Kinetic Modelling of Atmospheric Pressure Corona Discharges in Humid Air

Corona discharge is a self-sustained discharge of gaseous medium in inhomogeneous electric fields, which often occurs on transmission lines and has some adverse effect on the power transmission system. In this paper, a kinetic model of corona discharges is presented to simulate the evolution process of charged particles and neutral species in humid air. To investigate the effect of humidity, our model consists of 69 species and 393 chemical reactions which consider important reactions containing H₂O molecules and hydrates. In addition, CO₂ molecules are also included to improve the integrity of reaction database. A temporal evolution of reduced electric field strengths E/N, which are typical experimental values of corona discharges, is used as input. The simulation results show that H₃O⁺ is one of the dominant positive ions which is in qualitative agreement with previous experimental results. The effect of humidity and pulse width on the plasma chemistry is also discussed. It is found that the humidity affects the maximum density and life time of the specific species. Meanwhile, the plasma chemistry could be affected by different pulse widths of the input electric field.

     

Pyrolysis and Oxidation of Methane in a RF Plasma Reactor

The chemical kinetic effects of RF plasma on the pyrolysis and oxidation of methane were studied experimentally and computationally in a laminar flow reactor at 100 Torr and 373 K with and without oxygen addition into He/CH₄ mixtures. The formation of excited species as well as intermediate species and products in the RF plasma reactor was measured with optical emission spectrometer and Gas Chromatography and the data were used to validate the kinetic model. The kinetic analysis was performed to understand the key reaction pathways. The experimental results showed that H₂, C₂ and C₃ hydrocarbon formation was the major pathways for plasma assisted pyrolysis of methane. In contrast, with oxygen addition, C₂ and C₃ formation dramatically decreased, and syngas (H₂ and CO) became the major products. The above results revealed oxygen addition significantly modified the chemistry of plasma assisted fuel pyrolysis in a RF discharge. Moreover, an increase of E/n was found to be more beneficial for the formation of higher hydrocarbons while a small amount of oxygen was presented in a He/CH₄ mixture. A reaction path flux analysis showed that in a RF plasma, the formation of active species such as CH₃, CH₂, CH, H, O and O (¹D) via the electron impact dissociation reactions played a critical role in the subsequent processes of radical chain propagating and products formation. The results showed that the electronically excitation, ionization, and dissociation processes as well as the products formation were selective and strongly dependent on the reduced electric field.     

Plasma catalytic reaction of natural gas to C2 product over Pd-NiO/Al2O3 and Pt-Sn/Al2O3 catalysts

The decomposition of natural gas over Pd-NiO/Al₂O₃ and Pt-Sn/Al₂O₃ is carried out in a microwave catalytic reaction at room temperature. The decomposition of methane is caused by collision by excitation of unstable electronic state. Measuring the flow rate and plasma power can provide kinetic data and indicate the mechanism. The conversion of C₂ products increases from 47 to 63.7% in the microwave plasma catalytic reaction with electric field. Comparing the activities of catalysts, Pd-NiO/Al₂O₃ bimetallic catalyst is more active than Pt-Sn/Al₂O₃ catalyst because of modification of the surface of catalysts by carbon formation. The kinetic modeling of plasma of methane conversion seems related to the power of the electric discharge. It was also revealed that proper coking or polymeric carbon formation improves the catalytic activity; therefore, the conversion of methane may increase over Pd-Ni/Al₂O₃ catalyst in the plasma system.     

Experimental and kinetic study of shock initiated ignition in homogeneous methane–hydrogen–air mixtures at engine‐relevant conditions

The ignition delay time of two stoichiometric methane/hydrogen/air mixtures has been measured in a shock tube facility at pressures from 16 to 40 atm and temperatures from 1000 to 1300 K. Overall, the observed reduction in ignition delay with some methane replaced by hydrogen is relatively small given the large concentration of hydrogen involved in the current study. With a high hydrogen mole fraction (35% of the total fuel), a reduction of the ignition‐promoting effect was observed with reduced temperature. A detailed chemical kinetic mechanism was used to simulate ignitions of test mixtures behind reflected shocks. An analysis of the mechanism indicates that at higher temperatures, the rapid decomposition of hydrogen molecules leads to a quick formation of H radical pools, which promote the chain branching through H + O₂ ? O + OH. At lower temperatures, the branching efficiency of hydrogen is low; a weak effect of hydrogen on methane ignition could be result from the reaction between H₂ and methylperoxy CH₃O₂, which contributes extra H radicals to the reaction system. The effects of hydrogen also decrease with increasing pressure; this is related to the negative pressure dependence of hydrogen at the second ignition limit. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 221–233, 2006     

