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  • Physical Chemistry  (477)
  • Wiley-Blackwell  (477)
  • American Institute of Physics (AIP)
  • Springer
  • 1975-1979  (477)
Collection
Keywords
Publisher
  • Wiley-Blackwell  (477)
  • American Institute of Physics (AIP)
  • Springer
Years
Year
  • 1
    Electronic Resource
    Electronic Resource
    Vibration-Vibration energy exchange between N2O and CO (1975)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 1-13 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The temperature dependence of the vibration-vibration energy transfer between the v3 mode of N2O and the first vibrational level of CO was determined over a range of 780 to 1400°K using a shock tube. Several mixtures of CO-N2O were tested, diluted in 95% Ar. The Landau-Teller plot of the vibration-vibration relaxation times has a least squares line of \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} p\tau _{{\rm VV}} = 2.69T^{ - 1/3} - 1.70 $$\end{document} where pτvv is in atm ·μsec and T in °K. The measured kinetic reaction was determined to be \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm N}_{\rm 2} {\rm O(001) + CO(O)} \to {\rm N}_{\rm 2} {\rm O}(000) + {\rm CO(1) + 81cm}^{{\rm - 1}} $$\end{document} The transfer probabilities for this process were found to vary directly with temperature.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550070102
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  • 2
    Electronic Resource
    Electronic Resource
    Kinetics and mechanisms of substitution reactions with sulfur-containing nucleophiles in aqueous acid solutions. I - rates of reactions of some tetrahalopalladate (II) anions with thiourea and selenourea (1975)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 87-98 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The activation energy parameters for the reaction of PdX42- (X=Cl-, Br-) in aqueous halide acid solution with thiourea (tu) and selenourea (seu) have been determined. High rates of reaction parallel low enthalpies and appreciable negative entropy of activation. The rate law in each case simplifies to kobs=k[L] where L=tu or seu, and only ligand-dependent rate constants are observed at 25°C. The ligand-dependent rate constants for the first identifiable step in the PdCl42- + X system is (9.1±0.1) × 103 M-1 sec-1 and (4.5±0.1) × 104 M-1 sec-1 for X=tu and seu, respectively, while for the PdBr42- + X system it is (2.0±0.1) × 104 M-1 sec-1 and (9.0±0.1) × 104 M-1 sec-1 for X=tu and seu, respectively.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550070110
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  • 3
    Electronic Resource
    Electronic Resource
    The mechanism of the H2 + CL2 reaction: Ignition behind reflected shocks (1975)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 125-142 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed shock-tube investigation of the ignition in H2 + Cl2 + Ar mixtures in a shock tube is presented, and the mechanism of the reaction is discussed. Ignition delay times were determined from pressure and heat flux measurements behind reflected shock waves. The induction times measured ranged between 35 and 2100 μsec over the temperature range of 830-1260°K. The experimental results of close to seventy tests can be correlated by the relationship \documentclass{article}\pagestyle{empty}\begin{document}$$ t_{{\rm ig}} = 10^{ - 12.73} \exp (18.75 \times 10^3 /RT) \cdot [{\rm Cl}_{\rm 2}]^{ - 0.66} [{\rm H}_{\rm 2}]^{ - 0.60} [{\rm Ar]}^{{\rm 0}{\rm .40 }} \,\sec. $$\end{document} where the concentrations are expressed in mole/cm3. The above relationship served as a basis for a computer modeling of the ignition delay times. Ten calculations, simulating typical laboratory experiments, were run by the computer for each reaction scheme and the obtained temperature and composition dependence of the induction times were compared with the ones observed experimentally. A reaction scheme based on a simple exothermal chain propagation could not reproduce the experimental relationship. When the energy branching reaction HCl*(ν) + Cl2 → (HCl3) → HCl + Cl + Cl was added to the reaction scheme, a much better agreement with the experiment was obtained. It is believed that the above reaction does take place and that it is the main supplier of atoms to the system.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550070113
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  • 4
    Electronic Resource
    Electronic Resource
    Kinetics of the reactions Br2 + HCN, BrCN + I-, S(CN)2 + I- in aqueous acid solution (1975)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 205-214 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Spectrophotometric methods have been used to obtain rate laws and rate parameters for the following reactions: with ka, kb, Ea, Eb having the values 85±5 l./mole · s, 5.7±0.2 s-1 (both at 298.2°K), and 56±4 and 66±2 kJ/mole, respectively. with kc=0.106±0.004 l./mole ·s at 298.2°K and Ec=67±2 kJ/mole. with kd=(3.06 ±; 0.15) × 10-3 l./mole ·s at 298.2°K and Ed=66±2 kJ/mole.Mechanisms for these reactions are discussed and compared with previous work.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550070205
