studied and the importance of the V → R energy transfer leads to the classification of ω0 (band-center energy mismatch) into three categories small, medium, and large, according to the temperature dependence that the corresponding processes exhibit. The predictions of the theoretical model are compared to experimental data for the same system.
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    A critical review of the kinetics of the dissociation-recombination reactions of fluorine and chlorineThis work was supported by the Office of Standard Reference Data, N.B.S., and the Naval Ordnance Systems Command ORD 3311 as part of a program to foster production of tables of chemical kinetics. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 39-68 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A critical evaluation of the rates of the dissociation and recombination reactions of fluorine and chlorine is given. Data are presented graphically and in tabular form. The effect of various third bodies is discussed. Rate expressions for specified temperature ranges are recommended, while comparison with theoretical values obtained from the Benson and Fueno theory is made where applicable.
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    Hydrogen abstraction from organosilicon compounds. The reactions of fluoromethyl radicals with tetramethylsilane. Polar effects in gas phase reactions (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 69-84 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of 1,1,3,3-tetrafluoroacetone has been reinvestigated as a source of CHF2 radicals at temperatures up to 578°K, and the following rate constant ratio was determined for the reactions θ= 2.303 RT in kcal/mole. 1,1-Difluoro- and 1,1,3,3-tetrafluoroacetone were photolyzed in the presence of tetramethylsilane, and Arrhenius parameters were measured for the hydrogen abstraction reactions: R + Me4Si → RH + Me3SiCH2 TextRT(°K)E (kcal/mole)log A (mole-1cc sec-1)log k (500°K) (mole-1cc sec-1)CH2F473-58612.00 ± 0.3011.68 ± 0.126.44CHF2416-52610.18 ± 0.3311.65 ± 0.157.21By comparing with previous data on the CH3 and CF3 reactions, the activation energies were interpreted in terms of the enthalpy changes for the reactions and a polar effect operative between the attacking fluoromethyl radicals and the substrate which tends to reduce the activation energy progressively as the fluorine content of the radical increases. This polar effect, which decreases the activation energy for hydrogen abstraction from SiMe4 along the series CH3, CH2F, CHF2, and CF3, is in marked contrast to the polar repulsion between the fluorinated radicals and SiHCl3 which was tentatively proposed to explain the increase in activation energy observed in the same series of reactions with SiHCl3.
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    Chlorine-photosensitized oxidations of chloroethanes and chloroethylenes in the gas phase (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 89-96 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Long-chain chlorine-photosensitized oxidation has been observed in the gas phase at about 355°K for 1,1,2,2- and 1,1,1,2-C2H2Cl4, C2HCl5, and C2Cl4 but not for C2H6, 1,2-C2H4Cl2, 1,1,1-C2H3Cl3, C2H4, and 1,2-C2H2Cl2. This is shown to depend on the exothermicity of the dissociation of the chloroethoxy radicals which must be involved in each reaction system.
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    Masthead (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971) 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    The thermal isomerization of cyclobutenes. XVI. 1,2-bis(trimethylsiloxy)cyclobutene (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 85-88 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase thermal isomerization of 1,2-bis(trimethylsiloxy)cyclobutene has been studied in the temperature range 172°-204°C. The reaction is homogeneous, kinetically first order, and yields 2,3-bis(trimethylsiloxy)buta-1,3-diene as the only product. The rate constants fit the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {k = 10^{13.509 \pm 0.120} \exp \left( {{{ - 148,920 \pm 1060\,{\rm J}\,{\rm mole}^{ - 1} } \mathord{\left/ {\vphantom {{ - 148,920 \pm 1060\,{\rm J}\,{\rm mole}^{ - 1} } {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \right)\sec ^{ - 1} } \hfill \\ {\left[ {k = 10^{13.509 \pm 0.120} \exp \left( {{{ - 35,590 \pm 250\,{\rm cal mole}^{ - 1} } \mathord{\left/ {\vphantom {{ - 35,590 \pm 250\,{\rm cal mole}^{ - 1} } {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \right)\sec ^{ - 1} } \right]} \hfill \\ \end{array}$$\end{document} These results, taken with those obtained previously, demonstrate the insensitivity of the kinetics of the reaction to the nature of the groups substituted on the 1- and/or 2-positions of the cyclobutene ring.
