乙烯着火延迟的激波管测量与分子碰撞理论分析

在75%和96%两个不同的稀释度下,测量了乙烯/氧气/氩气混合气的着火延迟时间,实验当量比为1,压力为1.3-3.0 atm,温度为1092-1743 K.实验结果表明,着火延迟时间的对数与温度倒数呈良好的线性关系,在两个稀释度下,着火延迟时间随着温度增加而减少.通过回归分析,得到了乙烯着火关联式.计算得乙烯着火延迟在96%稀释度时是75%稀释度的5倍.采用分子硬球碰撞模型,计算了不同稀释度下,乙烯与氧分子的碰撞次数,在96%稀释度下,乙烯与氧气分子碰撞次数为1.53×10²⁹/（s·cm³）,而在75%稀释度下,该碰撞次数增加为5.99×10³⁰/（s·cm³）,约为前者40倍,而着火延迟时间的差异在两条件下仅为5倍的关系,可能由于位阻因子的影响所致.     

Experimental study and modeling of shock tube ignition delay times for hydrogen-oxygen-argon mixtures at low temperatures

Recent literature has indicated that experimental shock tube ignition delay times for hydrogen combustion at low-temperature conditions may deviate significantly from those predicted by current detailed kinetic models. The source of this difference is uncertain. In the current study, the effects of shock tube facility-dependent gasdynamics and localized pre-ignition energy release are explored by measuring and simulating hydrogen-oxygen ignition delay times. Shock tube hydrogen-oxygen ignition delay time data were taken behind reflected shock waves at temperatures between 908 to 1118 K and pressures between 3.0 and 3.7 atm for two test mixtures: 4% H₂, 2% O₂, balance Ar, and 15% H₂, 18% O₂, balance Ar. The experimental ignition delay times at temperatures below 980 K are found to be shorter than those predicted by current mechanisms when the normal idealized constant volume (V) and internal energy (E) assumptions are employed. However, if non-ideal effects associated with facility performance and energy release are included in the modeling (using CHEMSHOCK, a new model which couples the experimental pressure trace with the constant V, E assumptions), the predicted ignition times more closely follow the experimental data. Applying the new CHEMSHOCK model to current experimental data allows refinement of the reaction rate for H + O₂ + Ar ↔ HO₂ + Ar, a key reaction in determining the hydrogen-oxygen ignition delay time in the low-temperature region.     

The emission spectrum of HgI

The ultraviolet emission systems of HgI—C → X, D → X, F₃ → X, G → X, and H → X—are photographed and analyzed using tesla-discharge sources containing isotopically pure ²⁰⁰Hg. The previous assignment for F₃ → X is revised, the main change being a decrease by 3 units in the v″ numbering. Results for the other systems corroborate the existing interpretations, except that for C → X there are prominent intensity gaps in the unresolved rotational structure of the bands, not reported previously for “natural” HgI spectra. These gaps are attributed to perturbations of the C state by high levels (v ≈ 90) of the B state. The data for these systems are combined with existing B → X data for ²⁰⁰Hg¹²⁷I and ²⁰⁰Hg¹²⁹I and fitted simultaneously to yield optimal vibrational parameters for all states. In this analysis the X state is fitted to a mixed representation—a polynomial in ( ) for v ≤ 20 and a near-dissociation expansion for v ≥ 20, with G_v and its first derivative constrained to be continuous at v = 20. The revised estimate of _e for X is 2800 ± 40 cm⁻¹. The recommended vibrational parameters (cm⁻¹) for v ≤ 20 are ω_e = 125.41, ω_ex_e = 1.009, ω_ey_e = −0.0159.     

Mechanism of ignition by non-equilibrium plasma

The kinetics of ignition in stoichiometric C_nH_2n+2:O₂:Ar mixtures with 90% dilution for n = 1-5 has been studied experimentally and numerically under the action of a high-voltage nanosecond discharge. It was shown that the initiation of the discharge by a high-voltage pulse 115 kV in amplitude with a specific deposited energy of 10-30 mJ/cm³ leads to more than an order of magnitude decrease in the ignition delay time. The generation of atoms, radicals and excited and charged particles by the discharge was numerically described. The role of different atoms and radicals (O, H and C_nH_2n+1) was analyzed. The temporal evolution of the densities of intermediate components in the plasma assisted ignition was discussed.     

