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Chemiluminescent gas phase reactions involving electronically excited oxygen molecules trimethylaluminum and diborane near 3 millitorr
Recently the simplest amino acid, glycine, has been detected in interstellar clouds, ISC, although this has since been contested. In order to substantiate either of these claims, plausible routes to amino acids need to be investigated. For gas phase synthesis, the SIFT technique has been employed to study simple amino acids via ion-molecule reactions of several ions of interstellar interest with methylamine, ethylamine, formic acid, acetic acid, and methyl formate. Carboxylic acid type ions were considered in the reactions involving the amines. In reactions where the carboxylic acid and methyl formate neutrals were studied, the reactant ions were primarily amine ion fragments. It was observed that the amines and acids preferentially fragment or accept a proton whenever energetically possible. NH3(+), however, uniquely reacted with the neutrals via atom abstraction to form NH4(+). These studies yielded a body of data relevant to astrochemistry, supplementing the available literature. However, the search for gas phase routes to amino acids using conventional molecules has been frustrated. Our most recent research investigates the fragmentation patterns of several amino acids and several possible routes have been suggested for future study.
The Active Thermochemical Tables approach produces the enthalpy of formation of gas phase boron atom: Δ f H° 298 (B (g) ) = 570.48±0.61 kJ/mol and Δ f H° 0 (B (g) ) = 565.38±0.61 kJ/mol. This is about 5 kJ/mol higher and nearly an order of magnitude more accurate than the CODATA value. Here, while the ATcT value is in excellent agreement with the revisions proposed by Bauschlicher, Martin, and Taylor [J. Phys. Chem. A 103 (1999) 7715] and by Karton and Martin [J. Phys. Chem. A 111 (2007) 5936], it invalidates several earlier theoretical revisions that are too high by up to 5 kJ/mol.
Gas phase chemical reactions effect on heat transfer to charring ablator, deriving numerical solution for multicomponent stagnation point flow
Dynamic model for gas phase concentrations in porous fuel cell electrodes
Arylacetylides such as phenylacetylide (PhCC–, 1) are important nucleophiles used in synthetic chemistry yet rarely have they been studied as bare carbanions. In this work, the phenylacetylide anion was formed via electrospray ionization (ESI) or multistage mass spectrometry (MSn) experiments and subsequently examined in the gas phase by negative ion photoelectron spectroscopy (NIPES), ion-molecule reactions (IMR), alongside theoretical calculations to probe its fundamental structure and reactivity. Photoelectron spectra of PhCC– (1) revealed vertical (VDE) and adiabatic detachment energies (ADE), both of 3.220 eV. The latter value is also the electron affinity (EA) of the phenylethynyl radical (PhCC•) from which a bond dissociation energy (BDE) of phenylacetylene (PhCCH) was derived to be ca. 131.3 ± 1.7 kcal mol-1 using a gas-phase thermochemical cycle. Detachment of an electron from PhCC– at 266 nm likely results in resonant autodetachment, supported by Franck-Condon Factor (FCF) simulations. The phenylacetylide anion reacts with methyl iodide (CH3I) and allyl iodide (C3H5I) via SN2 nucleophilic displacement with measured rate coefficients of 4.29 and 3.66 × 10-10 cm3 molecule-1 s-1, respectively. The mechanisms associated with these displacement reactions are explained and understood in terms of the reaction kinetics, natural bond orbital (NBO) theory, and Density Functional Theory (DFT) calculations.
The effect of instillation of ultrafine TiO2 particles (10-nm anatase-TiO2 and 12-nm rutile-TiO2 (administered in doses from 60 to 1000 microg/rat and 500 microg/rat, respectively) on the respiratory tract of exposed rats was compared to the effects of larger (250 nm anatase-TiO2 and 220-nm rutile-TiO2 particles (given in doses 500 or 1000 microg/rat and 500 microg/rat, respectively). These effects were also compared to the effects of inhalation of 20-nm and 250-nm anatase-TiO2 particles and inhalation with surrogate gas phase components (HF and HCl). It was found that ultrafine TiO2 particles induced greater inflammatory reaction in the lung, had greater adverse effect on alveolar macrophage-mediated clearance function, and had a greater potential to induce mediators which can adversely affect other lung cells than did larger-sized particles. Inhalation of surrogate gas phase components caused injury only to the upper respiratory tract, in contrast to the ultrafine particles, which affected the deep lung.