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    Unexpectedly rapid vapor-phase reaction between bromine and methyl iodide (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 1047-1051 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The overall reaction (1) \documentclass{article}\pagestyle{empty}\begin{document}$$ Br_2 + CH_3 I \to IBr + CH_3 Br $$\end{document} occurs readily in the gas phase, even at room temperature in the dark. The reaction is much faster than the corresponding process \documentclass{article}\pagestyle{empty}\begin{document}$$ Br_2 + CF_3 I \to IBr + CF_3 Br $$\end{document} and does not involve the normal bromination mechanism for gas phase reactions. Reaction (1) is probably heterogeneous although other mechanisms cannot be excluded.The overall reactions (1) \documentclass{article}\pagestyle{empty}\begin{document}$$ Br_2 + CH_3 I \to IBr + CH_3 Br $$\end{document} (2) \documentclass{article}\pagestyle{empty}\begin{document}$$ Br_2 + 2CH_3 I \to I_2 + 2CH_3 Br $$\end{document} proceed, for all practical purposes, completely to the right-hand side in the vapor phase. The expected mechanism is (3) \documentclass{article}\pagestyle{empty}\begin{document}$$ Br_2 \to 2Br $$\end{document} (4) \documentclass{article}\pagestyle{empty}\begin{document}$$ Br + CH_3 I \to IBr + CH_3 $$\end{document} (5) \documentclass{article}\pagestyle{empty}\begin{document}$$ CH_3 + Br_2 \to CH_3 Br +Br $$\end{document} (6) \documentclass{article}\pagestyle{empty}\begin{document}$$ Br + IBr \to Br_2 +I $$\end{document} (7) \documentclass{article}\pagestyle{empty}\begin{document}$$ I + I + M \to I_2 + M $$\end{document} where reaction (3) is initiated thermally or photochemically. Reaction (4) is of interest because little kinetic data are available on reactions involving abstraction of halogen by halogen and also because an accurate determination of the activation energy E4 would prmit us to calculate an acccurate value of the bond dissociation energy D(CH3—I).
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    The methyl radical combination rate constant as determined by kinetic spectroscopy (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 1053-1065 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant for the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} + {\rm CH}_{\rm 3} + {\rm M}\mathop {\longrightarrow}\limits^{k_1 } {\rm C}_{\rm 2} {\rm H}_{\rm 6} + {\rm M} \,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\left( {{\rm M = He}} \right) $$\end{document} has been determined by means of vacuum ultraviolet flash photolysis and time-resolved kinetic spectroscopic observations of the 1504-Å absorption band of CH3. The measurements made using three different sources of methyl radicals (azomethane, dimethylmercury, and ketene-hydrogen) were in accord and yielded a value for the rate constant of k1 = (9.53 ± 1.17) × 10-11 cc molec-1 sec-1. A detailed error analysis is presented. The f-value for the 1504-Å band of CH3 is determined to be (2.5 ± 0.7) × 10-2.
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    Mechanism of oxidation of cyclohexanehexol (inositol) by quinquevalent vanadium (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 15-28 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of inositol by quinquevalent vandadium in acid medium is a first-order reaction both in vanadium (V) and inositol. The stoichiometry of the reaction is consistent with the use of two equivalents of vanadium (V) per mole of inositol with the formation of one mole of inosose. The reaction is catalyzed both by sulfuric and perchloric acid, but the rate is faster in sulfuric acid than in perchloric acid. In 1M-6M perchloric acid solutions the reaction has shown a variable order in H+, but in solutions of 2M-5M sulfuric and perchloric acid of constant ionic strength, the rate has a linear dependence on [H+]2. There is also a linear correlation between the rate and bisulfate ions in sulfuric acid at constant hydrogen ion concentration. The energy of activation is found to be 19 kcal/mole and a negative entropy value of - 14 e.u. A suitable mechanism, consistent with the kinetics in 2M-5M acid solutions, is suggested and the values of various rate constants are evaluated.
