Mitsuo Koshi

Catalytic decomposition of SiH4 on a hot filament

The products of SiH 4 decomposition on the surface of various filaments were directly detected by using vacuum ultraviolet (VUV) photo-ionization mass spectrometry under collision-free conditions. SiH 2 and SiH 3 were detected at filament temperatures of approximately T f ∼1300 K, where silicide formation on the filament was observed. At higher temperatures, the SiH 2 and SiH 3 signal intensities decreased and Si atom signal increased. It was confirmed that the Si atoms were the main species desorbed from the tungsten filament at T, > 1700 K. H atoms were also detected as a direct desorbed species from the filament by using the [2+1] resonance enhanced multi-photon ionization (REMPI) method combined with time-of-flight (TOF) mass spectrometry. Gas phase chemical reactions of SiH4 with desorbed radicals (Si and H atoms) were also investigated. Si 2 H 6 , Si 2 H 4 and Si 2 could be detected as products of gas phase reactions. A chemical kinetic mechanism starting with Si+SiH 4 and H+SiH 4 reactions was proposed to explain the formation of Si 2 H 6 and Si 2 H 4 .

Role of Phenyl Radicals in the Growth of Polycyclic Aromatic Hydrocarbons

To investigate the role of phenyl radical in the growth of PAHs (polycyclic aromatic hydrocarbons), pyrolysis of toluene with and without benzene has been studied by using a heatable tubular reactor couple with an in-situ sampling vacuum ultraviolet (VUV) single photon ionization (SPI) time-of-flight mass spectrometer (TOFMS) at temperatures 1155-1467 K and a pressure of 10.02 Torr with 0.56 s residence time. When benzene was added, a significant increase of phenyl addition products (biphenyl, terphenyl, and triphenylene) was observed and the mass spectra showed a clear regular sequence with an interval of approximately 74 mass number, corresponding to the phenyl addition (+C6H5) followed by H-elimination (-H) and cyclization (-H2). The analysis showed that the PAC (phenyl addition/cylization) mechanism is efficient for the growth of PAHs without a triple fusing site, for which the HACA (hydrogen abstraction/C2H2 addition) step is inefficient, and produces PAHs with five-membered rings. The PAC process was also suggested to be efficient in the subsequent growth of PAHs with five-membered rings. The role of the PAC mechanism in combustion conditions is discussed in relation to the importance of disordered five-membered ring structure in fullerene or soot core.

A highly efficient growth mechanism of polycyclic aromatic hydrocarbons

A highly efficient growth mechanism of polycyclic aromatic hydrocarbons (PAHs) initiated and accelerated by phenyl radicals has been investigated on the basis of kinetic analysis of gas phase reaction products of pyrolysis of benzene with and without addition of acetylene and acetylene only. Pyrolytic reactions were performed in a flow tube reactor and the resulting products were detected by an in situ direct sampling mass spectrometric technique using a vacuum ultraviolet (VUV) single photon ionization (SPI) time of flight mass spectrometry (TOFMS). The detected species varies from smaller to larger PAHs up to m/z = 454 (C(36)H(22)) including primary PAHs, polyphenyl-PAHs and cyclopentafused-PAHs (CP-PAHs). The peculiarity of this result is an appearance of mass peaks at regular mass number intervals of approximately 76 that correspond to phenyl-PAHs produced by phenyl radical addition (+C(6)H(5), +77) followed by hydrogen elimination (-H, -1). All such mass peaks were found diminishing with appearance of -2 mass number peaks with increasing temperatures, certainly due to a conversion of thermally rather unstable phenyl-PAHs into stable condensed PAHs through a dehydrocyclization (-H(2), -2) process. In the same way, in the case of only acetylene pyrolysis, mass peaks at regular mass number intervals of 24 corresponding to the HACA (hydrogen abstraction/C(2)H(2) addition) products, were observed. Kinetic analysis of formation pathways of those observed products showed the active role of PAC (phenyl addition/cyclization) because of its efficiency to continue the endless growth of PAHs, while the HACA was only found efficient for producing symmetrical PAHs by filling a triple fusing site (four carbon bay structure). Especially, acetylene was mixed with benzene to understand the impact of HACA on the PAC path ways that resulted in enhancement of phenyl-PAHs production in spite of trapping of active and chain carrier species phenyl radicals by C(2)H(2) to form phenylacetylene. The comparison of HACA and PAC concluded that PAC is a highly efficient mechanism for the growth of PAHs and lastly their combined roles in combustion have been discussed. Hopefully, PAC will be useful to understand the process of aromatic growth, from furnaces to stellar atmospheres.