Ignition delay times of methane and hydrogen highly diluted in carbon dioxide at high pressures up to 300 atm

The need for more efficient power cycles has attracted interest in super-critical CO₂ (sCO₂) cycles. However, the effects of high CO₂ dilution on auto-ignition at extremely high pressures has not been studied in depth. As part of the effort to understand oxy-fuel combustion with massive CO₂ dilution, we have measured shock tube ignition delay times (IDT) for methane/O₂/CO₂ mixtures and hydrogen/O₂/CO₂ mixtures using sidewall pressure and OH* emission near 306?nm. Ignition delay time was measured in two different facilities behind reflected shock waves over a range of temperatures, 1045–1578?K, in different pressures and mixture regimes, i.e., CH₄/O₂/CO₂ mixtures at 27–286 atm and H₂/O₂/CO₂ mixtures at 37–311 atm. The measured data were compared with the predictions of two recent kinetics models. Fair agreement was found between model and experiment over most of the operating conditions studied. For those conditions where kinetic models fail, the current ignition delay time measurements provide useful target data for development and validation of the mechanisms.     

Shock tube measurements of ignition delay times and OH time-histories in dimethyl ether oxidation

Ignition delay times and OH concentration time-histories were measured in DME/O₂/Ar mixtures behind reflected shock waves. Initial reflected shock conditions covered temperatures (T₅) from 1175 to 1900 K, pressures (P₅) from 1.6 to 6.6 bar, and equivalence ratios (?) from 0.5 to 3.0. Ignition delay times were measured by collecting OH^∗ emission near 307 nm, while OH time-histories were measured using laser absorption of the R₁(5) line of the A-X(0,0) transition at 306.7 nm. The ignition delay times extended the available experimental database of DME to a greater range of equivalence ratios and pressures. Measured ignition delay times were compared to simulations based on DME oxidation mechanisms by Fischer et al. [7] and Zhao et al. [9]. Both mechanisms predict the magnitude of ignition delay times well. OH time-histories were also compared to simulations based on both mechanisms. Despite predicting ignition delay times well, neither mechanism agrees with the measured OH time-histories. OH Sensitivity analysis was applied and the reactions DME ↔ CH₃O + CH₃ and H + O₂ ↔ OH + O were found to be most important. Previous measurements of DME ↔ CH₃O + CH₃ are not available above 1220 K, so the rate was directly measured in this work using the OH diagnostic. The rate expression k[1/s] =  1.61 × 10⁷⁹T^−18.4 exp(−58600/T), valid at pressures near 1.5 bar, was inferred based on previous pyrolysis measurements and the current study. This rate accurately describes a broad range of experimental work at temperatures from 680 to 1750 K, but is most accurate near the temperature range of the study, 1350-1750 K. When this rate is used in both the Fischer et al. and Zhao et al. mechanisms, agreement between measured OH and the model predictions is significantly improved at all temperatures.     

The rotational spectrum of BiO radical in its X1Π1/2 and X2Π3/2 states

Rotational spectra have been observed for BiO produced in a DC discharge through a low pressure mixture of O₂, Ar, and Bi vapor. Because of the highly non-thermal distribution of states, it has been possible to observe spectra arising from the X₁²Π_1/2 level up to v = 9 and for the X₂²Π_3/2 level up to v = 5 near 10 538 cm⁻¹. Precise rotational and hyperfine parameters have been determined for the observed states. By using available near infrared (NIR) data in a merged fit, the 0-0 and 1-1 fine structure intervals have been more precisely determined. Although the quality of the fit is very good, the interpretation of the hyperfine constants is complicated by relativistic effects and the interaction of the X₂ state with A₁⁴Π_3/2 state. The magnetic and quadrupole coupling constants will be compared with those of the Bi atom and related molecules.     

Future atmospheric neutrino data from Super-Kamiokande

Expected sensitivity of future atmospheric neutrino data from Super-Kamiokande on neutrino oscillation physics is discussed. We expect that the accuracy of the sin ²θ₂₃ measurement will be improved with (exposure time) . By analyzing high energy fully contained events, it could be possible to statistically demonstrate the existence of charged current ν_τ interactions at the 3 standard deviation level with a few more years of data. Subdominant ν_μ → ν_e oscillations could be observed if θ₁₃ is near the present limit. However, significantly more data will be required to observe a 3 standard deviation effect.     

