CO2 addition and pressure effects on laminar and turbulent lean premixed CH4 air flames

An experimental study on CH₄–CO₂–air flames at various pressures is conducted by using both laminar and turbulent Bunsen flame configurations. The aim of this research is to contribute to the characterization of fuel lean methane/carbon dioxide/air premixed laminar and turbulent flames at different pressures, by studying laminar and turbulent flame propagation velocities, the flame surface density and the instantaneous flame front wrinkling parameters. PREMIX computations and experimental results indicate a decrease of the laminar flame propagation velocities with increasing CO₂ dilution rate. Instantaneous flame images are obtained by Mie scattering tomography. The image analysis shows that although the height of the turbulent flame increases with the CO₂ addition rate, the flame structure is quite similar. This implies that the flame wrinkling parameters and flame surface density are indifferent to the CO₂ addition. However, the pressure increase has a drastic effect on both parameters. This is also confirmed by a fractal analysis of instantaneous images. It is also observed that the combustion intensity S_T/S_L increases both with pressure and the CO₂ rate. Finally, the mean fuel consumption rate decreases with the CO₂ addition rate but increases with the pressure.     

Measurement on CO<Subscript>2</Subscript> solution density by optical technology

The optical technology based on Mach-Zehnder interferometry was successfully applied to a high-pressure liquid CO₂ and water system to measure CO₂ solution density. Experiments were carried out at a pressure range of from 5.0 to 12.5 MPa, temperatures from 273.25 to 284.15 K, and CO₂ mass fraction in solution up to 0.061. CO₂ solution density data were obtained from two sets of experiments. These data were calculated through the fringe shifts induced by density changes inside of the high-pressure vessel, which were directly recorded during the experiments, and a modified version of Lorentz-Lorenz formulation. The experimental results indicated that the density ratio of CO₂ solution to that of pure water at the same pressure and temperature is monotonically linear with the CO₂ concentration in the solution. The slope of this linear function, calculated by the experimental data fitting, is 0.275.     

Estimating the entropy of liquids from atom–atom radial distribution functions: silica,beryllium fluoride and water

Molecular dynamics simulations of water, liquid beryllium fluoride and silica melt are used to study the accuracy with which the entropy of ionic and molecular liquids can be estimated from atom–atom radial distribution function data. The pair correlation entropy is demonstrated to be sufficiently accurate that the density–temperature regime of anomalous behaviour as well as the strength of the entropy anomaly can be predicted reliably for both ionic melts as well as different rigid-body pair potentials for water. Errors in the total thermodynamic entropy for ionic melts due to the pair correlation approximation are of the order of 10% or less for most state points, but can be significantly larger in the anomalous regime at very low temperatures. In the case of water, the rigid-body constraints result in larger errors in the pair correlation approximation, between 20 and 30%, for most state points. Comparison of the excess entropy, S _e, of ionic melts with the pair correlation entropy, S ₂, shows that the temperature dependence of S _e is well described by T ^?2/5 scaling across both the normal and anomalous regimes, unlike in the case of S ₂. The residual multiparticle entropy, ΔS = S _e ? S ₂, shows a strong negative correlation with tetrahedral order in the anomalous regime.     

Collision-induced Raman scattering in CO2 at the frequency of the v 2 and v 3 inactive vibrations

Experimental results on intensities and band shapes of collision-induced Raman scattering at the v ₂ and v ₃ vibrational transitions in gaseous and liquid CO₂ are reported and discussed. The CO₂ results are compared with new data for v ₃ in SF₆.     

Electron spin relaxation in solutions of manganese (II) ions

Measurements of the neutron scattering static structure factor S(Q) are reported for orthobaric liquid fluorine at 77K for an incident wavelength of 1·2Å. The observed S(Q) and the atom-atom correlation function are discussed and compared with those of other halogens and oxygen. From the d(r) pair distribution function it is shown that liquid fluorine has a coordination number of first neighbours more similar to liquid oxygen than halogens. The number of atoms in the first and second coordination shell is in good agreement with a close-packed arrangement of atoms.     

