H2 CARS thermometry in a fuel-rich,premixed, laminar CH4/air flame in the pressure range between 5 and 40 bar

To establish H₂ CARS thermometry at high pressure, accumulated H₂ Q-branch CARS spectra were recorded in the exhaust of a fuel-rich CH₄/air flame at pressures between 5 and 40 bar. Temperatures were deduced by fitting theoretical spectra to experimental data points. The Energy-Corrected Sudden (ECS) scaling law was employed to set up an empirical model for the calculation of H₂ linewidths in high-pressure hydrocarbon flames with H₂ as a minority species. Experimental H₂ CARS spectra could be simulated very accurately with this model. The evaluated temperatures agreed well with reference temperatures obtained by spontaneous rotational Raman scattering of N₂.     

Coarse-grain modelling using an equation-of-state many-body potential: application to fluid mixtures at high temperature and high pressure

ABSTRACT

A many-body, coarse-grain model, termed the product gas mixture model, is presented that accurately describes the thermodynamic behaviour of molecular mixtures. The coarse-grain model is developed by first approximating the mixture as a van der Waals one-fluid, and subsequently applying an exponential-6 equation-of-state to describe the forces and energies between particles in the spirit of the many-body model pioneered by Pagonabarraga and Frenkel. Isothermal dissipative particle dynamics simulations are carried out at thermochemical states that occur during decomposition of a prototypical energetic material, RDX (1,3,5-trinitro-1,3,5-triazinane). The product gas mixture model performance is assessed by comparing to an explicit-molecule model and a hard-core coarse-grain model based on the exponential-6 pair potential. Overall, the many-body, coarse-grain model is shown to accurately capture the structural and thermodynamic properties for the wide variety of thermochemical states considered, while the hard-core coarse-grain model cannot. The many-body, coarse-grain model overcomes the issues of transferability, scaling consistency and unphysical ordered phase behaviour that often afflict coarse-grain models. While specific thermochemical conditions related to RDX decomposition are considered, the results are generally applicable to the thermodynamic behaviour of other fluid mixtures at both moderate and extreme conditions.     

Fundamental burning velocities of meso-scale propagating spherical flames with H2, CH4 and C3H8 mixtures

This study is performed to experimentally examine the fundamental burning velocity characteristics of meso-scale outwardly propagating spherical laminar flames in the range of flame radius r_f approximately from 1 to 5 mm for hydrogen, methane and propane mixtures, in order to make clear a method for improving combustion of micro–meso scale flames. Macro-scale laminar flames with r_f > 7 mm are also examined for comparison. The mixtures have nearly the same laminar burning velocity (S_L0 = 25 cm/s) for unstretched flames and different equivalence ratios ?. The radius r_f and the burning velocity S_Ll of meso-scale flames are estimated by using sequential schlieren images recorded under appropriate ignition conditions. It is found that S_Ll of hydrogen and methane premixed meso-scale flames at the same r_f or the Karlovitz number Ka shows a tendency to increase with decreasing ?, whereas S_Ll of propane flames increases with ?. However, S_Ll tends to decrease with the Lewis number Le and the Markstein number Ma, irrespective of the type of fuel and ?. It also becomes clear that the optimum flame size and Ka to improve the burning velocity exist for some mixtures depending on Le and fuel types.     

Temperature measurements in CO2-laser-induced pyrolysis flames for SiC and ternary SiC/C/B powder synthesis by means of CARS

The hot luminescent reaction zones of CO₂-laser-induced pyrolysis flames using SiH₄/C₂H₂ gas mixtures with different silane to acetylene ratios and with and without diborane additives were investigated by means of H₂ Q-branch CARS spectroscopy, leading to spatial temperature profiles in gas flow direction. In the case of B₂H₆ additive to the stoichiometric SiH₄/C₂H₂ mixture a high temperature plateau ( 800–1000 K) of the reactant gas volume develops already several millimetres before reaching the CO₂-laser focus line. This precursor preheating zone could be explained by the catalytic effect of boron atoms or boron-containing intermediate species in the flame. A similar behaviour for acetylene-rich flames operating at half laser power was not observed.     

