Computations of turbulent lean premixed combustion using conditional moment closure

Conditional Moment Closure (CMC) is a suitable method for predicting scalars such as carbon monoxide with slow chemical time scales in turbulent combustion. Although this method has been successfully applied to non-premixed combustion, its application to lean premixed combustion is rare. In this study the CMC method is used to compute piloted lean premixed combustion in a distributed combustion regime. The conditional scalar dissipation rate of the conditioning scalar, the progress variable, is closed using an algebraic model and turbulence is modelled using the standard k-e{open} model. The conditional mean reaction rate is closed using a first order CMC closure with the GRI-3.0 chemical mechanism to represent the chemical kinetics of methane oxidation. The PDF of the progress variable is obtained using a presumed shape with the Beta function. The computed results are compared with the experimental measurements and earlier computations using the transported PDF approach. The results show reasonable agreement with the experimental measurements and are consistent with the transported PDF computations. When the compounded effects of shear-turbulence and flame are strong, second order closures may be required for the CMC. © 2013 Copyright Taylor and Francis Group, LLC.

Modelling of turbulent lifted jet flames using flamelets: A priori assessment and a posteriori validation

This study focuses on the modelling of turbulent lifted jet flames using flamelets and a presumed Probability Density Function (PDF) approach with interest in both flame lift-off height and flame brush structure. First, flamelet models used to capture contributions from premixed and non-premixed modes of the partially premixed combustion in the lifted jet flame are assessed using a Direct Numerical Simulation (DNS) data for a turbulent lifted hydrogen jet flame. The joint PDFs of mixture fraction Z and progress variable c, including their statistical correlation, are obtained using a copula method, which is also validated using the DNS data. The statistically independent PDFs are found to be generally inadequate to represent the joint PDFs from the DNS data. The effects of Z-c correlation and the contribution from the non-premixed combustion mode on the flame lift-off height are studied systematically by including one effect at a time in the simulations used for a posteriori validation. A simple model including the effects of chemical kinetics and scalar dissipation rate is suggested and used for non-premixed combustion contributions. The results clearly show that both Z-c correlation and non-premixed combustion effects are required in the premixed flamelets approach to get good agreement with the measured flame lift-off heights as a function of jet velocity. The flame brush structure reported in earlier experimental studies is also captured reasonably well for various axial positions. It seems that flame stabilisation is influenced by both premixed and non-premixed combustion modes, and their mutual influences. © 2014 Taylor & Francis.

Combined Effects of Hot Curing Conditions and Reaction Heat on Rubber Vulcanization Efficiency and Vulcanizate Uniformity

A mathematical model of the chemical kinetics of silicone rubber Vulcanization is developed, with the thermal effects being computed using the increment method, and the hot Vulcanization process estimated with the finite element method. The results show that the reaction heat of rubber vulcanization is important for energy saving, and that a proper curing medium temperature is important when considering both vulcanization efficiency and vulcanizate uniformity. The results also indicate that increases in the forced convective heat transfer coefficient have no significant effect above a certain level. The validity of the numerical model is indirectly proven by comparison with existing data.

