Articles written in Journal of Chemical Sciences

    • Kinetics of the thermal decomposition of tetramethylsilane behind the reflected shock waves between 1058 and 1194 K


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      Thermal decomposition of tetramethylsilane (TMS) diluted in argon was studied behind thereflected shock waves in a single pulse shock tube (SPST) in the temperature range of 1058–1194 K. The majorproducts formed in the decomposition are methane $ (CH_{4}$) and ethylene $(C_{2}H_{4})$; whereas ethane and propylenewere detected in lower concentrations. The decomposition of TMS seems to be initiated via Si-C bondscission by forming methyl radicals $ (CH_{3})$ and trimethylsilyl radicals $((CH_{3})_{3}Si)$. The total rate coefficientsobtained for the decomposition of TMS were fit to Arrhenius equation in two different temperature regions1058–1130K and 1130–1194 K. The temperature dependent rate coefficients obtained are $ k_{total}$ (1058–1130 K)

      =$ (4.61 ± 0.70) \times10^{18}$ exp (−(79.9 kcal mol−1 ± 3.5)/RT) s−1,$ k_{total}$ (1130-1194 K) =$ (1.33 ± 0.19) \times 10^{6}$ exp(−(15.3 kcal mol−1 ± 3.5)/RT) s−1. The rate coefficient for the formation of $CH_{4}$ is obtained to be $ k_{methane}$(1058–1194 K) =$ (4.36 ± 1.23) \ times10^{14}$ exp (−(61.9 kcal mol−1±4.9)/RT) s−1. A kinetic scheme containing 21species and 38 elementary reactions was proposed and simulations were carried out to explain the formation ofall the products in the decomposition of tetramethylsilane.

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