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  • 5
    Electronic Resource
    Electronic Resource
    Decarbonylation of complex iridium carbonyls in solution: A problem in chemical dynamics (1975)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 249-272 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of decarbonylation of [Ir(CO)(dp)2]Cl and [IrCl(CO)2(Ph3P)2] has been studied in different solvents, at temperatures between -25° and +70°C, by means of reactors of defined fluid dynamics which allow a separation to be made between “physical” and “chemical” rate constants. Chemical rate constants have been found to depend markedly on the diffusion coefficients of carbon monoxide in the various solvents. The process of decarbonylation has been described, for both reactions, by the sequence: structural isomerization, characterized by a very low preexponential factor, decomposition of the less stable isomer against the solvent's barrier, and diffusion of carbon monoxide to the gas-liquid interface. The kinetic problems involved in the determination of rate constants and their implications have been emphasized.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550070208
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  • 6
    Electronic Resource
    Electronic Resource
    Competitive study of the reactions Br + RFI → IBr + RF and determination of bond dissociation energies D(RF-I) where RF = CF3, C2F5, n-;C3F7, i-C3F7, and n-C4F9 (1975)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 287-300 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The overall photobromination reactions \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Br}_{\rm 2} + {\rm R}_{\rm F} {\rm I} \to {\rm IBr} + {\rm R}_{\rm F} {\rm Br} $$\end{document} have been studied using a competitive technique. Relative Arrhenius parameters were obtained for the rate-determining step These were placed on an absolute basis using previous-absolute values of A and E for RFI=CF3I. The activation energies were used to calculate bond dissociation energies D(R—I) with the following results: TextRF-E16D(RF-I)(kcal/mole)CF3I10.852.6C2F5I8.850.6n-C3F7I7.449.2i-C3F7I7.549.2n-C4F9I6.748.4E16 from [1]The D(RF-I) are compared with related D(R—I) and it is concluded that for a given alkyl group RH and the corresponding perfuloroalkyl group RF, D(RH-I) 〉 D(RF-I) whereas it has previously been found that D(RH-X;) 〈 D(RF-X) where X is not iodine.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550070210
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  • 7
    Electronic Resource
    Electronic Resource
    The Influence of solvent and crown polyethers on the nucleophilic reactivity of potassium tert-Butylperoxide, potassium tert-Butoxide, and some other oxygen bases (1975)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 341-349 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates of reaction of t-BuOOK, t-BuOK, n-BuOOK, and p-MeC6H4OKwith p-nitrophenyl diphenylphosphinate 1 and with p-nitrophenyl benzoate 2 have been measured in toluene both in the absence and in the presence of crown polyether dicyclohexyl-18-crown-6 3a. The rates of nucleophilic displacementon 1 by HOO-, t-BuOO-, and some “nonalpha” oxyanions in water have also been determined. Solvent transfer from water to toluene results in increasing the nucleophilic reactivity of the t-butyl hydroperoxide anion. Rate ratios QQa are given which allow one to estimate the enhanced reactivity of t-BuOO- (an α-nucleophile) compared to oxygen nucleophiles of comparable base strength toward 1 and 2. These are for substrate 1, Qα (water) ≃ 6.5 and Qα (toluene) ≃ 2.7; for substrate 2, Qα (water) ≃ 5.5 and Qα (toluene) ≃ 5. The hypothesis is advanced that solvation is not a major factor in determining the α-effect of the t-butylhydroperoxide anion.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550070304
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  • 8
    Electronic Resource
    Electronic Resource
    On the fast addition reactions of BH3 (1975)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 633-636 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550070412
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  • 9
    Electronic Resource
    Electronic Resource
    Masthead (1975)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975) 
    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.550070501
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  • 10
    Electronic Resource
    Electronic Resource
    Shift of the rate-determining step in a consecutive chemical reaction with variation of the reaction affinity (1975)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 463-471 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A consecutive single-route reaction is considered. When two (groups of) steps compete in controlling the overall reaction rate, there exists a general rule that the earlier step in the flow of the overall reaction tends to be rate-determining with the increase of the reaction affinity. The latter may, however, be distributed more or less evenly to both steps.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550070313
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