Zero Temperature Limits of Gibbs-Equilibrium States for Countable Alphabet Subshifts of Finite Type

Let Σ_A be a finitely primitive subshift of finite type on a countable alphabet. For appropriate functions f:Σ_A → IR, the family of Gibbs-equilibrium states (μ_tf)_t⩾1 for the functions tf is shown to be tight. Any weak^*-accumulation point as t→∞ is shown to be a maximizing measure for f.     

The ultraviolet emission spectrum of LaO

The ultraviolet emission spectrum of LaO, obtained under improved experimental conditions, has been reexamined. The high-resolution rotational analysis of the 0, 0 and 0, 1 F²Σ⁺ → X²Σ⁺ and 0, 0 D²Σ⁺ → X²Σ⁺ bands shows that the two excited electronic states F²Σ⁺ and D²Σ⁺ exhibit characteristic features of a b_βJ coupling scheme. A ligand field multiconfigurational calculation shows that these states arise mainly from the 7s and 8s configurations and gives theoretical support to the observed coupling case.     

Ignition limit and shock-to-detonation transition mode of n-heptane/air mixture in high-speed wedge flows

In this work, oblique detonation of n-heptane/air mixture in high-speed wedge flows is simulated by solving the reactive Euler equations with a two-dimensional (2D) configuration. This is a first attempt to model complicated hydrocarbon fuel oblique detonation waves (ODWs) with a detailed chemistry (44 species and 112 reactions). Effects of freestream equivalence ratios and velocities are considered, and the abrupt and smooth transition from oblique shock to detonation are predicted. Ignition limit, ODW characteristics, and predictability of the transition mode are discussed. Firstly, homogeneous constant-volume ignition calculations are performed for both fuel-lean and stoichiometric mixtures. The results show that the ignition delay generally increases with the wedge angle. However, a negative wedge angle dependence is observed, due to the negative temperature coefficient effects. The wedge angle range for successful ignition of n-heptane/air mixtures decreases when the wedge length is reduced. From two-dimensional simulations of stationary ODWs, the initiation length generally decreases with the freestream equivalence ratio, but the transition length exhibits weakly non-monotonic dependence. Smooth ODW typically occurs for lean conditions (equivalence ratio < 0.4). The interactions between shock/compression waves and chemical reaction inside the induction zone are also studied with the chemical explosive mode analysis. Moreover, the predictability of the shock-to-detonation transition mode is explored through quantifying the relation between ignition delay and chemical excitation time. It is demonstrated that the ignition delay (the elapsed time of the heat release rate, HRR, reaches the maximum) increases, but the excitation time (the time duration from the instant of 5% maximum HRR to that of the maximum) decreases with the freestream equivalence ratio for the three studied oncoming flow velocities. Smaller excitation time corresponds to stronger pressure waves from the ignition location behind the oblique shock. When the ratio of excitation time to ignition delay is high (e.g., > 0.5 for n-C₇H₁₆, > 0.3 for C₂H₂ and > 0.2 for H₂, based on the existing data compilation in this work), smooth transition is more likely to occur.     

High-Resolution Laser Spectroscopy of YbCl: The AΠ–XΣ Transition

The A²Π–X²Σ⁺ transition of ¹⁷⁴Yb³⁵Cl and ¹⁷²Yb³⁵Cl has been rotationally analyzed for the first time. Doppler-limited laser excitation spectroscopy with selective detection of fluorescence was used to obtain spectra of the 0–0 and 1–0 bands with a measurement accuracy of approximately 0.0035 cm⁻¹. Resolved fluorescence was used to record the 0–1, 0–2, and 0–3 bands and to unequivocally assign the rotational numbering, N, to the laser excitation spectra. In total, over 1300 line positions have been measured and assigned for each of the two isotopomers and employed in least-squares fits of molecular parameters. The principal results for the A²Π state are A_e = 1491.494(2) cm⁻¹ and R_e = 2.4433(1) Å, and for the X²Σ⁺ state, R_e = 2.4883(2) Å and γ_e = 4.59(2) × 10⁻³ cm⁻¹. The interaction between the X²Σ⁺ and A²Π states has been investigated and is shown to be the main contributor to the spin–rotation splitting in the ground state.     