Properties of halogen atoms for representing intermolecular electrostatic interactions related to halogen bonding and their substituent effects

The electrostatic properties of halogen atoms are studied theoretically in relation to their ability of halogen bonding, which is an attractive intermolecular interaction of a covalently bonded halogen atom with a negatively charged atom of a neighboring molecule. The electric quadrupole (of electronic origin) with a positive zz component Θ_zz of a covalently bonded halogen atom, where the z axis is taken along the covalent bond involving the halogen atom, is mainly responsible for the attractive electrostatic interaction with a negatively charged atom. This positive Θ_zz is an intrinsic property of halogen atoms with the p_x²p_y²p_z configuration of the valence electronic shell, as shown by ab initio molecular orbital calculations for isolated halogen atoms with this electronic configuration, and increases in the order of F < Cl < Br < I, in parallel with the known general sequence of the strength of halogen bonding. For halogen‐containing aromatic compounds, the substituent effects on the electrostatic properties are also studied. It is shown that the magnitude of Θ_zz and the electric field originating from it are rather insensitive to the substituent effect, whereas the electric field originating from atomic partial charges has a large substituent effect. The latter electric field tends to partially cancel the former. The extent of this partial cancellation is reduced in the order of Cl < Br < I and is also reducible by proper substitution on or within the six‐membered ring of halobenzene. Perspectives on the development of potential function parameters applicable to halogen‐bonding systems are also briefly discussed. © 2009 Wiley Periodicals, Inc. J Comput Chem 2010     

Plasma Assisted Low Temperature Combustion

This paper presents recent kinetic and flame studies in plasma assisted low temperature combustion. First, the kinetic pathways of plasma chemistry to enhance low temperature fuel oxidation are discussed. The impacts of plasma chemistry on fuel oxidation pathways at low temperature conditions, substantially enhancing ignition and flame stabilization, are analyzed base on the ignition and extinction S-curve. Secondly, plasma assisted low temperature ignition, direct ignition to flame transition, diffusion cool flames, and premixed cool flames are demonstrated experimentally by using dimethyl ether and n-heptane as fuels. The results show that non-equilibrium plasma is an effective way to accelerate low temperature ignition and fuel oxidation, thus enabling the establishment of stable cool flames at atmospheric pressure. Finally, the experiments from both a non-equilibrium plasma reactor and a photolysis reactor are discussed, in which the direct measurements of intermediate species during the low temperature oxidations of methane/methanol and ethylene are performed, allowing the investigation of modified kinetic pathways by plasma-combustion chemistry interactions. Finally, the validity of kinetic mechanisms for plasma assisted low temperature combustion is investigated. Technical challenges for future research in plasma assisted low temperature combustion are then summarized.     

Membrane catalytic deprotonation effects

Membrane catalytic deprotonation of water (water splitting) has been studied on the base of a new model which suggests that water molecules are prepolarized by H⁺-affinited and OH⁻-affinited fixed charged groups of membrane before their dissociation is enhanced by electric field. Introducing some anion selective groups such as Mg(OH)₂·xH₂O or amine into a cation selective perfluorosulfonated membrane can initiate a dramatic water splitting effect and give rise to new high frequency peaks on the OH and OD stretching region of IR spectra. This supports the hypothesis that some water molecules were affected by the surrounding electrical field from the bipolar membrane-like structure. Perfluorocarboxylic membrane was also tested in a electrolytic cell and it causes H⁺ ion fluxes much larger than Nafion-type membrane. We classify the effect as membrane catalytic deprotonation of carboxylic acid group.     

