Effect of laser-induced excitation of oxygen on ignition in HCCI engines analysed by numerical simulations

Lack of proven means to control ignition impedes practical implementation of homogenous charge compression ignition (HCCI) engines. In the present paper, we investigate if laser-induced excitation of oxygen might aid solution of the ignition control problem in HCCI engines. Simulations by previous researchers showed laser-induced excitation of oxygen enhances ignition in supersonic combustion. Based on this previous research, we extend a chemical kinetic mechanism for propane autoignition to include reactions for two excited oxygen states, O₂(a¹Δ _g ) and O₂(b¹Σ _g ⁺). Simulations examined the effect of each of these excited O₂ states upon ignition timing in an HCCI engine. Results indicate that achieving useful control of the combustion process requires substantial conversion of O₂ to either of the excited states. At the required level of excitation, the power required for the laser may lower engine efficiency.     

An insight into the reaction kinetics of CH3 + O2(a1Δg) and its enhancement effect on methane ignition

The reaction between CH₃ and O₂(a¹?_g) is crucial to understand the effects of electronically excited oxygen in plasma-assisted combustion of methane and other hydrocarbons. In the present work, multireference quantum chemical methods were used to investigate the potential energy surface of CH₃ + O₂(a¹?_g). The RRKM/master equation simulation was employed to compute the rate coefficients of various pathways to this reaction over the temperature range of 300–2000 K and a pressure range of 0.1–100 atm. Special attention has been paid to the nonadiabatic transition between the excited state and ground state, which directly leads to a quenching channel from CH₃ + O₂(a¹?_g) to CH₃ + O₂(X³∑_g^?). This quenching reaction has been overlooked by previous theoretical and kinetic modeling studies. We also conducted kinetic modeling to examine the effect of this reaction on the ignition enhancement of methane oxidation. Although the channel of CH₃ + O₂(a¹?_g) quenching to CH₃ + O₂(X³∑_g^?) has nonnegligible rate constants comparing with other reaction channels, modeling result with the inclusion of 5% O₂(a¹?_g) in molecular oxygen shows that the titled reactions shorten the ignition delay time of methane by more than twenty times at 900 K, 1 atm. The ignition enhancement is mainly from the chain branching channels to CH₂O + OH and CH₃O + O which has been greatly promoted by excess energy from O₂(a¹?_g). The present study uncovers the kinetic mechanism of this nonadiabatic reaction and provides reasonable rate coefficients for further kinetic modeling of plasma-assisted combustion of methane and other hydrocarbons.     

On combustion enhancement mechanisms in the case of electrical-discharge-excited oxygen molecules

Combustion intensification mechanisms in a supersonic flow of a hydrogen-oxygen mixture behind the oblique shock wave front are investigated for the case when vibrations and the a ¹Δ_g and b ¹Σ _g ⁺ electron states of a O₂ molecule are excited by an electrical discharge. The presence of vibrationally excited and electronically excited O₂ molecules in the oxygen plasma allows intensification of the chain mechanism in the H₂-O₂ mixture even if the energy put into O₂ molecules in the discharge is low. Excitation of O₂ molecules is several tens of times more efficient for acceleration of oxygen-hydrogen mixture combustion than mere heating of the gas by an electrical discharge. In addition, low-temperature inflammation of the mixture with electrical-discharge-excited O₂ molecules makes it possible to raise the efficiency of conversion of the reactant chemical energy to heat compared with the conventional way of combustion initiation by heating.     

Initiation of combustion of a hydrogen-air mixture with ozone impurity by UV laser radiation

The ignition kinetics of hydrogen-air mixtures with a small amount (0.5%) of ozone that are exposed to laser radiation with wavelength λ _I = 248.4 nm is analyzed. The formation of excited O(¹ D) atoms and O₂(a ¹Δ _g ) molecules due to O₃ molecule photodissociation is shown to greatly intensify the chain reactions and noticeably decrease the induction period and ignition temperature compared with the case when the radiation is absent even if the radiation energy applied to the gas is low, E _s = 0.5?1.0 eV per O₃ molecule. The efficiency of such a way of combustion initiation is much higher than at local heating of the medium by laser radiation but, at the same time, is considerably lower than the efficiency of the method based on excitation of O₃ molecule asymmetric oscillations.     

