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  • 1
    Electronic Resource
    Electronic Resource
    Pyrolytic production of Se (3P) from carbon diselenide. II. Rate of CSe2 decay (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1109-1130 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrolytic decay of carbon diselenide was monitored by ultraviolet absorption spectroscopy in reflected shock waves in the temperature range of 1600-2600°K. The temperature dependence of the absorption coefficient of CSe2 at 2308 Å was determined and was used to provide kinetic information along with a deconvolution procedure which accounted for and removed systematic distortions of the fast time-resolved absorbance profile. For temperatures of 1600-2600°K and argon densities of 1.5-7.0 × 10-5 mol/cm3 dilute (1.0-9.0 × 10-9 mol/cm3) CSe2 pyrolyzed with measured first-order decay rates in the range of log10 k1 (sec-1) = 3.0-5.7; at midrange (2100°K and 4.3 × 10-5 mol/cm3 in Ar) k1 ≈ 3 × 104 sec-1. The decay probably occurs via a unimolecular low-pressure process, first order in both CSe2 and Ar, for which k2 ± 109 cm3/mol·sec at 2100°K. The deconvoluted data yield Arrhenius activation energies of 53.2 kcal/mol under second-order treatment, but the activation energy is less reliable than the general magnitude of the rate constant. A comparison of CSe2 with other molecules which are isoelectronic in their valence shells (CO2, CS2, OCS, and N2O) is made.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550111009
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  • 2
    Electronic Resource
    Electronic Resource
    Pyrolytic production of Se (3P) from carbon diselenide. I. Equilibrium (1977)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 9 (1977), S. 671-687 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermodynamic characteristics of the dissociation of carbon diselenide are examined. Results of a shock-tube study of CSe2 pyrolysis are combined with previously unreported photoionization spectroscopy data on CSe2 and with a critical examination of the available literature on Se(g), Se2(g), CSe(g), CSe2(g), and CSe2(t). Based on the best currently available information, recommendations are made for the values of enthalpies, entropies, heat capacities, and derived functions. In particular, the most likely value for ΔH0 (CSe2(g) → CSe(g) + Se(g, 3P)) is +83 kcal/mol, and for Kp at 2000°K it is 0.018 atm.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550090415
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