A Priori Testing of Flamelet Generated Manifolds for Turbulent Partially Premixed Methane/Air Flames

To reduce high computational cost associated with simulations of reacting flows chemistry tabulation methods like the Flamelet Generated Manifold (FGM) method are commonly used. However, H₂, CO and OH predictions in RANS and LES simulations using the FGM (or a similar) method usually show a substantial deviation from measurements. The goal of this study is to assess the accuracy of low-dimensional FGM databases for the prediction of these species in turbulent, partially-premixed reacting flows. It will be examined to what extent turbulent, partially-premixed jet flames can be described by FGM databases based on premixed or counterflow diffusion flamelets and to what extent the chosen molecular transport model for the flamelet influences the accuracy of species mass fraction predictions in CFD-simulations. For LES and RANS applications a model that accounts for subgrid fluctuations has to be added introducing additional errors in numerical results. A priori analysis of FGM databases enables the exclusion of numerical errors (scheme accuracy, convergence) that occur in CFD simulations as well as the exclusion of errors originating from subgrid modeling assumptions in LES and RANS. Four different FGM databases are compared for H₂O, H₂, CO, CO₂ and OH predictions in Sandia Flames C to F. Species mass fractions will be compared to measurements directly and conditioned on mixture fraction. Special attention is paid to the representation of experimentally observed differential diffusion effects by FGM databases.     

Towards logistics systems parameter optimisation through the use of response surfaces

Logistics systems have to cope with uncertainties in demand, in lead times, in transport times, in availability of resources and in quality. Management decisions have to take these uncertainties into consideration. An evaluation of decisions may be done by means of simulation. However, not all stochastic phenomena are of equal importance. By design of simulation experiments and making use of response surfaces, the most important phenomena are detected and their influence on performance estimated. Once the influence of the phenomena is known, this knowledge may be used to determine the optimal values of some decision parameters. An illustration is given on how to use response surfaces in a real-world case. A model is built in a logistics modelling software. The decision parameters have to be optimised for a specific objective function. Experiments are run to estimate the response surface. The validity of the response surface with few observations is also tested.     

Matrix-isolation FT-IR study and theoretical calculations of the vibrational, tautomeric and H-bonding properties of hypoxanthine

The neutral compound hypoxanthine is investigated using the technique of matrix-isolation FT-IR spectroscopy combined with density functional theory (DFT) and ab initio methods. Two theoretical methods (RHF and DFT/B3-LYP) are compared for vibrational frequency prediction, and four methods (RHF//RHF, MP2//RHF, DFT//DFT and MP2//DFT) for prediction of the relative energies of the tautomers and the interaction energies of the complexes. All the possible tautomeric forms have been considered theoretically, and the results indicate that two oxo forms (O17 and O19) and one hydroxy form (H9-r1) are the three most stable forms. The experimental FT-IR spectra are consistent with this prediction, and nearly all the characteristic spectral features of these forms have been identified in the spectrum. A theoretical study of the H-bonded complexes of these three tautomers with water is also performed. Several structures have been found for each form and the results demonstrate that the closed complexes with two H-bonds are the most stable systems due to the H-bond cooperative effect.     

Tautomery and H-bonding characteristics of 2-aminopurine: a combined experimental and theoretical study

An experimental and theoretical RHF, MP2 and DFT/6-31++G^** study is described of the matrix FT-IR spectra of monomer 2-aminopurine and H-bonded complexes of 2-aminopurine with water. 2-aminopurine occurs in Ar predominantly as the amino-N9H tautomer, but small amounts of the amino-N7H tautomer are also present. An approximate K_T value for this tautomeric equilibrium is found to be 0.016 (RHF) and 0.015 (DFT) using the infrared intensity measurement. Four H-bonded complexes of the abundant amino-N9H form with water are detected in the experimental FT-IR spectrum by their characteristic predicted absorptions, i.e. the three closed complexes N3 ^... H-O ^... H-N9, N1 ^... H-O ^... H-NH, N3 ^... H-O ^... H-NH and the open complex N7 ^... H-OH. From the experimental results, the proton affinity of the N7 atom in 2-aminopurine can be estimated. The dependence of the H-bond strength on the H-bond linearity is demonstrated by a correlation between the N ^... H distance and the N ^... H-O angle in closed N ^... H-O ^... H-N complexes. Received 10 December 2001 Published online 13 September 2002     