Reactions of N(4S) atoms with NO and H2

Reactions of N(4S) atoms with NO and H2 have been investigated using direct detection of N atoms by the atomic resonance absorption technique in a shock tube apparatus, where N(4S) is generated by photodecomposition of NO by 193 nm laser radiation behind reflected shock waves. The rate constant of the reaction, N+NO→N2+O (1) has been determined using pseudo first‐order kinetic analysis to be k1=(1.3±0.3)×1013 (cm3 mol−1 s−1) over 1600–2300 K temperature range, which agrees very well with the estimation by Baulch et al. [Evaluated Kinetic Data for High Temperature Reactions (Butterworths, London, 1973), Vol. 2]. No (or very small) activation energy of this process was confirmed. Also, the rate constant of the reaction, N+H2→NH+H (2) has been decided by adding H2 to NO–Ar mixtures; it is k2=(2.8±0.2)×1014 exp(−Ea/RT) (cm3 mol−1 s−1), where Ea =33±7 kcal/mol. A quantum mechanical calculation performed in order to determine the mechanism of this reaction suggests that the reaction N(4S)+H2→NH+H proceeds via a...

Energy transfer rates and impact sensitivities of crystalline explosives

Abstract The energy transfer rates between phonons and vibrons in the “doorway region” could be the rate-determining step for impact-induced detonation of molecular crystalline explosives. To investigate the relationship between impact sensitivities and energy transfer, the overall rate of energy transfer in the doorway region is estimated on the basis of a simple theory in which the rate is proportional to a product of the number of states and the rate of population relaxation. We estimated frequencies of normal mode vibrations of PETN, β-HMX, RDX, Tetryl, TNT, FOX-7, m-DNB, ANTA, PN, NQ, NTO, and DMN by means of density functional theory calculations at the B3LYP/6-31G(d) level of theory. Normal mode vibrations of TATB were evaluated by using empirical intra-molecular potentials. The number of doorway modes in the regions of 200 to 700 cm −1 was evaluated by the direct counting method. It is found that the number of doorway modes shows a strong correlation with impact sensitivities obtained by drop hammer tests. This can be explained by the theory, if we assume that the rate of population relaxation is almost the same for all of the explosives investigated in the present work. This assumption is consistent with recent experimental measurements of energy transfer rates of explosives at low temperatures.

Rate coefficients of H-atom abstraction from ethers and isomerization of alkoxyalkylperoxy radicals

Group rate expressions for the hydrogen(H)-atom abstraction reactions from ethers by hydrogen atoms and hydroxyl(OH) radicals and the intramolecular hydrogen-transfer isomerization reactions of alkoxyalkylperoxy radicals, which result from the H-abstraction from ethers followed by the addition of O(2), have been evaluated based on the quantum chemical calculations and experimental data. With the relative method proposed in the present study, it was shown that the rate coefficients of the reactions, for which only poor experimental information is available, can be reliably evaluated by calculating and extracting the difference from the well-established reactions of alkane hydrocarbons. The major features on the H-abstraction reactions from O-adjacent sites of ethers compared to those from alkanes were the suppression of the activation energy due to the decrease of the C-H bond dissociation energy and non-next neighbor substituent effect from the alkyl group on the counter side of -O-. For the hydrogen transfer isomerization reactions, similar suppression of the activation energy as well as the change in the ring strain energy was found as a major feature.