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    Chemical lasers produced from O(3P) atom reactions. III. 5-μm CO laser emission from the O + CH reaction The preliminary results of this work were first reported at the International Conference on Chemiluminescence, Athens, Ga., October 1972. (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 1-14 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Very strong laser emission at 5 μm was detected when SO2 and CHBr3 were flash photolyzed in the vacuum ultraviolet (λ ≥ 165 nm) in the presence of a large amount of diluent (SF6, He, or Ar). About 110 vibration-rotation transitions ranging from Δv = 18 → 17 to 3 → 2, except 16 → 15, were identified. The primary reactions leading to the CO stimulated emission are as follows: The product analysis results and the variation of laser intensity with flash energy and SO concentration indicate that the following side reactions are also occurring. Addition of a small amount of O2 enhances the laser output by both eliminating these side reactions and simultaneously producing vibrationally excited CO via reaction (8), which has been previously shown to generate CO stimulated emission. The effects of various reactive (NO and H2) and inert (He, Ar, SF6, CO, N2, N2O, and CO2) gases have been examined. All additives (P ≤ 20 torr), except NO and H2, increase the total laser output. N2O enhances the power most efficiently, whereas CO, N2, and CO2 are less effective and have similar efficiencies. The enhancement of the laser intensity by these near-resonant gases is ascribed to the depletion of CO population at lower levels which thus increases the rates cascading from higher levels. NO and H2 quench the laser output by chemically reducing the concentration of the CH radical.
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    The collisional behaviour of the spin orbit states of the lead atom, Pb(63P1,2), studied by time-resolved attenuation of atomic resonance radiation (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 61-75 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic study of lead atoms in the spin orbit states, Pb(63P1) and Pb Pb(63P2), 0.969 and 1.320 eV, respectively, above the 63P0 ground state, has been carried out by atomic absorption spectroscopy. The electronically excited lead atoms were generated by the pulsed irradiation of lead tetraethyl and monitored photoelectrically by time-resolved attenuation of resonance radiation. The decay of the two atomic states has been studied in the presence of He, Ar, H2, D2, N2, O2, CO, NO, CO2, N2O, CH4, C2H4, C2H2 CF4, SF6, and PbEt4, and rate constants for the collisional quenching by these gases are reported. The resulting data are compared with those for the deactivation of other atomic spin orbit states of comparable energy. In general, the higher energy state, Pb(63P2), is found to be deactivated more rapidly. It would appear that the magnitude of the electronic energy to be transferred on collision governs the rates of quenching, at least where a weak interaction potential is involved, and that for most gases, deactivation of Pb(63P2) proceeds via Pb(63P1).
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    Kinetics of reactions of Schiff base complexes of iron(II). V. Reactions of the complex of the hexadentate ligand NN‴-bis-[α-(2-pyridyl)benzylidene]triethylenetetramine in acid solution and with hydroxide, cyanide, and peroxodisulphate (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 133-142 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation and characterization of the iron(II) complex of the hexadentate Schiff base ligand NN‴-bis-[α-(2-pyridyl)benzylidene]triethylenetetramine are reported. Kinetic patterns and rate constants for aquation of this complex, and for its reactions with hydroxide, cyanide, and peroxodisulphate have been determined. Activation parameters for the reaction with cyanide, in aqueous solution, are ΔH
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    Evaluated and estimated kinetic data for phase reactions of the hydroperoxyl radical (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 169-228 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methods are discussed for the production and detection of the hydroperoxyl radical for use in gas phase kinetic studies. Rate constants for gas phase reactions of the hydroperoxyl radical with itself, H2, H2O, CO, NO, SO2, O3, C2H6, C3H8, i-and n-C4H10, C2H4, i-C4H8, HCHO, C2H5CHO, n-C3H7CHO, Br, O, OH, and H are critically evaluated. Recommended or estimated rate constant expressions with associated error limits are given applicable over specified temperature ranges (normally 300-1000°K). The reactivity of HO2 compared with OH, O, H, F, Cl, Br, CH3, and CH3O is presented in tabular form and the implications for atmospheric chemistry are discussed.