Kinetics of processes in the middle atmosphere during the laser excitation of O2 molecules

Kinetic processes taking place in the atomic-molecular system O-O₂-O₃ in the middle atmosphere with the participation of oxygen molecules in the excited electronic states O₂(a ¹Δ_g) and O₂(b ¹Σ _g ⁺ ) are analyzed in detail. The possibility of increased ozone production under the influence of solar radiation during the laser excitation of O₂ molecules in the a ¹Δ_g state is demonstrated on the basis of numerical modeling. Upper and lower bounds are determined for the densities of O₂(a ¹Δ_g) molecules at which the ozone concentration increases in the irradiated zone. Zh. Tekh. Fiz. 68, 15–23 (August 1998)     

Kinetic mechanisms of initiating hydrogen-oxygen mixture combustion through the excitation of electronic degrees of freedom of molecular oxygen by laser radiation

Kinetic mechanisms resulting in the enhancement of combustion of H₂+O₂ mixtures when O₂ molecules are excited to the a ¹Δ_g and b ¹Σ _g ⁺ states with laser radiation (λ=1.268 and 0.762 μm) are analyzed. It is shown that the excitation of O₂ molecules by the laser radiation leads to the appearance of new O, H, and OH formation channels; promotes the ignition of the starting mixture; and reduces the self-ignition temperature. With initial pressures in the range P ₀=10³–10⁴ Pa, the self-ignition temperature can be reduced to 300 K even at relatively low energies of the laser radiation with λ=0.762 μm.     

Laser-initiated ignition of hydrogen-air mixtures

The subject of investigation is the kinetic mechanisms intensifying chain reactions that proceed in a hydrogen-air mixture when O₂ molecules dissociate under the action of laser radiation with wavelength λ _I = 193.3 nm and are excited into the b ¹Σ _g ⁺ electron state by radiation with λ _I = 762.346 nm. The efficiencies of both methods to initiate ignition are compared. Numerical simulation shows that the ignition temperature for the laser-induced excitation of O₂ molecules into theb ¹Σ _g ⁺ state is lower than for the dissociation of O₂ molecules by UV laser radiation, with the energy supplied to the mixture being the same. However, both photochemical methods are much more efficient than mere heating of the mixture by laser radiation or another source of heat.     

The kinetics of methane ignition in fuel-rich HCCI engines: DME replacement by ozone

Fuel-rich combustion of methane in a homogeneous-charge compression-ignition (HCCI) engine can be used as a polygeneration process producing work, heat, and useful chemicals like syngas. Due to the inertness of methane, additives such as dimethyl ether (DME) are needed to achieve ignition at moderate inlet temperatures and to control combustion phasing. Because significant concentrations of DME are then needed, a considerable part of the fuel energy comes from DME. An alternative ignition promotor known from fuel-lean HCCI is ozone (O₃). Here, a combined experimental and modelling study on the ignition of fuel-rich partial oxidation of methane/air mixtures at Φ = 1.9 with ozone and DME as additives in an HCCI engine is conducted. Experimental results show that ozone is a suitable additive for fuel-rich HCCI, with only 75 ppm ozone reducing the fuel-fraction of DME needed from 11.0% to 5.3%. Since ozone does not survive until the end of the compression stroke, the reaction paths are analyzed in a single-zone model. The simulation shows that different ignition precursors or buffer molecules are formed, depending on the additives. If only DME is added, hydrogen peroxide (H₂O₂) and formaldehyde (CH₂O) are the most important intermediates, leading to OH formation and ignition around top dead center (TDC). With ozone addition, methyl hydroperoxide (CH₃OOH) becomes very important earlier in the compression stroke under these fuel-rich conditions. It is then later converted to CH₂O and H₂O₂. Thus, ozone is a very effective additive not only for fuel-lean, but also for fuel-rich combustion. However, the mechanism differs between both regimes. Because less of the expensive additives are needed, ozone could help improving the economics of a polygeneration process with fuel-rich operated HCCI engines.     