Structural,elastic, and vibrational properties of phase H:A first-principles simulation

Phase H(MgSiO_4H_2), one of the dense hydrous magnesium silicates(DHMSs), is supposed to be vital to transporting water into the lower mantle. Here the crystal structure, elasticity and Raman vibrational properties of the two possible structures of phase H with Pm and P2/m symmetry under high pressures are evaluated by first-principles simulations. The cell parameters, elastic and Raman vibrational properties of the Pm symmetry become the same as the P2/m symmetry at～ 30 GPa. The symmetrization of hydrogen bonds of the Pm symmetry at ～ 30 GPa results in this structural transformation from Pm to P2/m. Seismic wave velocities of phase H are calculated in a range from 0 GPa to 100 GPa and the results testify the existence and stability of phase H in the lower mantle. The azimuthal anisotropies for phase H are A_(P0)= 14.7%,A_(S0)= 21.2%(P2/m symmetry) and A_(P0)= 16.4%, A_(S0)= 27.1%(Pm symmetry) at 0 GPa, and increase to A_(P30)= 17.9%,A_(S30)= 40.0%(P2/m symmetry) and A_(P30)= 19.2%, A_(S30)= 37.8%(Pm symmetry) at 30 GPa. The maximum V P direction for phase H is [101] and the minimum direction is [110]. The anisotropic results of seismic wave velocities imply that phase H might be a source of seismic anisotropy in the lower mantle. Furthermore, Raman vibrational modes are analyzed to figure out the effect of symmetrization of hydrogen bonds on Raman vibrational pattern and the dependence of Raman spectrum on pressure. Our results may lead to an in-depth understanding of the stability of phase H in the mantle.     

Multiplex rotational CARS of N2, O2, and CO with excimer pumped dye lasers: Species identification and thermometry in the intermediate temperature range with high temporal and spatial resolution

Pure rotational CARS spectra of N₂, O₂, air, and CO have been obtained using excimer laser pumped dye-lasers. The combination of the folded BOXCARS phase matching geometry with the broad-band laser multiplex method allowed high spatial and temporal resolution. Species and concentration analysis as well as thermometry up to 700 K is demonstrated, and possible applications are discussed.     

Theoretical evidence for a reentrant phase diagram in ortho-para mixtures of solid H2 at high pressure

We develop a multiorder parameter mean-field formalism for systems of coupled quantum rotors. The scheme is developed to account for systems where ortho-para distinction is valid. We apply our formalism to solid H2 and D2. We find an anomalous reentrant orientational phase transition for both systems at thermal equilibrium. The correlation functions of the order parameter indicate short-range order at low temperatures. As the temperature is increased the correlation increases along the phase boundary. We also find that even extremely small odd-J concentrations (1%) can trigger short-range orientational ordering.     

Ab initio simulation of phase transitions and dissociation of H2S at high pressure

By ab initio constant pressure molecular dynamics, we have identified the structure of phase V and phase VI of H2S at 35 and 65 GPa, respectively. The theoretical IR spectra of both phases are consistent with experimental findings and support our proposed structural models. We find that phase V is characterized by the presence of charged SH+3 and SH- species which are created and destroyed dynamically, whereas phase VI is no longer a molecular phase but consists of sheets of S with the majority of H intercalated between the layers. The stability of the two phases with respect to dissociation into elemental crystalline hydrogen and sulfur is discussed.     

The absorption line profiles of H2O near 1.39 μm in binary mixtures with N2, O2, and H2 at low pressures

The absorption line profiles of water vapor in binary mixtures with diatomic molecules H₂, N₂, and O₂ have been recorded on a diode laser spectrometer. The profiles of several lines of the 101 band have been studied near 1.39 μm with a spectral resolution of 3 × 10^?4 cm^?1. The pressure of the binary mixtures was varied from 0 to 200 Torr. The experimental data obtained have been used to test the Voigt, Rautian-Sobel’man, and Galatry theoretical models of a spectral line profile. The coefficients of collisional narrowing have been determined from the results of the fitting.     

Stochastic simulation of transport and chemical kinetics in turbulent CO/H2/N2 flames

The one-dimensional turbulence (ODT) model is applied to the study of turbulent jet CO/H₂/N₂ flames. The ODT model retains the full range of length scales and no assumption of scale separation is required. In the present case, the ODT model describes the evolution of the entire flowfield; the ability of ODT to model the flowfield evolution is discussed. Predictions of the conditional means and fluctuations of temperature and the species mass fractions are compared with measurements and the level of closure required to address certain phenomena is discussed. The ODT model is shown to be useful for studying extinction/re-ignition phenomena and differential diffusion. The streamwise evolution in multidimensional flows is affected by dilatation in a manner not captured by the ODT model, and this results in discrepancies between the ODT mixing rates and the mixing rates evident in the measurements.     