Infrared spectrum of the continuum and dimer absorption in the vicinity of the O2 vibrational fundamental in O2/CO2 mixtures

The intensities of the collision-induced absorption (CIA) bands associated with the electric-dipole forbidden O₂ fundamental and the CO₂ν₁/2ν₂ Fermi dyad monomer vibrational bands have been studied over the temperature range 193-360 K and the frequency range 1100-2000 cm⁻¹. As CO₂ is added to a pure O₂ sample, the intensity in the O₂ fundamental band region increases dramatically. At the lowest temperature studied, 193 K, the band-integrated CIA coefficient for enhancement of the Fermi dyad absorption from CO₂ to CO₂ collisions, S_CO2-CO2, is more than a factor of two larger than the band-integrated CIA coefficient for enhancement of the O₂ vibrational fundamental by CO₂ collisions, S_O2-CO2. Moreover, the S_CO2-CO2 coefficient shows a significantly larger temperature dependence, increasing by more than a factor of two from 345.6 to 193 K while S_O2-CO2 increases by less than one third. The band shapes and their temperature dependence provide clear evidence for the formation of CO₂-CO₂ and CO₂-O₂ complexes. The CO₂-CO₂ dimer feature is most striking, contributing significantly to the infrared absorption near the expected CO₂ monomer fundamentals. Evidence for the more weakly bound CO₂-O₂ complex is seen on the O₂ CIA band, particularly at the lowest temperatures studied. The shapes for both dimer bands display sharp a-type Q branch central profiles and broad P and R branch like structure attributed to b-type Q branches for the CO₂-CO₂ complex and a-type P and R branch structure for the CO₂-O₂ complex. The present results stress the importance of including bound and metastable dimer absorption in any theoretical modeling of CIA, particularly when one of the collision partners has a large electrostatic moment, such as CO₂ with its large electric quadrupole moment.     

Synchrotron small angle X-ray scattering study on the conformation of polystyrene in compressed CO<Subscript>2</Subscript>-toluene mixture

Synchrotron small angle X-ray scattering (SAXS) was performed to investigate the effect of dissolved CO₂ in toluene on the conformation of polystyrene (PS) in the solution. It has been found that the second virial coefficientA ₂ and the radius of gyrationR _g decrease with the increasing antisolvent CO₂ pressure. The scattering intensity of PS chain followedI(h) ∞h ^−α under different antisolvent pressures (0, 0.6, 1.5, 2.4, 3.3, and 4.2 MPa), suggesting that the PS chain has self-similar structure behavior or a fractal structure in the presence of antisolvent CO₂. All this reveals a large effect of antisolvent pressure or the solubility of CO₂ in the solution on PS structure. The fractal dimensions increase with the increasing antisolvent pressure, indicating that the polymer chain changes from a swollen coil into a rather dense globule in the course of adding antisolvent CO₂.     

Stimulated raman scattering of fuel droplets

The strong stimulated Raman scattering (SRS) from diesel fuel droplets has the potential of providing the relative concentration of multicomponent fuel and the absolute size of individual droplets. The morphology-dependent resonances (MDRs) of a sphere cause the droplet to act as an optical resonator which greatly lowers the SRS threshold. The number density, quality factor, and frequency shift of several MDRs are calculated as a function of the ratio of the index of refraction of the liquid and the surrounding gas, which approaches unity at the thermodynamic critical condition for the fuel spray. The SRS spectra of monodispersed droplets of toluene, pentane, Exxon-Aromatic-150, and Mobil D-2 are presented. The exponential growth region of the SRS intensity I _1S as a function of the input laser intensity I _input is investigated for the toluene carbon ring breathing mode v ₂ and the pentane C-H stretching region. The I _1S ratio of toluene and pentane is measured as a function of the ratio of the toluene and pentane concentration for monodispersed droplets. The reduced fluctuation in I _1S when I _input is changed from multimode to single-mode is displayed as a histogram of the I _1S of the v ₂ mode of toluene droplets.     