A simulation model for the analysis of gas-phase trace contaminants in the cabin air of the NASA Space Station Reference Configuration was developed at the NASA Langley Research Center. The model predicts changes in trace contaminant concentrations from both physical and chemical sources and sinks as a function of time. Simulations were performed in which values for relative humidity, temperature, radiation intensity, pressure, and initial species concentrations were constrained to values for these parameters measured and modeled in the continental tropics at the earth's surface. Species concentrations simulated using the model compared favorably with concentrations in the continental tropics which demonstrated that the chemical mechanism in the trace contaminant model approximates changes in atmospheric species concentrations. The sensitivity of initial species concentrations to producing changes in additional species concentrations was also assessed. Results from the model indicated that chemical reactions will be important in determining the composition of cabin air in the Space Station. It is anticipated that the trace contaminant model will be useful in assessing the impact of experiments and commercial operations on the composition of the cabin air in the Space Station.
Graphite and C-H-O gas phase equilibrium at high temperatures and pressures in implication of Earth ocean and atmosphere development
Context: The condensation of inorganic dust grains in the winds of evolved stars is poorly understood. As of today, it is not yet known which molecular clusters form the first dust grains in oxygen-rich (C/O < 1) asymptotic giant branch (AGB) winds. Aluminium oxides and iron-free silicates are often put forward as promising candidates for the first dust seeds. Aims: We aim to constrain the dust formation histories in the winds of oxygen-rich AGB stars. Methods: We obtained Atacama Large Millimeter/sub-millimeter array (ALMA) observations with a spatial resolution of 120 × 150mas tracing the dust formation region of the low mass-loss rate AGB star, R Dor, and the high mass-loss rate AGB star, IK Tau. We detected emission line profiles of AlO, AlOH, and AlCl in the ALMA data and used these line profiles to derive a lower limit of atomic aluminium incorporated in molecules. This constrains the aluminium budget that can condense into grains. Results: Radiative transfer models constrain the fractional abundances of AlO, AlOH, and AlCl in IK Tau and R Dor. We show that the gas-phase aluminium chemistry is completely different in both stars with a remarkable difference in the AlO and AlOH abundance stratification. The amount of aluminium locked up in these three molecules is small, ≤1.1×10−7 w.r.t. H2, for both stars, i.e. only ≤2% of the total aluminium budget. An important result is that AlO and AlOH, which are the direct precursors of alumina (Al2O3) grains, are detected well beyond the onset of the dust condensation, which proves that the aluminium oxide condensation cycle is not fully efficient. The ALMA observations allow us to quantitatively assess the current generation of theoretical dynamical-chemical models for AGB winds. We discuss how the current proposed scenario of aluminium dust condensation for low mass-loss rate AGB stars within a few stellar radii from the star, in particular for R Dor and W Hya, poses a challenge if one wishes to explain both the dust spectral features in the spectral energy distribution (SED) in interferometric data and in the polarized light signal. In particular, the estimated grain temperature of Al2O3 is too high for the grains to retain their amorphous structure. We advocate that large gas-phase (Al2O3)n clusters (n > 34) can be the potential agents of the broad 11µm feature in the SED and in the interferometric data and we propose potential formation mechanisms for these large clusters.
This work presents a semi-detailed kinetic model to address the pyrolytic gas-phase reactivity of volatiles formed during thermal degradation of polyethylene (PE). The model builds on a validated multi-step condensed-phase model and employs validated lumping approaches. Short-chain compounds are modelled with high detail, while long-chain ones are described by surrogate species representative of diesel-cuts (NC16H32) and waxes (NC30H60). The reactivity of short chains is described through the comprehensive CRECK kinetic model, updated to align C5-C7 olefins based on recent literature experimental data. Due to the lack of experimental data for longer olefins, their reactivity is modeled by analogy to the shorter ones, ensuring an asymptotic behavior with increasing carbon numbers. The semi-detailed model is validated through experimental data on PE pyrolysis, assuming an instantaneous mixing of the inert inlet flow with released volatiles, followed by a segregated plug-flow behavior. Validation across different reactor setups confirms the model’s capability to predict detailed product distributions. Despite minor discrepancies, the proposed model effectively captures experimental trends. Further work will address modelling the reactivity in oxygen-containing environments.