水-岩土反应的力学与环境效应研究

The research on mechanical effects of water-rock and soil interaction on deformation and failure of rocks and soils involves three aspects of mechanics, physics and chemistry. It is the cross between geochemistry and rock mechanics and soil mechanics. To sum up, the mechanical effects of water-rock and soil interaction is related to many complex processes. Research in this respect has been being an important forward field and has broad prospects. In connection with the mechanism of the effects of the chemical action of water-rock on deformation and failure of rocks and soils, the research significance, the present state, the developments in this research domain are summarized. Author prospects the future of this research. The research of the subject should be possessed of important position in studying engineering geology and will lead directly to a new understand on geological hazard and control research. In order to investigation the macroscopic mechanics effects of chemical kinetics of water-rock interaction on the deformation and failure, calcic rock, red sandstone and grey granite reacting chemically with different aqueous solution at atmospheric temperature and atmospheric pressure are uniaxially compressed. The quantitative results concerning the changes of uniaxially compressive strength and elastic modulus under different conditions are obtained. It is found that the mechanical effects of water on rock is closely related to the chemical action of water-rock or the chemical damage in rock, and the intensity of chemical damage is direct ratio to the intensity of chemical action in water-rock system. It is also found that the hydrochemical action on rock is time-dependent through the test. The mechanism of permeation and hydrochemical action resulting in failure of loaded rock mass or propagation of fractures in rocks would be a key question in rock fracture mechanics. In this paper, the fracture mechanical effects of chemical action of water-rock and their time- and chemical environment-dependent behavior in grey granite, green granite, grey sandstone and red sandstone are analyzed by testing K_(IC) and COD of rock under different conditions. It is found that: ①the fracture mechanical effect of chemical action of water-rock is outstanding and time-dependent, and high differences exist in the influence of different aqueous solution, different rocks, different immersion ways and different velocity of cycle flow on the fracture mechanical effects in rock. ②the mechanical effects of water-rock interaction on propagation of fractures is consistent with the mechanical effects on the peak strength of rock. ③the intensity of the mechanical fracture effects increases as the intensity of chemical action of water-rock increases. ④iron and calcium ion bearing mineral or cement in rock are some key ion or chemical composition, and especially iron ion-bearing mineral resulting in chemical action of water-rock to be provided with both positive and negative mechanical effects on rock. Through the above two tests, we suggest that primary factors influencing chemical damage in rock consist of the chemical property of rock and aqueous solution, the structure or homogeneity of rocks, the flow velocity of aqueous solution passing through rock, and cause of formation or evolution of rock. The paper explores the mechanism on the mechanical effects of water-rock interaction on rock by using the theory of chemistry and rock fracture mechanics with chemical damage proposed by author, the modeling method and the energy point of view. In this paper, the concept of absorbed suction between soil grains caused by capillary response is given and expounded, and the relation and basic distinction among this absorbed suction, surface tension and capillary pressure of the soil are analyzed and established. The law of absorbed suction change and the primary factors affecting it are approached. We hold that the structure suction are changeable along with the change of the saturation state in unsaturated soils. In view of this, the concept of intrinsic structure suction and variable structure suction are given and expounded, and this paper points out: What we should study is variable structure suction when studying the effective stress. By IIIy κHH's theory of structure strength of soils, the computer method for variable structure suction is analyzed, the measure method for variable structure suction is discussed, and it reach the conclusions: ①Besides saturation state, variable structure suction is affected by grain composition and packing patter of grains. ②The internal relations are present between structure parameter N in computing structure suction and structure parameter D in computing absorbed suction. We think that some problems exit in available principle of effective stress and shear strength theory for unsaturated soil. Based on the variable structure suction and absorbed suction, the classification of saturation in soil and a principle of narrow sense effective stress are proposed for unsaturated soils. Based on generalized suction, the generalized effective stress formula and a principle of generalized effective stress are proposed for unsaturated soils. The experience parameter χ in Bishop's effective stress formula is defined, and the principal factors influencing effective stress or χ. The primary factor affecting the effective stress in unsaturated soils, and the principle classifying unsaturated soils and its mechanics methods analyzing unsaturated soils are discussed, and this paper points out: The theory on studying unsaturated soil mechanics should adopt the micromechanics method, then raise it to macromechanics and to applying. Researching the mechanical effects of chemical action of water-soil on soil is of great importance to geoenvironmental hazard control. The texture of soil and the fabric of soil mass are set forth. The tests on physical and mechanical property are performed to investigate the mechanism of the positive and negative mechanical effects of different chemical property of aqueous solution. The test results make clear that the plastic limit, liquid limit and plasticity index are changed, and there exists both positive and negative effects on specimens in this test. Based on analyzing the mechanism of the mechanical effects of water-soil interaction on soil, author thinks that hydrochemical actions being provided with mechanical effects on soil comprise three kinds of dissolution, sedimentation or crystallization. The significance of these tests lie in which it is recognized for us that we may improve, adjust and control the quality of soils, and may achieve the goal geological hazard control and prevention.The present and the significance of the research on environmental effects of water-rock and soil interaction. Various living example on geoenvironmental hazard in this field are enumerated. Following above thinking, we have approached such ideals that: ①changing the intensity and distribution of source and sink in groundwater flow system can be used to control the water-rock and soil interaction. ②the chemical action of water-rock and soil can be used to ameliorate the physical and mechanical property of rocks and soils. Lastly, the research thinking and the research methods on mechanical effects and environmental effects of water-rock and soil interaction are put forward and detailed.