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    Determination of D[C6F5-I] by the toluene carrier method (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 257-263 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of C6F5I has been studied by the toluene carrier method over the temperature range of 900-978°K with contact times of 0.4-2.0 seconds and total pressures of 11.2-19.5 torr. Percent decomposition ranged from 8.6 to 97.7%. With toluene-to-C6F5I molar ratios of greater than 150, 85-100% of the C6F5 released abstracts a hydrogen atom from toluene to produce C6F5H. No significant quantities of I2 were observed and the only major gaseous product was HI. Within the limits of the experimental method the decomposition of C6F5I was first order and homogeneous.Least squares analysis of log k1 and 103/T(C6F5I → C6F5 + I) values gives \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log}\,k_1 ({\rm s}^{- 1}) = 15.9 - 69,200/4.576T $$\end{document} while a weighted line of best fit yields. \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log}\,k_1 ({\rm s}^{- 1}) = 15.4 - 67,000/4.576T$$\end{document} Based on this latter equation D[C6F5—I] at 298°K is estimated as 66.2 kcal/mole.
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    The kinetics of free radical chain reactions in solutions of trichlorofluorethylene in cyclohexane (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 265-277 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gamma-radiation-induced free radical chain reaction in solutions of C2Cl3F in cyclohexane (RH) was investigated over a temperature range of 87.5-200°C. The following rate constants and rate constant ratios were determined for the reactions: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm (2a)}} & {{\rm R} + {\rm C}_{\rm 2} {\rm Cl}_{\rm 3} {\rm F} \to {\rm RCClFCCl}_{\rm 2}} \\ \end{array}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {(2{\rm b})} & \to \\ \end{array}{\rm RCCl}_{\rm 2} {\rm CClF}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c}{{\rm (3a)}} & {{\rm RCClFCCl}_{\rm 2} \to {\rm RCF}}\\ \end{array}{\raise1pt\hbox{$\Relbar \kern-4pt{\Relbar}$}}{\rm CCl}_{\rm 2} + {\rm Cl}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm (4a)}} & {{\rm RCClFCCl}_{\rm 2} + {\rm RH} \to {\rm RCClFCCl}_{\rm 2} {\rm H} + {\rm R}} \\ \end{array}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k_{2a} ({\rm mole}^{{\rm - 1}} 1.\,{\rm sec}^{{\rm - 1}}) = (8.64 \pm 0.35) - (6.38 \pm 0.41)/\theta ^1$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k_{{\rm 2b}} /k_{{\rm 2a}} = (- 0.03 \pm 0.15) - (2.39 \pm 0.28)/\theta$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm (}k_{3{\rm a}} /k_{4{\rm a}})({\rm mole}\,1.^{{\rm - 1}}) = (6.17 \pm 0.10) - (10.14 \pm 0.18)/\theta$$\end{document} In competitive experiments in ternary solutions of C2Cl4 and C2Cl3F in cyclohexane the rate constant ratio k2c/k2a was determined \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm (2c)}} & {{\rm R} + {\rm C}_{\rm 2} {\rm Cl}_{\rm 4} \to {\rm RC}_{\rm 2} {\rm Cl}_{\rm 4}} \\ \end{array}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k_{{\rm 2c}} /k_{{\rm 2a}} = (0.13 \pm 0.06) - (1.20 \pm 0.12)/\theta$$\end{document} By comparing with previous data for the addition of cyclohexyl radicals to other chloroethylenes it is shown that in certain cases the trends in activation energies for cyclohexyl radical addition can be correlated with the C—Cl bond dissociation energies in the adduct radicals.