Ab initio Quantum Mechanics/Molecular Mechanics Molecular Dynamics Simulation of CO in the Heme Distal Pocket of Myoglobin

Myoglobin has important biological functions in storing and transporting small diatomic molecules in human body. Two possible orientations of carbon monoxide (CO) in the heme distal pocket (named as B₁ and B₂ states) of myoglobin have been experimentally indicated. In this study, ab initio quantum mechanics/molecular mechanics (QM/MM) molecular dynamics simulation of CO in myoglobin was carried out to investigate the two possible B states. Our results demonstrate that the B₁ and B₂ states correspond to Fe…CO (with carbon atom closer to iron center of heme) and Fe…OC (with oxygen atom closer to Fe), by comparing with the experimental infrared spectrum. QM electrostatic polarization effect on CO brought from the protein and solvent environment is the main driving force, which anchors CO in two distinctive orientations and hinders its rotation. The calculated vibrational frequency shift between the state B₁ and B₂ is 13.1 cm^-1, which is in good agreement with experimental value of 11.5 cm^-1. This study also shows that the electric field produced by the solvent plays an important role in assisting protein functions by exerting directional electric field at the active site of the protein. From residue-based electric field decomposition, several residues were found to have most contributions to the total electric field at the CO center, including a few charged residues and three adjacent uncharged polar residues (namely, HIS64, ILE107, and PHE43). This study provides new physical insights on rational design of enzyme with higher electric field at the active site.     

Ethylene pyrolysis and oxidation: A kinetic modeling study

Ethylene oxidation and pyrolysis was modeled using a comprehensive kinetic reaction mechanism. This mechanism is an updated version of one developed earlier. It includes the most recent findings concerning the kinetics of the reactions involved in the oxidation of ethylene. The proposed mechanism was tested against ethylene oxidation experimental data (molecular species concentration profiles) obtained in jet stirred reactors (1–10 atm, 880–1253 K), ignition delay times measured in shock tubes (0.2–12 atm, 1058–2200 K) and ethylene pyrolysis data in shock tube (2–6 atm, 1700–2200 K). The general prediction of concentration profiles of minor species formed during ethylene oxidation is improved in the present model by using more accurate kinetic data for several reactions (principally: HO₂ + HO₂ → H₂O₂ + O₂, C₂H₄ + OH → C₂H₃ + H₂O, C₂H₂ + OH → Products, C₂H₃ → C₂H₂ + H).     

Negative Electron Mobility in Attachment-Dominated Plasmas

The temporal evolution of the electron velocity-distribution function(EVDF), the concentration, mean energy, and the drift velocity of theelectrons is studied on a kinetic basis in a weakly ionized Ar/F₂mixture plasma under conditions when the electron concentration temporallydecreases as a result of the electron attachment to fluoride molecules. Usingan appropriate relaxation model, the time-dependent electron Boltzmannequation was solved in multiterm and two-term approximations of the velocitydistribution function. The multiterm results confirmed predictions on theoccurrence of negative electron mobilities in such a decaying Ar/F₂plasma, which were made in a former study using the conventional two-termapproximation. The investigations particularly showed that this approximationgives almost accurate results for the EVDF and related electron swarm parametersexcept for in the very beginning of the relaxation process. It has been furthershown that for a certain range of the reduced electric field strength, thedrift velocity becomes negative in the process of temporal evolution and remainsnegative even when approaching the hydrodynamic stage of the electronswarm. In addition, the role played by the back heating from the gas byelastic collisions on the EVDF formation is studied and various comparisonswith corresponding Monte Carlo results are performed.     

Kinetic model of the H2-O2 surface reaction on platinum at high partial pressure

Heterogeneous ignition temperature of H₂/O₂/N₂ mixture on polycrystalline platinum was measured for a wide range of composition at 101,330 Pa. We propose a new surface kinetic model of H₂ oxidation on platinum by modification of the traditional surface reaction model. This revised version was published online in June 2006 with corrections to the Cover Date.     