塔里木盆地塔中地区寒武-奥陶系烃源岩古地温及成烃演化史研究

The present maturity of Cambrian and Ordovician source rocks in Tazhong area, Tarim basin, is studied using several organic petrology methods and conodont CAI method. The highest palaeotemperature that the Cambrian-Ordovician undergone is revealed by Laser Roman Microprobe (LRM) analysis and by simulating experiment of the kerogen chemical kinetics. In according to all above study, the thermal history of Cambrian and Ordovician is reconstructed based on numerical simulating approaches. The characteristics of secondary hydrocarbon generating are studied by inclusions analysis. The reflectances of the samples in the drills located in Tazhong area show that the maturities of Cambrian source rocks are in the stages of condense oil-dry gas, and that of Ordovician source rocks range from peak of oil generating to wet gas stage. The palaeotemperature data of Cambrian-Orovician source rocks from well Tacan 1, based on LRM analysis, are in coincidence with that from other methods. Also are the palaeotemperature data of Cambrian-Orovician source rocks in well Tacan 1 based on the simulating experiments of kerogen pyrolysis, similar to the homogenization temperatures of inclusions in the source rocks. Aaccording to the vitrinite inflectance data of the TZ12 well and Tacan 1 well, the paleotemperature gradients are analysized and reconstructed. These data show that the paleotemperature gradient in Tazhong area was the highest during Cambrian-Ordovician period, it was up to 3.5°C/100m. Following, the temperature gradient descended gradually and it reached to the lowest at present (2.2°C/100m). The histories of maturation and hydrocarbon generation of Cambrian and Ordovician source rocks in Tazhong area are researched systematically and quantitatively, the results show that periods of oil generation from Cambrian and Ordovician source rocks lasted for a long time from Ordovician to Carbonferious periods because the central Cambrian stratum in the north slope of Tazhong area is buried differently in depth. The top of the Cambrian entered into the peak of oil generation in middle-late Ordovician, and most area of the north slope of Tazhong area entered into the peak of oil generation in Carbonferious period, and on the uplift belt some of source rocks entered into the peak of oil generation in Permian period. In early Devonian, the central of the Lower Ordovician source rocks near the Manjiaer depression reached the peak of oil generation and near the top of the Tazhong uplift did not reached the peak of oil generation until early Cretaceous. The middle-upper Ordovician entered into the peak of oil generation in early-middle Jurassic. The time of the middle-upper Ordovician in the top of the uplift belt entering into the peak of oil generation was delayed, because the source rock was buried shallowly, and it did not reached the peak of oil generation until middle Cretaceous. Middle-upper Ordovician in the top of the north slope has been in the peak of oil generation now, it is consistent with the maturity (1.0-1.2%Ro) of the source rocks. The characteristics of the inclusions formed by kerogens are different from that by crystal-enclosed organic matters(OM) during secondary hydrocarbon generation of Cambrian and Ordovician source rocks. The secondary hydrocarbon generation mainly occurred in Mesozoic-Cenozoic period, in an area of about 9000km2 in the north slope. The intensity of the secondary hydrocarbon generation of Cambrian and Ordovician is up to 21kg/torg and 36kg/torg) respectively. Using the staged gas chromatography, the high-over maturated carbonate source rocks are analysized to release the adsorbed OM, inclusions OM and crystal-enclosed OM, respectively, and to evaluate their relative contributions to secondary hydrocarbon generation. The three periods of oil and gas migration and petroleum pools formation in Tazhong area are determined according to organic inclusions and solid bitumen.