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    Kinetics and mechanism of the reaction between N-and N,N′-methyl ethylenediamines and palladium(II) chloro complexes in aqueous acid medium (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 323-336 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The substitution of N-alkyl substituted ethylenediamines for chloride ions in the rapidly equilibrating system \documentclass{article}\pagestyle{empty}\begin{document}$${\rm PdCl}_{\rm 4} ^{{\rm 2 - }} {\rm + H}_{\rm 2} {\rm O}\rightleftharpoons{\rm PdCl}_{\rm 3} ({\rm H}_2 {\rm O)}^{\rm - } + {\rm Cl}^{\rm - }$$\end{document} has been investigated in aqueous acid medium. The kinetic data can be accommodated by the general rate law \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm obs}} = \left\{ {\frac{k}{{\left[{{\rm H}^{\rm + }} \right]}} + \frac{{k'}}{{\left[{{\rm H}^{\rm + } } \right]\left[{{\rm Cl}^{\rm - } } \right]}}} \right\}\left[{{\rm N}_{\rm n} {\rm N}_{\rm m} {\rm en}} \right]_{{\rm total}}$$\end{document} where n = 0, 1, or 2 and m = 0, 1, or 2, depending on whether none, one, or two methyl groups are attached to the two nitrogen atoms of ethylenediamine. Reaction with the most heavily substituted ethylenediamine, namely, N2N2en discloses a change of the mentioned rate law to \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm obs}} = \left\{ {\frac{{k''}}{{\left[{{\rm H}^{\rm + } } \right]}} + \frac{{k'''\left[{{\rm Cl}^{\rm - } } \right]}}{{\left[{{\rm H}^{\rm + } } \right]}}} \right\}\left[{{\rm N}_{\rm 2} {\rm N}_{\rm 2} {\rm en}} \right]_{{\rm total}}$$\end{document} on going from a lower to a higher chloride ion concentration range. This change in the mathematical form of the rate law can be explained in terms of an ion-pair association of N2N2enH+ and free chloride ions.
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    Initiation process in the system Fe3+ + H2O2 (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 383-394 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An inhibitor method for measuring the initiation rate is proposed for the system Fe3+ + H2O2. C(NO2)4 was used as inhibitor. The number of chains terminated by one C(NO2)4 molecule was estimated in specific photochemical experiments and found to be unity. The initiation appeared to involve two processes. The first is proportional to the first power of ferric ion concentration, and the second to the second power. The rate constants and activation energies of these processes are determined. Allowance for the second initiation process permitted qualitative and quantitative description of various reported data on H2O2 decomposition rates over a wide range of Fe3+, H2O2, and H+ concentrations.
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    The reaction of trichloromethyl radicals with hydrogen chlorid and a new estimation of the rate of combination of trichloromethyl radicals (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 493-506 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of the addition of hydrogen chloride on the photolysis of carbon tetrachloride in the presence of cyclohexane has been investigated in a companion paper. The data enable the rate constant ratio k8/(k5)1/2 to be determined. Since k-8 is well established, k5 can be estimated from known thermochemical data. The validity of the thermochemical derivation is checked by applying it to trifluoromethyl radicals. The photolysis of bromotrichloromethane and carbon tetrachloride in the presence of hydrogen chloride has been investigated over a range of temperatures. From these results and assuming reaction (5) has no activation energy, Arrhenius parameters for reaction (8) have been determined: The activation energies for the reaction of methyl, trichloromethyl, and trifluoromethyl radicals with hydrogen chloride are compared, and at first sight surprising results are rationalized in terms of relative electronegativity.
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    On the accuracy of the hydroperoxide method of determining absolute rate constants for hydrogen atom abstraction by the tert-butylperoxy radical (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 527-530 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Measurements of rates of oxygen absorption and steady-state peroxy radical concentrations for the autoxidation of tetralin in the presence of tert-butyl hydroperoxide have shown that the rate constant for reaction of the tert-butylperoxy radical with tetralin at 60°C is approximately 11.0 M-1 s-1. This rate constant is about a factor of 4 larger than the value recently reported by Niki, Okayasu, and Kamiya for this reaction.The present work emphasizes that great care should be taken when the hydroperoxide method is used to estimate cross-propagation rate constants for a substrate as reactive as tetralin at a temperature as high as 60°C.