Acceleration of methane–oxygen mixture ignition by adding singlet oxygen produced in a chemical generator

Ignition acceleration in a methane–oxygen mixture flow with added oxygen in the electronic excited state O₂(a ¹Δ _g ), produced in a chemical generator, was experimentally demonstrated for the first time.     

O2分子激发态a1Δg和b1Σ+g态的分析势能函数

以aug-cc-pVQZ,cc-pV5Z,6-311++g（d,p）和6-311++g（3df,3pd）等为基函数,采用多组态相互作用（MRCI）方法对O₂分子最低的两个激发态¹Δ_g和¹Σ⁺_g的平衡结构、谐振频率和势能曲线进行了计算.并选用Murrell-Sorbie势能函数对曲线进行拟合,利用拟合的参数值计算出了力常数和光谱数据.结果表明计算值与实验值符合较好. 关键词： MRCI 势能函数 力常数 光谱数据     

Discharged generator of singlet oxygen for oxygen-iodine laser. Transport kinetics of O2(a 1δg) and O2(b 1σ g + ) molecules and O(3 P) atoms in Ar:O2 and He:O2 flows excited by a 13.56-MHz discharge

To understand and reveal the basic physical factors providing the possibility of scaling of a discharged singlet oxygen generator (DSOG) in an oxygen-iodine laser, the production, and transport kinetics of metastable O₂(a ¹δ_g) and O₂(b ¹σ _g ⁺ ) molecules, as well as O(³ P) atoms, were investigated in Ar:O₂ and He:O₂ gas flows excited by a 13.56-MHz discharge in a wide range of pressures (4–40 Torr) and oxygen percentages. It is shown that the densities and transport kinetics of O₂(a ¹δ_g), O₂(b ¹σ _g ⁺ ), and O(³ P) appear similar for oxygen mixtures with argon and helium in the same conditions independent of discharge mode. Compared to pure O₂, the dilution of oxygen with an inert gas allows higher energy inputs per an oxygen molecule to achieved, especially under conditions of the homogeneous discharge mode (α-mode), which gives a higher efficiency of O₂(a ¹δ_g) excitation in Ar:O₂ and He:O₂ mixtures. But the maximum attainable yield of singlet oxygen in Ar:O₂ and He:O₂ at fixed partial O₂ pressure is found to be comparable with the O₂(a ¹δ_g) yield in pure oxygen at the same pressure. The reason for this is the increased three-body deactivation of O₂(a ¹δ_g) by atomic oxygen in the mixtures because of the greater total pressure. The estimation of the rate constant of O₂(a ¹δ_g) three-body quenching by O(³ P) in Ar:O₂ and He:O₂ mixtures as (1.5 ± 0.5) × 10^?32 cm⁶/s was carried out from the analysis of transport kinetics of singlet and atomic oxygen in the discharge afterglow at high pressures exceeding ～10 Torr. A similar analysis for the lower pressures has revealed that losses both of metastable O₂(a ¹δ_g) and O₂(b ¹σ _g ⁺ ) molecules, and of O(³ P) atoms on the surface of the discharge tube, are determined by the density of each of the components. The obtained loss probabilities of O₂(a ¹δ_g), O₂(b ¹σ _g ⁺ ), and O(³ P) on the silica surface show that the surface loss probabilities of all the species can increase noticeably under the discharge exposure. Thus, the key parameters determining the maximal O₂(a ¹δ_g) yield in the DSOG are a homogeneous volumetric mode of the discharge, energy input per oxygen molecule in this mode, and a low rate of O₂(a ¹δ_g) quenching. Just three-body quenching of O₂(a ¹δ_g) by O(³ P) limits the singlet oxygen yield with increasing pressure. The fast removal of atomic oxygen both in discharge and in the earlier afterglow could provide DSOG scaling with pressure.     