A collision model for DNA separation by capillary electrophoresis in dilute polymer solution

A theoretical description. based on chemical kinetics and electrochemistry, is given of DNA separation in dilute polymer solution by capillary electrophoresis. A self-consistent model was developed leading to predictions of the DNA electrophoretic velocity as a function of the experimental conditions - polymer concentration, temperature, and electric field strength. The effect of selected experimental variables is discussed. The phenomena discussed are illustrated for the example of 100 bp DNA ladder separation in dilute HPMC solution by capillary electrophoresis. This model is the first single model that can fully explain the dependence of DNA electrophoretic velocity on electrophoretic conditions.

Simulação de um processo de pirólise rápida de biomassa

Mestrado em Engenharia Química - Ramo Optimização Energética na Indústria Química

Kinetic studies of the effect of organic sulphides on the oxidation of other sulphides /

The rates of oxidation of three Organic sulphides viz. methyl phenyl sulphide, (P), p -me thoxyphenyl methyl sulphide (M) and methyl p-nitrophenyl sulphide (N). have been obtained in ethanol using MoO-(acac)- as catalyst and Bu OOH as the oxidizing agent. A Hammett plot gave a rho value of -2.1 and the activation energies for the oxidation of P, M and N were estimated to be 63.60, 40.12 and 197.46 Kj mol respectively. The effect of organic sulphide on the oxidation of another sulphide was also ascertained. Positive and negative deviations were observed from the expected slope.

Thermodynamics and log–contrast analysis in fluid geochemistry

There are two principal chemical concepts that are important for studying the natural environment. The first one is thermodynamics, which describes whether a system is at equilibrium or can spontaneously change by chemical reactions. The second main concept is how fast chemical reactions (kinetics or rate of chemical change) take place whenever they start. In this work we examine a natural system in which both thermodynamics and kinetic factors are important in determining the abundance of NH+4 , NO−2 and NO−3 in superficial waters. Samples were collected in the Arno Basin (Tuscany, Italy), a system in which natural and antrophic effects both contribute to highly modify the chemical composition of water. Thermodynamical modelling based on the reduction-oxidation reactions involving the passage NH+4 -> NO−2 -> NO−3 in equilibrium conditions has allowed to determine the Eh redox potential values able to characterise the state of each sample and, consequently, of the fluid environment from which it was drawn. Just as pH expresses the concentration of H+ in solution, redox potential is used to express the tendency of an environment to receive or supply electrons. In this context, oxic environments, as those of river systems, are said to have a high redox potential because O2 is available as an electron acceptor. Principles of thermodynamics and chemical kinetics allow to obtain a model that often does not completely describe the reality of natural systems. Chemical reactions may indeed fail to achieve equilibrium because the products escape from the site of the rection or because reactions involving the trasformation are very slow, so that non-equilibrium conditions exist for long periods. Moreover, reaction rates can be sensitive to poorly understood catalytic effects or to surface effects, while variables as concentration (a large number of chemical species can coexist and interact concurrently), temperature and pressure can have large gradients in natural systems. By taking into account this, data of 91 water samples have been modelled by using statistical methodologies for compositional data. The application of log–contrast analysis has allowed to obtain statistical parameters to be correlated with the calculated Eh values. In this way, natural conditions in which chemical equilibrium is hypothesised, as well as underlying fast reactions, are compared with those described by a stochastic approach

Critical thoughts on computing atom condensed Fukui functions

Different procedures to obtain atom condensed Fukui functions are described. It is shown how the resulting values may differ depending on the exact approach to atom condensed Fukui functions. The condensed Fukui function can be computed using either the fragment of molecular response approach or the response of molecular fragment approach. The two approaches are nonequivalent; only the latter approach corresponds in general with a population difference expression. The Mulliken approach does not depend on the approach taken but has some computational drawbacks. The different resulting expressions are tested for a wide set of molecules. In practice one must make seemingly arbitrary choices about how to compute condensed Fukui functions, which suggests questioning the role of these indicators in conceptual density-functional theory

Evaluation of data for atmospheric models: master equation/RRKM calculations on the combination reaction, BrO+NO2 -> BrONO2, a conundrum

