1. Tests of the coupled shock tube/mass-spectrometer technique ; 2. The pyrolysis of neopentane by atomic resonance absorption spectrophotometry

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Virginia Polytechnic Institute and State University

Part 1

The coupled shock-tube/mass spectrometer apparatus is characterized in terms of its capabilities for chemical kinetic studies. Criteria for doing kinetic measurements by this experimental technique are discussed.

The characterization experiments showed that our apparatus was capable of giving plausible signal shapes for non-reactive dynamic shots at P₁ = 5 torr. Measurements of ion current under static conditions showed that response of the quadrupole mass spectrometer was linear over a range of P₁ = 0-5 torr. Schlieren measurements indicated that the shock wave velocity was erratic and non-reproducible over the last 5 feet of the test section and that the velocity at the endwall could not be predicted from the schlieren data. The electron beam width was found to be ~.1" and the implications of this measurement for further studies on the free jet are outlined. The present beam width is suitable for jet studies in which bulk ionization of gas from a cross-section of the jet is performed. Design improvements needed for future reactive studies on our system are reviewed.

In addition, experimental studies of jet risetime with a pulsed molecular beam apparatus showed poor agreement between the experimental and theoretical jet risetimes. The apparent discrepancy is discussed and possible explanations for it are given.

Part 2

The rate constant k₁ for the reaction C₅H₁₂ → C₄H₉ + CH₃ was determined from reflected shock experiments (1100-1300°K) in which the progress of reaction was monitored by the appearance of H atoms. Atomic resonance absorption spectrophotometry at the Lyman-α line was performed on three mixtures (20 ppm, 10 ppm, 5 ppm) of neopentane in argon to give k₁ = .17 x 10¹⁸ exp (-84800±6200/RT) sec⁻¹. This result is in very good agreement with earlier single pulse shock tube experiments.

In addition, calibration experiments for H atom were performed by shock-heating two mixtures (10 ppm and 5 ppm) of neopentane in argon. The results obtained were in good agreement with previous calibration data.