Intensification of shock-induced combustion by electric-discharge-excited oxygen molecules: numerical study

Mechanisms of combustion enhancement in a supersonic H₂–O₂ reactive flow behind an oblique shock wave front are investigated when vibrational and electronic states of O₂ molecule are excited by an electric discharge. The analysis is carried out on the base of updated thermally nonequilibrium kinetic model for the H₂–O₂ mixture combustion. The presence of vibrationally and electronically excited O₂ molecules in the discharge-activated oxygen flow allows to intensify the chain mechanism and to shorten significantly the induction zone length at shock-induced combustion. It makes possible, for example, to ignite the atmospheric pressure H₂–O₂ mixture at the distance shorter than 1 m behind the weak oblique shock wave at a small energy E_s = 1.2 × 10^–2 J · cm^–3 input to O₂ molecules. At higher pressure it is needed to put greater specific energy into the gas in order to ignite the mixture at appropriate distances. It is shown that excitation of O₂ molecules by electric discharge is much more effective for accelerating the hydrogen–oxygen mixture combustion than mere heating the gas.     

Study of collisional deactivation of O2(b 1Σ g + ) molecules in a hydrogen-oxygen mixture at high temperatures using laser-induced gratings

Collisional deactivation of O₂(b ¹Σ _g ⁺ ) molecules resonantly excited by a 10 ns pulse of laser radiation with a wavelength of 762 nm in H₂/O₂ mixtures is experimentally studied. The radiation intensity and hence the molecule excitation efficiency have a spatially periodic modulation that leads to the formation of laser-induced gratings (LIGs) of the refractive index. The study of LIG temporal evolution allows collisional relaxation rates of molecular excited states and gas temperature to be determined. In this work, the b ¹Σ _g ⁺ state of O₂ molecules deactivation rates are measured in a 4.3 vol % H₂ mixture at the number density of 2 amg in the temperature range 291–850 K. The physical deactivation is shown to dominate in the collisions of H₂ with O₂(b ¹Σ _g ⁺ ) and O₂(a ¹Δ _g ) up to temperatures of 780–790 K at time delays up to 10 μs after the excitation pulse. The parameters of the obtained temperature dependence of the (b ¹Σ _g ⁺ state deactivation rate agree well with the data of independent measurements performed earlier at lower temperatures (200–400 K). Tunable diode laser absorption spectroscopy is used to measure the temperature dependence of the number density of the H₂O molecules which appear as the mixture, as the result of the dark gross reaction with O₂ molecules in the ground state, O₂ + 2H₂ → 2H₂O. The measurements show that this reaction results in complete transformation of H₂ into H₂O at temperatures of 790–810 K.     

Kinetics of low-temperature initiation of H<Subscript>2</Subscript>/O<Subscript>2</Subscript>/H<Subscript>2</Subscript>O mixture combustion upon the excitation of molecular vibrations in H<Subscript>2</Subscript>O molecules by laser radiation

The initiation of H₂/O₂/H₂O mixture combustion when asymmetric vibrations in H₂O molecules are excited by a resonant IR laser radiation is considered. It is shown that the vibrational excitation of the molecules gives rise to new efficient channels for the formation of chemically active O and H atoms and OH radicals. As a result, the chain mechanism of combustion in the mixtures is enhanced and, as a consequence, the induction time is cut and the ignition temperature is lowered. Even at a minor radiant energy flux delivered to the gas (E_in≈2.5 J/cm²), the ignition temperature of the stoichiometric H₂/O₂ mixture containing only 5% of H₂O may become as low as 300 K.     

Initiation of combustion of a methane-air mixture in a supersonic flow behind a shock wave during laser excitation of O<Subscript>2</Subscript> molecules

The possibility of initiating detonation of CH₄ + air in a supersonic flow behind an oblique shock wave under the exposure of the mixture to laser radiation with wavelengths λ_I=1.268 μm and 762 nm is analyzed. It is shown that this irradiation leads to excitation of O₂ molecules to the a ¹Δ_g and b ¹Σ _g ⁺ states, which intensifies the chain mechanism of combustion of CH₄/O₂ (air) mixtures. Even for a small value of the laser radiation energy absorbed by an O₂ molecule (∼0.05–0.1 eV), detonation mode of combustion in a poorly inflammable mixture such as CH₄/air can be realized at a distance of only 1 m from the primary shock wave front for relatively small values of temperature (∼1100 K) behind the front under atmospheric pressure.     