Quasielastic light scattering by flexible polymers in the presence of a sinusoidal driving field: internal relaxation modes

Application of an applied electric field to a system of charged molecules superimposes a constant drift velocity on the random thermal motions of the molecules. The spectral density of light scattered from this system is frequency shifted by an amount proportional to the electrophoretic mobility of the molecule. Current theories consider only the application of a square-wave field and the effect on the center-of-mass motion of the molecule. A theory is developed in the present communication that considers the effect of a sinusoidal field on the internal motions of random coils. If the applied frequency is greater than ω_D=μEKcos(θ/2), then the center-of-mass motion remains random whereas internal modes may be “driven” by the applied field. Furthermore, the amplitude of the Doppler-shifted peak position diminishes if ωτ_m > 1, where τm is the relaxation time of the mth mode. It is possible, therefore, to obtain precise values for the number of relaxation modes present and their characteristic relaxation times.     

Effect of electric field on phase separation of polymer dispersed liquid crystal

The kinetics of the polymerization induced phase separation of liquid crystal (LC)/monomer mixture has been investigated by means of depolarized light intensity technique and polarized light microscope (PLM). To examine the effect of the electric field, a DC electric field was applied across the mixtures during the phase separation process. The kinetic study indicates that the phase separation process is accelerated when the electric field is applied. The morphologies of the formed polymer dispersed liquid crystal (PDLC) films were observed by PLM. The electric field applied during the phase separation process yields the PDLC with small LC domains and fine morphologies. The clearing temperature (T_NI) of the formed PDLC films was measured by the PLM and it is found that the T_NI increases with the applied electric field intensity.     

Method for the simultaneous characterization of texture,orientation of electric field gradient,and/or magnetic field from the57Fe/57Co Mössbauer spectrum of pellets having a cylindrical texture typical of YBa2Cu3O7−x superconductors

A method using Mössbauer spectroscopy has been developed for estimating the degree of cylindrical texture in pellets of materials exemplified by the superconductor YBa₂Cu₃O_7–x.The procedure can also be used to determine unambiguously the sign and orientation of the electric field gradient of a nonmagnetic species coexisting with a magnetically ordered one (or coexisting with another nonmagnetic species for which the sign and the orientation of the electric field gradient are known).     

Thermal Studies on Energetic Compounds

The nitrate complexes of copper, nickel and zinc with diethylenetriamine (dien) i.e. [Cu(dien)₂](NO₃)₂, [Ni(dien)₂](NO₃)₂·2H₂O and [Zn(dien)₂](NO₃)₂ have been prepared and characterised. Thermal studies were undertaken using TG-DTG, DSC, ignition delay (t _id) and ignition temperature (IT) measurements. Impact sensitivity was measured using drop mass technique. The kinetic parameters for both non-isothermal and isothermal decomposition of the complexes were evaluated by employing Coats-Redfern (C-R) method and Avrami-Erofeev (A-E) equations (n=2 and 3), respectively. The kinetic analysis, using isothermal TG data, was also made on the basis of model free isoconversional method and plausible mechanistic pathways for their decomposition are proposed. Rapid process was assessed by ignition delay measurements. All these complexes were found to be insensitive towards impact of 2 kg mass hammer up to the height limit (110 cm) of the instrument used. The heat of reaction (?H) for each stage of decomposition was determined using DSC.     

Effect of the Electric Conductivity of a Catalyst on Methane Activation in a Dielectric Barrier Discharge Reactor

The influence of catalyst electric conductivity on methane activation in a planar-type dielectric barrier discharge reactor is investigated by empirically comparing the degree of methane conversion of bare Al₂O₃ with that of Pt/Al₂O₃; from this, it is determined that the latter catalyst converts less methane owing to the presence of Pt. Calculations and comparisons of electric fields with and without Pt show that the presence of a Pt catalyst results in a lower electric field than does bare Al₂O₃. An analysis of product gases based on the correlation between the fragmentation of radicals and the electric field also indicates that the electric field is decreased by using Pt. From these results, it can be concluded that the synergies between the plasma and the conductive catalysts need to be reassessed for different electric field conditions, and that further studies of non-conductive catalysts that can enhance methane activation and synergistic effects are needed.     