Raman signatures of strong and weak hydrogen bonds in binary mixtures of phenol with acetonitrile,benzene and orthodichlorobenzene

The present study aims at investigating the effect of hydrogen bonds of phenol in binary mixtures of phenol with three solvents viz. acetonitrile, orthodichlorobenzene and benzene respectively in order of decreasing hydrogen bond strength. Raman spectroscopy in correlation with density functional theory (DFT) calculations has led to a profound understanding of changes in structure, energy, dipole moment and other physical and chemical properties of phenol pertaining to hydrogen bond formation in solution. The spectral variation in wavenumber and linewidth of ring deformation, ring stretching, C≡N stretching and C―H stretching modes have been analyzed in detail. The breaking of self association of phenol in solution and formation of strong or weak hydrogen bonds depending on the nature of the solvent has been discussed by comparing the Raman and DFT results for three different solvents. Copyright © 2016 John Wiley & Sons, Ltd.     

Experimental and theoretical study of the structure and vibrational spectra of valpromide,C7H15CONH2

In this work, we present results of the conformational and vibrational properties of valpromide (Vpd), an amide with antiepileptic activity, studied by IR and Raman spectroscopy at 300 and 77 K, and 300 K, respectively. Experimental data are compared against ab initio calculations performed at B3LYP level with the inclusion of solvatation effects. Experimental results, reinforced by theoretical calculations, point out that Vpd has three conformers on the potential energy surface, with different structures that can be identified in the CO and NH spectral regions. These conformers are defined by different angular arrays of the dihedral angles formed with the CO, C N and C〈 H, C C of the aliphatic chain bonds. The existence of different conformations and structures are discussed on the basis of results derived from electronic localization function (ELF) and natural orbital bond (NBO) analysis. Copyright © 2008 John Wiley & Sons, Ltd.     

The non-coincidence effect in N,N-dimethylformamide-CCl4 highly diluted binary mixtures. Experimental and theoretical results

We report results on the concentration dependence of the non-coincidence effect in the v(C=O) mode in N,N-dimethylformamide-CCl₄ mixtures. This study has been mainly addressed to the investigation of the experimentally observed sign inversion for this quantity in the low concentration range of chemical mixtures, which is also reported in the literature. We argue that the sign inversion of the non-coincidence effect in N,N-dimethylformamide-CCl₄ mixtures is an artefact originated by the presence of an intrinsic asymmetry which with dilution moves from the blue to the red side of the band. The Logan theory for the thermodynamic state dependence of the non-coincidence effect in chemical mixtures offers a valuable tool for the interpretation of the results in the whole concentration range. Different models are compared and discussed.     

Turbulent scalar fluxes in H2-air premixed flames at low and high Karlovitz numbers

The statistical behaviour and closure of sub-grid scalar fluxes in the context of turbulent premixed combustion have been assessed based on an a priori analysis of a detailed chemistry Direct Numerical Simulation (DNS) database consisting of three hydrogen-air flames spanning the corrugated flamelets (CF), thin reaction zones (TRZ) and broken reaction zones (BRZ) regimes of premixed turbulent combustion. The sub-grid scalar fluxes have been extracted by explicit filtering of DNS data. It has been found that the conventional gradient hypothesis model is not appropriate for the closure of sub-grid scalar flux for any scalar in the context of a multispecies system. However, the predictions of the conventional gradient hypothesis exhibit a greater level of qualitative agreement with DNS data for the flame representing the BRZ regime. The aforementioned behaviour has been analysed in terms of the properties of the invariants of the anisotropy tensor in the Lumley triangle. The flames in the CF and TRZ regimes are characterised by a pronounced two-dimensional anisotropy due to strong heat release whereas a three-dimensional and more isotropic behaviour is observed for the flame located in the BRZ regime. Two sub-grid scalar flux models which are capable of predicting counter-gradient transport have been considered for a priori DNS assessment of multispecies systems and have been analysed in terms of both qualitative and quantitative agreements. By combining the latter two sub-grid scalar flux closures, a new modelling strategy is suggested where one model is responsible for properly predicting the conditional mean accurately and the other model is responsible for the correlations between model and unclosed term. Detailed physical explanations for the observed behaviour and an assessment of existing modelling assumptions have been provided. Finally, the classical Bray–Moss–Libby theory for the scalar flux closure has been extended to address multispecies transport in the context of large eddy simulations.     