Selectivity of nitro versus fluoro substitution in arenes in their reactions with charged O‐ and S‐nucleophiles

The relative mobility of nitro and fluoro substituents in 1,3‐dinitro‐ and 1‐fluoro‐3‐nitrobenzenes, 3,5‐dinitro‐ and 3‐fluoro‐5‐nitrobenzotrifluorides under the action of the nucleophiles (2ArYH)·K₂CO₃ and ArY^?K⁺ in solution and the nucleophiles ArYH·K₂CO₃ (Y = O, S) under heterogeneous conditions was studied by a competitive method in DMF at 40–140 °C. The unique dependences of ΔΔH^≠ on ΔΔS^≠ and ΔΔH^≠ on ΔΔG^≠ were determined for all the substrates and nucleophiles. The dependence of the mechanistic pathway on the nucleophile is discussed. Two results are relevant to the reactions studied: (i) substituent effects in the nucleophiles (2ArYH)·K₂CO₃ and ArYH·K₂CO₃ on the activation entropies suggest that the entropy favours the displacement of nitro group; (ii) the negative signs of ΔΔH^≠ and ΔΔS^≠ for the reactions of the nucleophiles ArY^?K⁺ indicate that the enthalpy determines the displacement of nitro group. It is concluded that the selectivity of the reactions with aryloxide and arylthioxide ions cannot be explained by the hard–soft acid–base principle only. Copyright © 2007 John Wiley & Sons, Ltd.     

Radiation scattering data on liquid metals

The scattering of radiation by liquid metals provides data on both the microscopic and the macroscopic properties of the metal. The macroscopic properties are obtained as a limit in which the momentum transferred by the radiation to the liquid is vanishingly small, while the microscopic structure and dynamical behaviour are obtained from data at higher momenta.

An outline of the theory of radiation scattering will be given which emphasizes the relation between neutron and x-ray results. The possibility of studying electron shell movements by measuring the ratio of x-ray to neutron intensities is discussed.

In general there are two types of experiment: those in which the intensity is measured as a function of the momentum transfer only (S(Q)), and those in which the intensity is measured as a function of both energy and momentum transfer (S(Q, θ)). The former experiments are used to obtain information on atomic positions while the latter experiments (coupled with the former) are used to derive dynamical information. Both kinds of experiment will be discussed and some methods of interpreting (S(Q)) and S(Q, θ)) will be described.

The cooperative modes of motion in the system, particularly for wavelengths of the order of the spacing between atoms, may be observed as peaks in S(Q, θ). Several recent experiments of this kind on liquid lead will be discussed, particularly those in which the temperature variation was studied. In addition, information on the velocity correlation function for the metal atoms may be obtained. The spectral density of the velocity correlation will be considered and compared to predictions based on the cooperative mode picture.

It is concluded that while much information has been obtained from these experiments there is a more detailed and extensive work to be done with both neutrons and x-rays.     

Time-dependent triplet correlations in dense nitrogen gas

The inelastic neutron scattering cross section for dense nitrogen gas at several pressures near 240 atmospheres and room temperature has been measured in the region of the first diffraction peak. The Van Hove self-correlation function is calculated from models and subtracted from these cross sections to yield ?S _d(Q, ω)/?p. This derivative is related to an integral over the time-dependent triplet correlation function and models for the triplet function are tested. A simple model, based on pair functions, gives moderate agreement.     

Isochoric temperature coefficient of surface tension andS o-parameter of quasi-spherical molecular liquids

The Sharma parameterS _o which is characteristic of molten alkali halides and polymers has also been shown to be characteristic of a wide variety of liquids. Calculated data using the volume expansivity of the liquid establish the constancy of theS _o-parameter which retains, on an average, a constant value of 1·11 for quasi-spherical molecular liquids. It is shown thatS _o-parameter is also related to volume expansivity of the surface layer of the liquid, temperature coefficient of surface tension of liquids and describes the temperature and volume or pressure dependence of thermodynamic Grüneisen parameter and isochoric heat capacity with significant contribution for influencing the thermoacoustic and surface tension properties of liquids.     