The effect of the electric field on the kinetics of dichlorosilane oxidation in the absence of discharge

A constant electric field incapable of discharge generation affects the kinetics of the ignition and combustion of dichlorosilane-oxygen mixtures: near the lower self-ignition limit, the induction period decreases and the region of the oscillating combustion regimes is enlarged. These phenomena depend on the material and state of the reactor surface. The lower self-ignition limitP ₁ over the CuSO₄ and ZnSO⁴ surfaces abruptly increases with an increase in the voltage of the constant electric field.     

Dual Tunability for Uncatalyzed N-Alkylation of Primary Amines Enabled by Plasma-Microdroplet Fusion

The fusion of non-thermal plasma with charged microdroplets facilitates catalyst-free N-alkylation for a variety of primary amines, without halide salt biproduct generation. Significant reaction enhancement (up to >200×) is observed over microdroplet reactions generated from electrospray. This enhancement for the plasma-microdroplet system is attributed to the combined effects of energetic collisions and the presence of reactive oxygen species (ROS). The ROS (e.g., O₂⋅⁻) act as a proton sink to increase abundance of free neutral amines in the charged microdroplet environment. The effect of ROS on N-alkylation is confirmed through three unique experiments: (i) utilization of radical scavenging reagent, (ii) characterization of internal energy distribution, and (iii) controls performed without plasma, which lacked reaction acceleration. Establishing plasma discharge in the wake of charged microdroplets as a green synthetic methodology overcomes two major challenges within conventional gas-phase plasma chemistry, including the lack of selectivity and product scale-up. Both limitations are overcome here, where dual tunability is achieved by controlling reagent concentration and residence time in the microdroplet environment, affording single or double N-alkylated products. Products are readily collected yielding milligram quantities in eight hours. These results showcase a novel synthetic strategy that represents a straightforward and sustainable C−N bond-forming process.     

Activation of Au–Ag Plasmonic Bimetallic Nanocatalysts with Cold Plasma: The Role of Loading Sequence of Plasmonic Metals and Discharge Atmosphere

The activation of Au–Ag plasmonic bimetallic nanocatalyst can make the nanocatalyst exhibit superior visible-light (VL) photocatalytic activity. An efficient activation of Au–Ag nanocatalyst by cold plasma requires the restructuring of Au and Ag species over catalyst surface to form Au–Ag alloy nanoparticles while suppressing agglomeration of the nanoparticles. We here report that the loading sequence of Au and Ag components on titanium dioxide (TiO₂) support during catalyst preparation and discharge atmosphere play important roles in the plasma activation. Preparation of AuAg/TiO₂ nanocatalyst by depositing Ag and Au in sequence could avoid the undesired loss of Ag component, and ensure an effective restructuring of Au and Ag species in O₂ plasma activation. Compared with the reductive (H₂) and inert (Ar and N₂) plasmas, discharge in oxidative O₂ establishes Coulomb field with the negatively charged species over catalyst surface and enable the restructuring and intimate interaction of Au and Ag species. The catalyst characterization and density functional theory calculations suggest that O₂ plasma endows AuAg/TiO₂ nanocatalyst with large numbers of Au–Ag alloy nanoparticles, small size of plasmonic nanoparticles, high density of coordinatively unsaturated sites, and high content of surface oxygen species in the activation, which facilitates the adsorption and activation of O₂, and thus CO oxidation reaction under VL irradiation.

     

Excitation of Electronic States of N<Subscript>2</Subscript> in Radio-Frequency Electric Field by Electron Impact

Excitation of electronic states of the N₂ molecule by electron impact is recognized as an essential process in nitrogen plasmas that strongly impacts their chemical reactivity and other properties. Many surface and coating technologies are based on radio-frequency plasma discharges in nitrogen. In this paper the electron impact excitation rate coefficients for singlet and triplet electronic states of the N₂ molecule have been calculated in non-equilibrium conditions in the presence of a radio-frequency electric field. A Monte Carlo simulation has been performed in order to determine non-equilibrium electron energy distribution functions within one period of the electric field. By using these distribution functions, the excitation rate coefficients have been obtained in the frequency range from 13.56 up to 500 MHz, at reduced electric field values from 200 to 700 Td.