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    The decomposition of acetylenedicarboxylic acid in acetophenone (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 567-572 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of acetylenedicarboxylic acid in acetophenone was studied in the temperature range of 100-130°C. The rate constants and activation parameters for the consecutive pair of first-order steps (each yielding carbon dioxide) were calculated. Hydrogen kinetic isotope effects were also studied. Comparisons were made with the decompositions of oxalic acid and malonic acid. An intramolecular H—C transfer is believed to be the main part of the reaction coordinate in addition to the C—C bond breaking.
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    The photolysis of N2O at 1470 Å (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 269-282 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of pure N2O, N2O and N2, and N2O and C3H6 mixtures at 1470 Å and room temperature has been studied to determine the relative importance of the primary processes. The results are where φ{O(1D)} = 0.515 represents both the O(1D) produced in the primary act and that produced by collisional quenching of O(1S); φ{N2(3Σ)} = 0.084 represents only that portion of N2(3φ) which dissociates N2O on deactivation; and φ{O(1S)} = 0.38 - ±{N(2D)} represents only that portion of O(1S) which enters into chemical reaction with N2O. If the reaction of O(1S) with N2O yields only N2 and O2 as products, which seems likely from potential-energy curve considerations then ±{O(1S)} = 0.135 ± 0.06 and φ{N(2D)} = 0.245 ± 0.06. Young and coworkers [4] have found from spectroscopic observations that the total quantum yield of O(1S) is about 0.5. Thus it can be concluded that collisional removal of O(1S) by N2O yields mainly O(1D) with chemical reaction being less important. Furthermore, most of the O(1D) is produced this way, and the true primary yield of O(1D) is about 0.15. The metastable N(2D) is not deactivated by N2O, but is removed by chemical reaction to produce N2 and NO. The results further indicate that N2(3Σ) dissociates N2O at least 80% of the time during quenching. The relative efficiency of N2O compared to N2 is about 2 for the removal of O(1D). O(1S) is removed about 90 times as efficiently by C3H6 as by N2O.
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    Some hydrogen abstraction reactions of the trichloromethyl radical (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 283-289 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase photolysis of CCl4 in the presence of several alkanes has been used to obtain Arrhenius parameters for the abstraction of hydrogen atoms by the CCl3 radical: The following log k4 values were obtained: TextRHlog k4c-C5H10,\documentclass{article}\pagestyle{empty}\begin{document}$$12.00 \pm 0.21 - \frac{{10,700 \pm 400}}{{2.3RT}}$$\end{document}n-C6H14\documentclass{article}\pagestyle{empty}\begin{document}$$11.81 \pm 0.18 - \frac{{10,800 \pm 300}}{{2.3RT}}$$\end{document}2,3-Dimethylbutane\documentclass{article}\pagestyle{empty}\begin{document}$$10.88 \pm 0.11 - \frac{{8,200 \pm 200}}{{2.3RT}}$$\end{document}c-C7H14\documentclass{article}\pagestyle{empty}\begin{document}$$12.07 \pm 0.43 - \frac{{9,900 \pm 800}}{{2.3RT}}$$\end{document}Methylcyclohexane\documentclass{article}\pagestyle{empty}\begin{document}$$11.75 \pm 0.26 - \frac{{9,900 \pm 500}}{{2.3RT}}$$\end{document}c-C8H16\documentclass{article}\pagestyle{empty}\begin{document}$$12.11 \pm 0.29 - \frac{{9,600 \pm 500}}{{2.3RT}}$$\end{document}The results are compared to those for CH3 and CF3 radicals.
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    Masthead (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971) 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Abstraction of hydrogen by methyleneThis work was partially supported by the U.S. Atomic Energy Commission and the National Aeronautics and Space Administration. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 293-305 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of CD2CO at 313 nm in the presence of neopentane was carried out over the temperature range 576-706 K. Analysis of the products and isotopic analysis of the methanes demonstrate abstraction of H from neopentane and D from CD2CO by methylene. The relative kinetics of abstraction of H and D have been measured over the temperature range, and the absolute value for the collision yield of the abstraction of H from neopentane by CD2 at 653 K has been been estimated to be about 1.5 × 1011 mole-1 cm3 sec-1, a value 103 times larger than the corresponding reaction of CH3.