Calculation of correlation functions in the Heisenberg spin-1/2 antiferromagnetic model

We derive the exact expression of the four-spinon contribution S ₄ to the dynamical correlation function S of the spin 1/2 isotropic (XXX) He isenberg model in the antiferromagnetic regime using the quantum group symmetry of the model. We first give the exact expression for the n-spinon contribution in the form of contour integrals and display known results regarding the two-spinon contribution S ₂. Then we specialize the n-spinon formula to the case n = 4 and compute three sum rules for S ₄ that the total S is known to satisfy exactly. These are: the total integrated intensity, the first frequency moment and the nearest-neighbor correlation function. We find that S ₄ corrects only by a small amount the contribution from S ₂. Presented at the International Colloquium “Integrable Systems and Quantum Symmetries”, Prague, 16–18 June 2005.     

H++CO2散射在30电子伏能量下电荷转移和非电荷转移的非绝热分子动力学模拟

在大气化学、天体物理学和癌症质子疗法中都涉及到高能H⁺+CO₂散射反应.本文在最简电子-核动力学（SLEND）基础上系统研究在30 eV下的H⁺+CO₂散射.SLEND用经典力学描述核,用单行列式Thouless波函数描述电子.本文模拟了CO₂在42个取向共3402条轨线,为理解H⁺+CO₂散射中的各个反应过程和机制提供了系统描述：非电荷转移散射（NCTS）,电荷转移散射（CTS）和C=O双键的断裂,这些关于反应的有用信息不能完全从实验中获取.本文提供了散射的详尽细节,包括随CO₂取向不同主彩虹角和次彩虹角的出现和合并.SLEND NCTS和CTS的微分散射截面通过高等半经典方法计算,显示NCTS散射截面对所有散射角都同实验符合得很好,而CTS散射截面只大散射角时同实验结果符合得很好而在小角散射时稍差.无论是CTS还是NCTS SLEND都预言了主彩虹角的特征,这同实验完全一致.     

Degeneracy of Resonances: Branch Point and Branch Cuts in Parameter Space

The rich phenomenology of crossings and anticrossings of energies and widths, observed in an isolated doublet of resonances when one control parameter is varied, is fully explained in terms of the topological properties of the energy hypersurfaces close to the degeneracy point. The hypersurface representing the complex resonance eigenvalues, as functions of the control parameters, has an algebraic branch point of rank one, and branch cuts in its real and imaginary parts, in parameter space. Associated with this singularity in parameter space, the scattering matrix, S _ℓ (E), and the Green’s function, G _ℓ ⁽⁺⁾(k; r,r'), have one double pole in the unphysical sheet of the complex energy plane. We characterize the universal unfolding or deformation of any degeneracy point of two unbound states in parameter space by means of a universal 2-parameter family of functions which is contact equivalent to the pole position function of the isolated doublet of resonances at the exceptional point and includes all small perturbations of the degeneracy condition up to contact equivalence.     

Investigations of magnetic excitations in a La2CuO4 single crystal

A detailed neutron scattering study is carried out of magnetic excitations in pure La₂CuO₄ in the low energy region up to 15 meV, at temperatures in the vicinity of the transition temperatureT _N to the paramagnetic state. In particular the question of existence of propagating spin waves in this energy region is addressed. The experimental results show that the energy region studied (up to 15 meV) is characterized by aquasielastic peak of the width of order 4 meV (at 300 K). Thus the magnetic correlation function has relaxational behavior in the studied energy region, no indications for propagating spin waves are obtained. The measured quasielastic width agrees well with existing theories. Polarized neutrons and polarization analysis are also used to identify the magnetic origin of the observed scattering.     

Carbon-13 Kinetic Isotope Effects in the Decarbonylation Of Liquid Formic Acid in Water Solution