Approach for simulating gas-liquid-like flows under supercritical pressures using a high-order central differencing scheme

This study proposes an approach for simulations of cryogenic fluid mixing under supercritical pressures using high-order schemes. In this approach, we introduce a pressure evolution equation and consistently construct numerical diffusion terms to maintain the velocity and pressure equilibriums at fluid interfaces. The interfaces with high density and temperature ratio are successfully captured without the generation of spurious oscillations, while a high-order central differencing scheme resolves the flow fields. The present method preserves the mass and momentum conservation properties, while the poor energy conservation property is recognized. The one-dimensional single and multi-species interface advection and two-dimensional cryogenic jet mixing problems demonstrate the superiority and robustness of the present method over a conventional fully conservative method.

Role of methyl radicals in the growth of PAHs

The role of methyl radicals in the networking of sp2 carbons has been explored through kinetic analysis of mass spectra of the gas-phase products of the pyrolysis of toluene and toluene/acetone mixtures. Pyrolytic reactions were performed in a flow tube reactor at temperatures of 1140–1320 K and a constant total pressure of 10.38 Torr with a residence time of 0.585 s. On addition of acetone, methyl substituted products and their derivatives were enhanced. Mass peaks were observed in several sequences at an interval of 14 mass units; these ions correspond to methyl substituted products formed as a result of hydrogen abstraction (−H) followed by methyl radical addition (+CH3). Each major peak was usually preceded by a peak at two mass units lower, which was likely produced through dehydrogenation/dehydrocyclization (−H2) of methyl substituted products. Detected species include a large number of alkyl, cyclotetrafused (CT), cyclopentafused (CP) mono-, di-, and polycyclic aromatic hydrocarbons (PAHs) along with primary PAHs. The analysis showed that MAC (methyl addition/cyclization) has a unique capacity to induce the sequential growth of hexagonal networks of sp2 carbons from all fusing sites [1] of a PAH. Moreover, MAC was found capable of answering an important question in PAH growth, which is expansion of the CT → CP → hexagonal network for which other reported mechanisms are inefficient.

Updated Kinetic Mechanism for High-Pressure Hydrogen Combustion

A chemical kinetic model for high-pressure combustion ofH2=O2 mixtures has been developed by updating some of the rate constants important under high-pressure conditions without any diluent. The revised mechanism is validated against experimental shock-tube ignition delay times and laminar flame speeds. Predictions of the present modelarealsocomparedwiththosebyseveralotherkineticmodelsproposedrecently.Althoughpredictionsofthose models (including the present model) agree quite well with each other and with the experimental data of ignition delay times and flame speeds at pressures lower than 10 atm, substantial differences are observed between recent experimental data of high-pressure mass burning rates and model predictions, as well as among the model predictions themselves. Different pressure dependencies of mass burning rates above 10 atm in different kinetic models result from using different rate constants in these models for HO2 reactions, especially for H HO2 and OH HO2 reactions.TherateconstantsforthereactionH HO2 involvingdifferentproductchannelswerefound to be very important for the prediction of high-pressure combustion characteristics. An updated choice of rate constants for those reactions is presented on the basis of recent experimental and theoretical studies. The role of O 1 D, which can be produced by the H HO2 reaction, in the high-pressure combustion of H2 is discussed.

Rate constants for the reactions of hydrogen atoms with SiHnF4 − n (n = 4, 3, 2)

Abstract A VUV LIF detection of H atoms has been applied to the direct measurements of rate constants for the title reactions in ArF laser photolysis experiments at T = 293±2 K. The observed rate constants were k (H + SiH 4 ) = (2.2±0.2) × 10 −13 , k (H + SiH 3 F) = (1.1±0.2) × 10 −13 , and k (H + SiH 2 F 2 ) = (2.1±0.6) × 10 −14 cm 3 molecule −1 s −1 . These rate constants were compared to those of other H atom abstraction reactions and linear correlations were found between log k and SiH bond dissociation energies for reactions of H + RH → R + H 2 , as was already suggested for hydrogen abstraction reactions in single-bond hydrocarbons.