High-Resolution Study of the BaI AΠ Electronic State

Near-infrared and visible spectra of the A²Π–X²Σ⁺, C²Π_1/2–A²Π_1/2, C²Π_1/2–B²Σ⁺, and C²Π_1/2–X²Σ⁺ band systems of the BaI molecule were recorded by using Fourier transform spectroscopy (FTS). The spectra were produced from the chemiluminescent reaction Ba + I₂ and also by using laser-induced fluorescence (LIF) technique in which the laser sources were a Ti:sapphire single-mode laser, a dye single-mode laser, and a Kr⁺ multimode ion laser. Resolved rotational data, originating from 19 vibrational levels (0 ≤ v ≤ 5 and 7 ≤ v ≤ 19) of the A²Π state, 24 vibrational levels (0 ≤ v ≤ 18 and 20 ≤ v ≤ 24) of the X²Σ⁺ state, and 8 vibrational levels (1 ≤ v ≤ 2 and 9 ≤ v ≤ 14) of the C²Π state, were used in the final analysis. Previously recorded data for the B²Σ⁺–X²Σ⁺ and C²Π–X²Σ⁺ systems, taken from R. F. Gutterres, J. Vergès, and C. Amiot, J. Mol. Spectrosc. 196, 29–44 (1999) and from C. A. Leach, A. A. Tsekouras, and R. N. Zare, J. Mol. Spectrosc. 153, 59–72 (1992), were added to the present work data field. Accurate and improved molecular constants, for the X²Σ⁺, B²Σ⁺, A²Π, and C²Π states, were derived from a simultaneous treatment of the whole data set.     

The reaction of CH3 + O2: experimental determination of the rate coefficients for the product channels at high temperatures

The reaction of methyl radicals (CH₃) with molecular oxygen (O₂) has been investigated in high-temperature shock tube experiments. The overall rate coefficient, k₁ = k_1a + k_1b, and individual rate coefficients for the two high-temperature product channels, (1a) producing CH₃O + O and (1b) producing CH₂O + OH, were determined using ultra-lean mixtures of CH₃I and O₂ in Ar/He. Narrow-linewidth UV laser absorption at 306.7 nm was used to measure OH concentrations, for which the normalized rise time is sensitive to the overall rate coefficient k₁ but relatively insensitive to the branching ratio of the individual channels and to secondary reactions. Atomic resonance absorption spectroscopy measurements of O-atoms were used for a direct measurement of channel (1a). Through the combination of measurements using the two different diagnostics, rate coefficient expressions for both channels were determined. Over the temperature range 1590–2430 K, k_1a = 6.08 × 10⁷T^1.54 exp (−14005/T) cm³ mol⁻¹ s⁻¹ and k_1b = 68.6 T^2.86 exp (−4916/T) cm³ mol⁻¹ s⁻¹. The overall rate coefficient is in close agreement with a recent ab initio calculation and one other shock tube study, while comparison of k_1a and k_1b to these and other experimental studies yields mixed results. In contrast to one recent experimental study, reaction (1b) is found to be the dominant channel over the entire experimental temperature range.     

A new electronic transition of antimony chloride in the visible region

The emission spectrum of SbCl has been photographed at high resolution in the region 400 to 640 nm. In addition to bands of two previously reported transitions in this region, A₁-X and A₂-X, 36 bands of a new system have been identified. A vibrational analysis has been made with ν₀₀ ≈ 20 679 cm⁻¹, and 7 of the bands have been rotationally analyzed. The electronic transition has ΔΩ = 0 with lower state constants which match published data for the ground state X³Σ⁻(0⁺). The upper state is characterized by the following ¹²¹Sb³⁵Cl molecular parameters: B′₀ = 0.0922 cm⁻¹, D′₀ = 3.1 × 10⁻⁸ cm⁻¹.     