Abstract

Carbon-13 kinetic isotope effects (¹³C KIEs) in the decarbonylation of formic acid diluted with water 1:1 (V:V) has been studied in the 130–181°C temperature interval in sealed vacuum all glass reactions vessels. The experimental ¹³C KIEs are higher than the ¹³C KIEs values extrapolated from low 50–100°C temperature interval ¹³C KIEs observed in the decarbonylation of water free liquid formic acid but less than ¹³C KIEs expected theoretically assuming the complete carbon—oxygen (¹³C[sbnd]¹⁶O) bond rupture in the transition state. For instance the (k₁₂/k₁₃) KIE found in this study is 1.0375 at 170.2°C while the “full” ¹³C KIE is expected to be 1.0429 at this temperature. The ¹³C KIE extrapolated to 170.2°C from the low temperature data published earlier is 1.0299. - The Arrhenius activation energy for the decarbonylation of formic acid in 1:1 water solution E = 31.3 kcal/mol is by 6 kcal/mol higher than that which was obtained with 99,9% pure formic acid (E = 25,660 kcal/mol). The entropy of activation ΔS ^≠ increased from -21.4 e.u. (pure formic acid) to -15.3 e.u. in the decarbonylation of formic acid diluted with water 1:1. The increases of the enthalpy of activation, of the entropy of activation and partly of the carbon-13 kinetic isotope effect observed in the decarbonylation of formic acid in water solution have been rationalized by suggesting isotopic equilibria interfering the pure kinetic fractionation of ¹³C and intervention of the water molecules into the process of transfer of protons to the formic acid molecules lowering the absolute rate of their decomposition.     

飞秒时间分辨拉曼光谱用于研究β-胡萝卜素单重激发态内转换和振动弛豫过程

搭建了飞秒时间分辨受激拉曼光谱(FSRS)装置,并用于研究全反式β-胡萝卜素单重电子激发态超快内转换和振动弛豫过程.基于三脉冲“抽运-探测”方案搭建的时间分辨受激拉曼光谱装置同时实现了150fs的时间分辨率和23.7cm^-1的光谱分辨率,光谱检测范围为300—4000cm^-1.对全反式β-胡萝卜素电子激发态的飞秒时间分辨拉曼光谱研究表明,β-胡萝卜素被激发到S₂态后,经由寿命约为0.3ps的中间态S_X态实 关键词： 飞秒时间分辨拉曼光谱 β-胡萝卜素 激发态内转换 振动弛豫     

Neutron,x-ray and lattice dynamical studies of paraelectric Sb2S3

Neutron and x-ray diffraction studies of Sb₂S₃ indicate extensive diffuse scattering in the plane perpendicular to the chain axis of polymer-like (Sb₄S₆) _n molecules. The crystal structure of the paraelectric phase is said to be orthorhombic with space group D _2h ¹⁶ with four molecules per unit cell. The observed diffuse scattering may be due to static disorder or some dynamical effects. In this paper the authors have examined the possible dynamical origin by recourse to lattice dynamical studies. Dispersion relation of phonons along the three symmetry directionsa*,b* andc* is evaluated based on a lattice dynamical model incorporating Coulomb, covalent and a Born-Mayer-like short range interactions. Group theoretical analysis based on the group of neutral elements of crystal sites (GNES) was essential in order to examine and aid in the numerical computations. The group theoretical technique involving GNES extended to ‘pseudo-molecular’ systems is also discussed in this context. The phonon dispersion relation shows that there are rather flat TA-TO branches of very low frequency in thea andc directions which may give rise to diffuse scattering. The branches along theb-axis are quite dissimilar to those alonga andc axes because of anisotropy. Variation of the potential parameters leads to instability of the lowest TA-TO branch. This is suggestive of a temperatures or pressure-dependent phase transition. However since these modes are optically ‘silent’ one needs to carry out either high resolution neutron scattering or ultrasonic studies to confirm various aspects of the theoretical studies.     

The structure factor for liquid nitrogen and liquid oxygen from neutron scattering studies

The structure factor, S(Q), has been measured for liquid nitrogen at 77 K and liquid oxygen at 84 K by neutron diffraction over a range of momentum transfer, Q, from 0·3 to 7·3 Å^-1. In the case of oxygen a correction for magnetic scattering has been included.

The liquid structure factor for nitrogen compares well with that obtained from X-ray diffraction measurements but there are significant discrepancies in the case of oxygen. These may be partially attributed to uncertainty in the form factor for paramagnetic scattering.

The data have been analysed in terms of several different models for the orientational correlation between neighbouring molecules. The results are particularly sensitive to uncertainties in the absolute normalization of the data, the inter-nuclear distance for the molecular structure and Placzek corrections; the effect of these errors is considered in detail. It is shown that some form of orientation correlation must exist but its precise nature could not be obtained from the present data.