Influence of ethanol on cannabinoid pharmacokinetic parameters in chronic users

Cannabis is not only the most widely used illicit drug worldwide but is also regularly consumed along with ethanol. In previous studies, it was assumed that cannabis users develop cross-tolerance to ethanol effects. The present study was designed to compare the effects of ethanol in comparison to and in combination with a cannabis joint and investigate changes in pharmacokinetics. In this study, 19 heavy cannabis users participated and received three alcohol dosing conditions that were calculated to achieve steady blood alcohol concentrations (BAC) of about 0, 0.5 and 0.7 g/l during a 5-h time window. Subjects smoked a Δ⁹-tetrahydrocannabinol (THC) cigarette (400 μg/kg) 3 h post-onset of alcohol dosing. Blood samples were taken between 0 and 4 h after smoking. During the first hour, samples were collected every 15 min and every 30 min thereafter. Mean steady-state BACs reached 0, 0.36 and 0.5 g/l. The apparent elimination half-life of THC was slightly prolonged (1.59 vs. 1.93 h, p < 0.05) and the concentration 1 h after smoking was slightly lower (24 vs. 17 ng/ml, p < 0.05) with the higher ethanol dose. The prolonged THC elimination might be explained by a small ethanol-mediated change in distribution to and from deep compartments. Concentrations and pharmacokinetics of 11-hydroxy-THC and 11-nor-9-carboxy-THC (THCA) were not significantly influenced by ethanol. However, THCA concentrations appeared lower in both ethanol conditions, which might also be attributable to changes in distribution. Though not significant in the present study, this might be relevant in the interpretation of cannabinoid concentrations in blood.     

Neutral and zwitterionic glycine.H(2)O complexes: A theoretical and matrix-isolation Fourier transform infrared study

The H-bond interaction between glycine and H2O has been studied by a combined theoretical (DFT(B3LYP)/6-31++G(**)) and experimental (matrix-isolation FT-IR) methodology. The 1:1 and 1:2 complexes of the most stable conformation (I) of glycine appear to be neutral complexes which have been vibrationally characterized in detail. The higher stoichiometry complexes (glycine).(H2O)n with n larger than 3 are demonstrated to be zwitterionic H-bonded complexes. A set of characteristic IR absorption bands for this zwitterionic structure has been observed in low-temperature Ar matrices. This would be the first experimental IR evidence for proton transfer occurring between the NH2 and COOH groups of amino acids by a H-bonded water molecular channel in isolated conditions.     

A theoretical and matrix-isolation FT-IR investigation of the conformational landscape of N-acetylcysteine

The conformational landscape of N-acetylcysteine (NAC) has been investigated by a combined experimental matrix-isolation FT-IR and theoretical methodology. This combination is a powerful tool to study the conformational behavior of relatively small molecules. Geometry optimizations at the HF/3-21 level resulted in 438 different geometries with an energy difference smaller than 22 kJ mol⁻¹. Among these, six conformations were detected with a relative energy difference smaller than 10 kJ mol⁻¹ at the DFT(B3LYP)/6-31++G∗∗ level of theory. These were finally subjected to MP2/6-31++G∗∗ optimizations which resulted in five minima. The vibrational and thermodynamical properties of these conformations were calculated at both the DFT and MP2 methodologies. Experimentally NAC was isolated in an argon matrix at 16 K after being sublimated at 323 K. The most stable MP2 form appeared to be dominant in the experimental spectra but the presence of three other conformations with ΔE_MP2 < 10 kJ mol⁻¹ was also demonstrated. The experimentally observed abundance of the H-bond containing conformations appeared to be in good accordance with the predicted MP2 value.     

Stratified turbulent Bunsen flames: flame surface analysis and flame surface density modelling

In this paper it is investigated whether the Flame Surface Density (FSD) model, developed for turbulent premixed combustion, is also applicable to stratified flames. Direct Numerical Simulations (DNS) of turbulent stratified Bunsen flames have been carried out, using the Flamelet Generated Manifold (FGM) reduction method for reaction kinetics. Before examining the suitability of the FSD model, flame surfaces are characterized in terms of thickness, curvature and stratification.

All flames are in the Thin Reaction Zones regime, and the maximum equivalence ratio range covers 0.1?φ?1.3. For all flames, local flame thicknesses correspond very well to those observed in stretchless, steady premixed flamelets. Extracted curvature radii and mixing length scales are significantly larger than the flame thickness, implying that the stratified flames all burn in a premixed mode. The remaining challenge is accounting for the large variation in (subfilter) mass burning rate.

In this contribution, the FSD model is proven to be applicable for Large Eddy Simulations (LES) of stratified flames for the equivalence ratio range 0.1?φ?1.3. Subfilter mass burning rate variations are taken into account by a subfilter Probability Density Function (PDF) for the mixture fraction, on which the mass burning rate directly depends. A priori analysis point out that for small stratifications (0.4?φ?1.0), the replacement of the subfilter PDF (obtained from DNS data) by the corresponding Dirac function is appropriate. Integration of the Dirac function with the mass burning rate m=m(φ), can then adequately model the filtered mass burning rate obtained from filtered DNS data. For a larger stratification (0.1?φ?1.3), and filter widths up to ten flame thicknesses, a β-function for the subfilter PDF yields substantially better predictions than a Dirac function. Finally, inclusion of a simple algebraic model for the FSD resulted only in small additional deviations from DNS data, thereby rendering this approach promising for application in LES.     

A propeller-like uranyl metallomesogen

Uranyl triflate forms with three imidazo[4,5-f]-1,10-phenanthroline ligands a propeller-like complex that exhibits a hexagonal columnar phase. The ligand is not liquid-crystalline, but a mesophase is induced upon complex formation with the uranyl salt. The thermal behavior has been investigated by polarizing optical microscopy and by high-temperature X-ray diffraction. A model of the stacking of the molecules in the mesophase is proposed.