Abstract
A kinetic investigation of the second-order reactions Ca(1S) + Cl2(1 ) →(k1Ca) CaCl + Cl and Sr(1S) + Cl2(1 ) →(k1Sr) SrCl + Cl was carried out in a fast-flow reactor in the temperature ranges of respectively 303−1038 K and 303−991 K. The calcium and strontium atoms in the gas phase were generated by thermal evaporation of the solid metal pellets. The concentration of the gas-phase metal atoms was followed by means of atomic absorption spectroscopy (AAS) at wavelengths of 422.7 nm for calcium and 460.7 nm for strontium atoms. Both reactions show an Arrhenius behavior and the rate constants are given by k1Ca = [(6.0 ± 0.8) × 10-10]exp(−0.2 ± 0.5 kJ mol-1/RT)cm3 molecule-1 s-1 and k1Sr = [(7.3 ± 0.6) × 10-10]exp(−0.4 ± 0.4 kJ mol-1/RT)cm3 molecule-1 s-1. The results are interpreted in terms of the electron-jump mechanism. For both the Ca/Cl2 and the Sr/Cl2 reactions, the experimental rate constants are too high to be quantitatively explained by the classical electron-jump mechanism. However, the modified el...
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