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    The reactions of CF3 and CD3 radicals with boron trimethyl (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 307-317 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydrogen abstraction from boron trimethyl has been studied using the abstracting radicals CF3 and CD3, from the photolysis of the corresponding ketones over the temperature range of 150° to 300°C. The following Arrhenius parameters were obtained: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} {\rm (CD}_{\rm 3} {\rm + BME}_{\rm 3} {\rm); log }A{\rm = 11}{\rm .8, }E{\rm = 9}{\rm .98 kcal/mole} \\ {\rm (CF}_{\rm 3} {\rm + BMe}_{\rm 3} {\rm); log }A{\rm = 11}{\rm .6, }E{\rm = 6}{\rm .59 kcal/mole} \\ \end{array}$$\end{document} The difference ECD3 - ECF3 in the case of BMe3 is considered due, in part, to polar effects. An exchange reaction is proposed for both CF3 and CD3 in collisions with BMe3: \documentclass{article}\pagestyle{empty}\begin{document}$${\rm R} + {\rm B}({\rm Me})_3 \to {\rm Me} + {\rm RBMe}_2$$\end{document} Radical combination of CF3 and CH2BMe2 leads to a hot molecule which undergoes a β-fluoro rearrangement elimination process, or a stabilized molecule which can thermally decompose:
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    The mercury-sensitized oxidation of carbon monoxide (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 319-341 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mercury-photosensitized oxidation of CO was studied at 275°C over a wide range of [O2]/[CO] ratios in the absence and presence of the oxygen atom scavenger 2-trifluoromethylpropene (TMP) and at 25°C at low [O2]/[CO] ratios in the presence of TMP. By following the quantum yield of CO2 production, Φ {CO2}, as a function of the [O2]/[CO] ratio, the reactions of vibrationally excited CO (v υ 9) and electronically excited O2, probably in the c1Σ-u state, were studied. At low [O2]/[CO] ratios the predominant reactions are of vibrationally excited CO (v υ 9). Relative rate constants for chemical reaction versus deactivation of CO (v υ 9) were obtained. At higher [O2]/[CO] ratios, the principal reactions are of electronically excited O2. Relative rate constants for chemical reactions and deactivation of this electronically excited O2 with CO, O2, and TMP were obtained. From the effect of total pressure on Φ {CO2}, it is proposed that an intermediate CO3 is formed in the reaction of electronically excited O2 with CO.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550030404
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    The free-radical reaction of tri-n-butyltin hydride with peroxidesIssued as NRCC Number 12000. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 343-357 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the tri-n-butyltin radical (Sn ·) induced decomposition of a number of peroxides have been measured in benzene at 10°C. The values range from ∼100 M-1 sec-1 for di-t-butyl peroxide to 2.6 × 107 M-1 sec-1 for di-t-butyl diperoxyisophthalate. The majority of the peroxides, including diethyl peroxide, diacetyl peroxide, and t-butyl peracetate, have rate constants of ∼105 M-1 sec-1. It is shown that di-n-alkyl disulfides are ten times as reactive toward Sn · as di-n-alkyl peroxides, although the exothermicities of these reactions are ∼15 and ∼39 kcal/mole, respectively. The enhanced reactivity of the disulfides is attributed to the easier formation of an intermediate or transition state with 9 electrons around sulfur, compared with an analogous species with 9 electrons around oxygen.The following bond strengths (kcal/mole) have been estimated: D[Sn—OR] = 77; D[Sn—H] = 82; D[Sn—SR] = 83; and D[Sn—OC(O)R] = 86, where R = alkyl. Rate constants for reaction of Sn · with some benzyl esters have also been measured. It has been found that t-butoxy radicals can add to benzene and abstract hydrogen from benzene at ambient temperatures.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550030405
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  • 100
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    Report on the international colloquium on chemically induced dynamic nuclear polarization and its impact on the study of reaction mechanisms, Brussels, Belgium, March 18-19, 1971 (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 375-376 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550030407
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