This work presents a semi-detailed kinetic model to address the pyrolytic gas-phase reactivity of volatiles formed during thermal degradation of polyethylene (PE). The model builds on a validated multi-step condensed-phase model and employs validated lumping approaches. Short-chain compounds are modelled with high detail, while long-chain ones are described by surrogate species representative of diesel-cuts (NC16H32) and waxes (NC30H60). The reactivity of short chains is described through the comprehensive CRECK kinetic model, updated to align C5-C7 olefins based on recent literature experimental data. Due to the lack of experimental data for longer olefins, their reactivity is modeled by analogy to the shorter ones, ensuring an asymptotic behavior with increasing carbon numbers. The semi-detailed model is validated through experimental data on PE pyrolysis, assuming an instantaneous mixing of the inert inlet flow with released volatiles, followed by a segregated plug-flow behavior. Validation across different reactor setups confirms the model’s capability to predict detailed product distributions. Despite minor discrepancies, the proposed model effectively captures experimental trends. Further work will address modelling the reactivity in oxygen-containing environments.
A comparison of ozone determinations based on ultraviolet absorption photometry and gas-phase titration (GPT) shows good agreement between the two methods. Together with other results, these findings indicate that three candidate reference methods for ozone, UV photometry, IR photometry, and GPT are in substantial agreement. However, the GPT method is not recommended for routine use by air pollution agencies for calibration of ozone monitors because of susceptibility to experimental error.
Results are presented and discussed for a number of gas phase free radical reactions where H/D isotope effects provide valuable mechanistic insights. The cases considered are (1) the reactions of OH, NO3, and Cl with atmospheric reduced sulfur compounds, (2) the reactions of OH and OD with CH3CN and CD3CN, and (3) the reactions of alkyl radicals with HBr and DBr.
This is an index to the literature for gas phase bimolecular positive ionmolecule reactions. Over 2300 references are cited. Reaction rate coefficients and product distributions of the reactions are abstracted out of the original citations where available. This index is intended to cover the literature from 1936 to 2003. This is a continuation of several surveys: the original (Huntress Astrophys. J. Suppl. Ser., 33, 495 (1977)), an expansion (Anicich and Huntress, Astrophys. J. Suppl. Ser. 62, 553 (1986)), a supplement (Anicich, Astrophys. J. Suppl. Ser. 84, 215 (1993)), and an evaluation (Anicich, V. G. J. Phys. Chem. Ref. Data 22,1469 (1993b). The Table of reactions is listed by reactant ion.
A combined experimental/theoretical study is presented of the onset conditions for gas phase reaction and particle nucleation in hot substrate/cold gas CVD of transition metal oxides. Homogeneous reaction onset conditions are predicted using a simple high activation energy reacting gas film theory. Experimental tests of the basic theory are underway using an axisymmetric impinging jet CVD reactor. No vapor phase ignition has yet been observed in the TiCl4/O2 system under accessible operating conditions (below substrate temperature Tw = 1700 K). The goal of this research is to provide CVD reactor design and operation guidelines for achieving acceptable deposit microstructures at the maximum deposition rate while simultaneously avoiding homogeneous reaction/nucleation and diffusional limitations.
It has been observed that water can react with activated gas-phase lanthanide tetranitrato complexes ([Ln(NO3)4]-) to form a hydroxylated species. These reactions, which are proposed to involve water splitting, are observed for most -- but not all -- of the lanthanides. Thus, study of this system could yield insight into how small changes in electronic structure (through variation of the lanthanide species) influences water-splitting reactions, help guide development of new materials used to convert water to hydrogen using electricity. The mechanism proposed in the literature is: (Step 1) [Ln(NO3)4]- ? [LnO(NO3)3]- + ?NO2 (Step 2) [LnO(NO3)3]- + H2O ? [LnOH(NO3)3]- + ?OH The purpose of this study is to determine if the reaction mechanism really does involve splitting of water or proceeds through an alternative pathway.
Gas phase pressure effects on the apparent thermal conductivity of a JSC-1A/air mixture have been experimentally investigated under steady state thermal conditions from 10 kPa to 100 kPa. The result showed that apparent thermal conductivity of the JSC-1A/air mixture decreased when pressure was lowered to 80 kPa. At 10 kPa, the conductivity decreased to 0.145 W/m/degree C, which is significantly lower than 0.196 W/m/degree C at 100 kPa. This finding is consistent with the results of previous researchers. The reduction of the apparent thermal conductivity at low pressures is ascribed to the Knudsen effect. Since the characteristic length of the void space in bulk JSC-1A varies over a wide range, both the Knudsen regime and continuum regime can coexist in the pore space. The volume ratio of the two regimes varies with pressure. Thus, as gas pressure decreases, the gas volume controlled by Knudsen regime increases. Under Knudsen regime the resistance to the heat flow is higher than that in the continuum regime, resulting in the observed pressure dependency of the apparent thermal conductivity.