Hydrostatic high pressure applied to food sterilization III: Application to spices and spice mixtures

Abstract

The response of suspensions of spices and spice mixtures in water to high pressure treatment was investigated. Inactivation of the microbial load–mainly aerobic and unaerobic spore formers–was strongly dependent on water activity and temperature. Samples were completely decontaminated after three pressure cycles (30 min at 80 MPa followed by 30 min at 350 MPa) at 70 °C at a minimum water activity of 0.91. Pressure treated samples were examined for sensory and chemical changes. No significant changes in odour and appearance were recognized by a trained sensory panel, nor were changes in the volatile compounds of the samples detected by static headspace gaschromatography.     

Structures,energetics and vibrational spectra of (H2O)32 clusters: a journey from model potentials to correlated theory

Empirical model potentials are found to be very useful for generating most competitive minima of large water clusters, whereas correlated (e.g. second order-Møller–Plesset perturbation (MP2) theory or higher) calculations are necessary for predicting their accurate energetics and vibrational features. The present study reports the structures and energetics of (H₂O)₃₂ clusters at MP2 level using aug-cc-pvDZ basis set, starting with low-lying structures generated from model potentials. Such high-end and accurate calculations are made feasible by the cost-effective fragment-based molecular tailoring approach (MTA) in conjunction with the grafting procedure. The latter is found to yield electronic energies with a sub-millihartree accuracy with reference to their full calculation counterparts. The vibrational spectra of nine low-lying (H₂O)₃₂ isomers are obtained from the corresponding MTA-based Hessian matrix. All these low-lying isomers show almost similar spectral features, which are in fair agreement with the experiment. The experimental spectrum of (H₂O)₃₂ is thus better understood from the vibrational features of this set of very closely spaced isomers. The present case study of (H₂O)₃₂ clearly demonstrates the efficacy in obtaining accurate structures, energetics and spectra at correlated level of theory by combining model potential-based structures with fragmentation methods.     

Oscillatory convection in binary mixtures: Thermodiffusion,solutal buoyancy,and advection

The role of thermodiffusive generation of concentration fluctuations via the Soret effect, their contribution to the buoyancy forces that drive convection, the advective mixing effect of the latter, and the diffusive homogenisation are compared and elucidated for oscillatory convection. Numerically obtained solutions of the field equations in the form of spatially extended relaxed traveling waves, of standing waves, and of the transient growth of standing waves and their transition to traveling waves are discussed as well as spatially localized convective states of traveling waves that are surrounded by the quiescent fluid.     

Laser-induced fluorescence thermometry and concentration measurements on NOA–X (0-0) transitions in the exhaust gas of high pressure CH4/air flames

Laser-Induced Fluorescence (LIF) excitation spectra in the NOA–X (0-0) band were used for temperature measurements in the postflame region of high-pressure CH₄/air flames. To improve the quality of the measured spectra and to perform reliable line-shape measurements, the initial mixture was doped with approximately 400 ppm NO. At pressures up to 18 bar, excellent agreement was obtained between NO LIF temperatures and NARS/rotational Raman temperatures. Effective broadening coefficients were also determined in these flames. Problems with quantitative concentration measurements of NO and single-pulse temperature measurements at high pressures are discussed.     

Laser on nitrogen-electronegative gas mixtures, pumped by inductive energy storage generator: Experiment and theoretical model

The advantages of inductive energy storage (IES) generators for increasing the pulse energy, power, and duration for nitrogen laser pumped by self-sustained transverse discharge have been experimentally demonstrated. A theoretical model is developed and the operation of IES-pumped laser on nitrogen-electronegative gas mixtures is numerically simulated. It is shown experimentally and theoretically that, adding electronegative gases, one can control the pulse shape of lasing on the C³II _u -B³II _g transition in nitrogen. The increase in the electric field strength in the laser gap in N₂-NF₃ and N₂-SF₆ mixtures produced 337.1-nm laser pulses consisting of two spaced peaks and 40–50-ns pulses close to rectangular. The increase in the laser active volume to 6 l (discharge cross section to 6×10 cm²) in N₂–SF₆ mixtures made it possible to obtain the maximum output energy (Q=110 mJ) and UV power (P _las =6 MW). In N₂-NF₃ mixtures, the laser pulse duration was up to ∼100 ns with an energy up to Q=30 mJ.