No abstract

The thermal decompositions of furfural and benzaldehyde have been studied in a heated microtubular flow reactor. The pyrolysis experiments were carried out by passing a dilute mixture of the aromatic aldehydes (roughly 0.1%-1%) entrained in a stream of buffer gas (either He or Ar) through a pulsed, heated SiC reactor that is 2-3 cm long and 1 mm in diameter. Typical pressures in the reactor are 75-150 Torr with the SiC tube wall temperature in the range of 1200-1800 K. Characteristic residence times in the reactor are 100-200 μsec after which the gas mixture emerges as a skimmed molecular beam at a pressure of approximately 10 μTorr. Products were detected using matrix infrared absorption spectroscopy, 118.2 nm (10.487 eV) photoionization mass spectroscopy and resonance enhanced multiphoton ionization. The initial steps in the thermal decomposition of furfural and benzaldehyde have been identified. Furfural undergoes unimolecular decomposition to furan + CO: C4H3O-CHO (+ M) → CO + C4H4O. Sequential decomposition of furan leads to the production of HC≡CH, CH2CO, CH3C≡CH, CO, HCCCH2, and H atoms. In contrast, benzaldehyde resists decomposition until higher temperatures when it fragments to phenyl radical plus H atoms and CO: C6H5CHO (+ M) → C6H5CO + H → C6H5 + CO + H. The H atoms trigger a chain reaction by attacking C6H5CHO: H + C6H5CHO → [C6H6CHO]* → C6H6 + CO + H. The net result is the decomposition of benzaldehyde to produce benzene and CO.

A heated SiC microtubular reactor has been used to decompose acetaldehyde and its isotopomers (CH(3)CDO, CD(3)CHO, and CD(3)CDO). The pyrolysis experiments are carried out by passing a dilute mixture of acetaldehyde (roughly 0.1%-1%) entrained in a stream of a buffer gas (either He or Ar) through a heated SiC reactor that is 2-3 cm long and 1 mm in diameter. Typical pressures in the reactor are 50-200 Torr with the SiC tube wall temperature in the range 1200-1900 K. Characteristic residence times in the reactor are 50-200 μs after which the gas mixture emerges as a skimmed molecular beam at a pressure of approximately 10 μTorr. The reactor has been modified so that both pulsed and continuous modes can be studied, and results from both flow regimes are presented. Using various detection methods (Fourier transform infrared spectroscopy and both fixed wavelength and tunable synchrotron radiation photoionization mass spectrometry), a number of products formed at early pyrolysis times (roughly 100-200 μs) are identified: H, H(2), CH(3), CO, CH(2)=CHOH, HC≡CH, H(2)O, and CH(2)=C=O; trace quantities of other species are also observed in some of the experiments. Pyrolysis of rare isotopomers of acetaldehyde produces characteristic isotopic signatures in the reaction products, which offers insight into reaction mechanisms that occur in the reactor. In particular, while the principal unimolecular processes appear to be radical decomposition CH(3)CHO (+M) → CH(3) + H + CO and isomerization of acetaldehyde to vinyl alcohol, it appears that the CH(2)CO and HCCH are formed (perhaps exclusively) by bimolecular reactions, especially those involving hydrogen atom attacks.

A silicon carbide microtubular reactor has been used to measure branching ratios in the thermal decomposition of furan, C4H4O. The pyrolysis experiments are carried out by passing a dilute mixture of furan (roughly 0.01 %) entrained in a stream of helium through the heated reactor. The SiC reactor (0.6 mm i.d, 2 mm o.d., 2.5 cm long) operates with continuous flow. Experiments were performed with a reactor inlet pressure of 100-300 Torr and a "chemical temperature" within the reactor of approximately 1100-1400 K; characteristic residence times in the reactor are 100-200 µsec. Tunable synchrotron radiation photoionization mass spectrometry is used to monitor the products, measure the branching ratio of the two carbenes as well as the ratio of [HCCCH2]/[HC≡CCH3]. The results of our experiments clearly demonstrate a preference for the decomposition channel through a β-carbene. At temperatures of 1100-1200 K, only HC≡CCH3 is produced. As the temperature rises to 1300-1400 K, roughly 10 % of the flux through the β-carbene channel goes to HCCCH2 radicals.

Synthetic lubricants are widely used for applications that require high thermal and oxidative stability. In order to facilitate new designs and applications for these fluids, we are measuring a suite of thermophysical and transport properties for lubricant base fluids and mixtures. As part of the property measurements, here, we report the global thermal decomposition kinetics of four polyol ester lubricant base oils, in addition to a fully qualified (MIL-PRF-23699) formulation. The fluids were heated in stainless steel ampule reactors and the extent of decomposition was measured by gas chromatography coupled with flame ionization detection (GC-FID), from which pseudo-first-order rate constants were derived. The rate constants for decomposition ranged from 1 × 10–8 s–1 at 500 K to 2 × 10–4 s–1 at 675 K. Arrhenius parameters across this temperature regime are also reported. Other techniques for chemical characterization applied in this work include gas chromatography with mass spectrometry (GC-MS), nuclear magnetic resonance (NMR) spectroscopy, and Karl Fischer titration.