Shock-tube study of the decomposition of tetramethylsilane using gas chromatography and high-repetition-rate time-of-flight mass spectrometry.

The decomposition of tetramethylsilane was studied in shock-tube experiments in a temperature range of 1270-1580 K and pressures ranging from 1.5 to 2.3 bar behind reflected shock waves combining gas chromatography/mass spectrometry (GC/MS) and high-repetition-rate time-of-flight mass spectrometry (HRR-TOF-MS). The main observed products were methane (CH4), ethylene (C2H4), ethane (C2H6), and acetylene (C2H2). In addition, the formation of a solid deposit was observed, which was identified to consist of silicon- and carbon-containing nanoparticles. A kinetics sub-mechanism with 13 silicon species and 20 silicon-containing reactions was developed. It was combined with the USC_MechII mechanism for hydrocarbons, which was able to simulate the experimental observations. The main decomposition channel of TMS is the Si-C bond scission forming methyl (CH3) and trimethylsilyl radicals (Si(CH3)3). The rate constant for TMS decomposition is represented by the Arrhenius expression ktotal[TMS → products] = 5.9 × 1012 exp(-267 kJ mol-1/RT) s-1.

A single-pulse shock tube coupled with high-repetition-rate time-of-flight mass spectrometry and gas chromatography for high-temperature gas-phase kinetics studies.

Shock tubes are frequently used to investigate the kinetics of chemical reactions in the gas phase at high temperatures. Conventionally, two complementary arrangements are used where either time-resolved intermediate species measurements are conducted after the initiation of the reaction or where the product composition is determined after rapid initiation and quenching of the reaction through gas-dynamic processes. This paper presents a facility that combines both approaches to determine comprehensive information. A single-pulse shock tube is combined with high-sensitivity gas chromatography/mass spectrometry for product composition and concentration measurement as well as high-repetition-rate time-of-flight mass spectrometry for time-dependent intermediate concentration determination with 10 µs time resolution. Both methods can be applied simultaneously. The arrangement is validated with investigations of the well-documented thermal unimolecular decomposition of cyclohexene towards ethylene and 1,3-butadiene at temperatures between 1000 and 1500 K and pressures ranging from 0.8 to 2.4 bars. The comparison shows that the experimental results for both detections are in very good agreement with each other and with literature data.