Infrared absorption of silane,ammonia, acetylene and diborane in the range of the CO2 laser emission lines: Measurements and modelling

Absorption spectra of the gases SiH₄, NH₃, C₂H₂ and of SiH₄/Ar and SiH₄/B₂H₆ mixtures have been measured in the spectral range of the CO₂ laser from 9.2 to 10.8 µm. In agreement with literature, silane shows the highest absorption (absorption coefficient = 3.3 × 10^–2 Pa^–1 m^–1). The deviation of the measured absorption behaviour of silane from literature, as far as the pressure dependence is concerned, can be explained by the enhanced spectral energy density in our experiment. This is confirmed by a rate-equation model involving the basic mechanisms of V-V and V-T energy transfer between vibrationally excited silane molecules. In contrast to silane, the absorption coefficient of NH₃ at the 10P(20) laser line is 4.5 × 10^–4 Pa^–1 m^–1 atp = 20 kPa and has its maximum of 4.5 × 10^–3 Pa^–1 m^–1 at the 10R(6) laser line. For C₂H₂ and B₂H₆, is even less ( 2.1 Ò 10^–5 Pa^–1 m^–1 for C₂H₂).     

New Investigations of the AΔ-XΠ Band System in the CH Radical and a New Reduction of the Vibration-Rotation Spectrum of CH from the ATMOS Spectra

Seven bands of the A²Δ-X²Π system of the CH radical have been photographed in emission from a Geissler tube using conventional spectroscopic techniques. Under high resolution and using Th lines as standards, as well as an interferometric comparator equipped with a photoelectric scanning device, the 0-0, 1-1, 2-2, 0-1, and 1-2 bands have been rephotographed and the 3-3 and 2-3 bands, with a total number of 144 lines, have been recorded for the first time. In the previously reported (J. Mol. Spectrosc.134, 305, 1989; 147, 16, 1991) evaluation of the ATMOS spectrum of CH for determining the molecular parameters we found total interparameter correlations between some of them, due to the absence of high-J lines of the P and Q branches. With the help of the precise constants obtained from our 0-0 band measurements (12 branches with J_max = 24.5, f = 181, σ = 0.0025 cm⁻¹) of the A²Δ-X²Π transition, we have been able to remove the correlations and obtain more accurate molecular parameters for the X²Π ground state. These constants have subsequently been used to derive new exact molecular parameters for the A²Δ , ν = 1, 2, and 3 levels of CH. The Λ-doubling constants in the A²Δ state were obtained for the first time. The complex vibrational analysis has been carried out to determine the equilibrium molecular constants. Also, RKR potentials and r-centroids have been calculated for both the combining states, as well as Franck-Condon factors for the A-X system.     

The spectra and structure of indium iodide: The rotational and vibrational constants of the A0 state

The rotational constants of the A0⁺ state of InI are reported for the first time as B_e = 0.038077 cm⁻¹ and α_e = 0.0002373 cm⁻¹, while T_e = 24402.91 cm⁻¹ for the A0⁺-X0⁺ transition. Accurate vibrational constants for both the A0⁺ and X0⁺ states are computed from the derived band origins.     

Formation and quenching mechanisms of excited particles in an oxygen-iodine laser medium

New values of a number of kinetic constants of processes proceeding in oxygen-iodine laser media are presented. The total probabilities of formation of I₂(X, 15 ≤ v ≤ 24) and I₂(X, 25 ≤ v ≤ 47) molecules in the course of quenching of I* atoms by I₂(X) are found to be 0.9 and 0.1, respectively. The quantum yield of singlet oxygen in the reaction O(¹ D) + N₂O → N₂ + O₂(a ¹Δ) is close to 100%. The quenching rate constants of I₂(A’) by O₂, H₂O, CO₂, I₂, and Ar and of I(² P _1/2) by O(³ P), O₃, NO₂, N₂O₄, and N₂O are presented.     

Unravelling the visible spectrum of strontium monomethoxide

The bands of the A²E–X²A₁ and B²A₁–X²A₁ electronic transitions of SrO¹²CH₃ and the B²A₁–X²A₁ transition of SrO¹³CH₃ have been recorded at high resolution using a laser ablation jet source. The optical–optical double resonance population depletion technique was used to facilitate the assignment of the spectra. Rotational levels with K = 0, ±1 in the X²A₁ and B²A₁ states and K = 0, 1 and 2 in the A²E state have all been characterised. A perturbation affecting the B²A₁ state caused a reversal of the ordering of the spin-rotation components, F₁ and F₂, in the SrO¹²CH₃ isotopologue. This required the introduction of a modified rotational constant B_mod, affecting only the K = 1, F₂ component of the B²A₁ state, in order to model the SrO¹²CH₃ data in a global fit of the A²E–X²A₁ and B²A₁–X²A₁ transitions.