Negative Ions,Ozone, and Metastable Components in dc Oxygen Glow Discharge

In a dc glow discharge in oxygen, the concentrations of minor components of O₂(a¹Δ_g), O₂(b¹ Σ_g), O₃, O(¹D), as well as nagative ions and electrons have been measured. Balance equations have been derived which describe satisfactorily the stationary concentrations of these components as functions of gas pressure and discharge current. For the first time, the rate constants of important aeronomical reactions (a) O^? + O₂(a¹Δ_g) → O₃ + e, (b) O₂^? + O₂(a¹Δ_g) → 2O₂ + e and (c) e + O₃ → O₂^? +O have been measured as functions of gas temperature T and mean energies of ions E_i and electron E₆: K_a = (2.5 ± 0.5) · 10^?9 · (T/300)^{4 ± 0.4}· (E_i/0.04)^{?2.6 ± 0.4} cm³/s for T = 385?605 K and E_i = 0.10 ? 0.66 eV; K_b = (1.0 ± 0.3) · 10^?10 · (T/300)^{?2 ± 0.5} · (E_i/0.04)^{0.23 ± 0.05} cm³/s for T = 330?605 K and E_i = 0.09 + 1.5 eV; K_c for E_e = 0.8÷5 eV.     

A comparative study of singlet-oxygen generation by С<Subscript>60</Subscript> and С<Subscript>70</Subscript> fullerenes

The results of comparative investigations of singlet-oxygen generation by С₆₀ and С₇₀ fullerenes in tetrachloromethane solutions, aqueous suspensions, and solid-phase powders of fullerenes optically excited by cw diode arrays with different wavelengths and by pulsed xenon lamps with a band filter are presented. The measurements were performed by recording singlet-oxygen phosphorescence at the O²(¹Δ_g)–O₂(³Σ_g) transition (λ = 1270 nm).     

Kinetics of energy deactivation in the O2(1Δ)-I medium

The kinetics of energy-exchange and quenching processes in the O₂(¹Δ)-I medium plays an important role in the operation of the chemical oxygen-iodine laser. However, up to now, many of the key processes in this medium are not fully understood. In this work, the flow tube technique is used to determine the rate of excitation energy deactivation in the O₂(¹Δ)-I medium in the presence of small concentrations of water and carbon dioxide. The concentrations of electronically excited species are measured with spectrometers calibrated in absolute spectral responsivity. The effective rate constant for the deactivation of O₂(¹Δ) molecules in processes involving iodine atoms is determined. The results are compared to those obtained in previous works.     

Dynamic electron polarization created by the radical-triplet pair mechanism: Application to the studies on excited state deactivation processes by free radicals

The radical-triplet pair mechanism for chemically induced dynamic electron polarization (CIDEP) created in the quenching of excited state molecules by free radicals is explained on the basis of recent time-resolved electron spin resonance spectroscopic results and theoretical studies. The CIDEP of 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO) and galvinoxyl radicals exhibit various CIDEP patterns of net and mutliplet types and CIDEP phases of absorption and emission. The CIDEP patterns are described by the quartet-doublet state mixings within the radical-triplet encounter pairs. The mixings by the spin-dipolar and the hyperfine interactions are responsible for the net and the multiplet patterns, respectively. The factors controlling the CIDEP phases are the spin multiplicity of the excited state quenched by radicals and the sign of the intermolecular exchange interaction of the radical-triplet encounter pairs. In particular, the intermolecular charge transfer effect on the exchange interaction is discussed much in detail from the viewpoints of CIDEP magnitudes and phases. A CIDEP creation in the O₂(¹Δ_g)-TEMPO system is also introduced and is described by the radical-triplet pair mechanisms. Applications of this CIDEP used as a probe of O₂(¹Δ_g) in condensed phase are mentioned.