Experimental data for the title reaction were modeled using master equation (ME)/RRKM methods based on the Multiwell suite of programs. The starting point for the exercise was the empirical fitting provided by the NASA (Sander, S. P.; Finlayson-Pitts, B. J.; Friedl, R. R.; Golden, D. M.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Molina, M. J.; Moortgat, G. K.; Orkin, V. L.; Ravishankara, A. R. Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 15; Jet Propulsion Laboratory: Pasadena, California, 2006)(1) and IUPAC (Atkinson, R.; Baulch, D. L.; Cox, R. A.: R. F. Hampson, J.; Kerr, J. A.; Rossi, M. J.; Troe, J. J. Phys. Chem. Ref. Data. 2000, 29, 167) 2 data evaluation panels, which represents the data in the experimental pressure ranges rather well. Despite the availability of quite reliable parameters for these calculations (molecular vibrational frequencies (Parthiban, S.; Lee, T. J. J. Chem. Phys. 2000, 113, 145)3 and a. value (Orlando, J. J.; Tyndall, G. S. J. Phys. Chem. 1996, 100,. 19398)4 of the bond dissociation energy, D-298(BrO-NO2) = 118 kJ mol(-1), corresponding to Delta H-0(circle) = 114.3 kJ mol(-1) at 0 K) and the use of RRKM/ME methods, fitting calculations to the reported data or the empirical equations was anything but straightforward. Using these molecular parameters resulted in a discrepancy between the calculations and the database of rate constants of a factor of ca. 4 at, or close to, the low-pressure limit. Agreement between calculation and experiment could be achieved in two ways, either by increasing Delta H-0(circle) to an unrealistically high value (149.3 kJ mol(-1)) or by increasing , the average energy transferred in a downward collision, to an unusually large value (> 5000 cm(-1)). The discrepancy could also be reduced by making all overall rotations fully active. The system was relatively insensitive to changing the moments of inertia in the transition state to increase the centrifugal effect. The possibility of involvement of BrOONO was tested and cannot account for the difficulties of fitting the data.

Gas-phase rate coefficients for the reactions of O(3P), S(3P), Se(3P), and Te(3P) with alkenes: application of perturbation frontier molecular orbital theory, correlations, and structure-activity relations (SARs)

The kinetics of the reactions of the atoms O(P-3), S(P-3), Se(P-3), and Te((3)p) with a series of alkenes are examined for correlations relating the logarithms of the rate coefficients to the energies of the highest occupied molecular orbitals (HOMOs) of the alkenes. These correlations may be employed to predict rate coefficients from the calculated HOMO energy of any other alkene of interest. The rate coefficients obtained from the correlations were used to formulate structure-activity relations (SARs) for reactions of O((3)p), S(P-3), Se (P-3), and Te((3)p) with alkenes. A comparison of the values predicted by both the correlations and the SARs with experimental data where they exist allowed us to assess the reliability of our method. We demonstrate the applicability of perturbation frontier molecular orbital theory to gas-phase reactions of these atoms with alkenes. The correlations are apparently not applicable to reactions of C(P-3), Si(P-3), N(S-4), and Al(P-2) atoms with alkenes, a conclusion that could be explained in terms of a different mechanism for reaction of these atoms.

A intermediação da noção de probabilidade na construção de conceitos relacionados à cinética química

Este trabalho procurou identificar como estudantes do Ensino Médio se apropriam de conceitos e elaboram determinados modelos inseridos em cinética química, especificamente o modelo cinético de colisão de partículas numa reação (Teoria das Colisões). Esta análise e as reflexões que a seguiram foram baseadas, sobretudo, nos estudos realizados por Piaget, Piaget e Inhelder, Jun e Fischbein. Utilizamos como documentos as transcrições das entrevistas (pré e pós-testes) realizadas individualmente com cada aluno. Inicialmente, os estudantes foram entrevistados (pré-testes) com o intuito de identificar a familiaridade com a noção de evento probabilístico ou aleatório. Numa segunda etapa (pós-testes), esse conhecimento (ou a ausência parcial/total dele) foi posto à prova numa tentativa de se estabelecerem relações com um conteúdo específico da Química (Teoria das Colisões). Os resultados obtidos apontam para grandes discrepâncias entre o modelo cinético de colisões elaborado pelos estudantes e aquele cientificamente aceito.

Optical and electrical diagnostics measurements of plasmas generated in aromatic compounds

Plasmas generated in de discharges in aromatic compounds have been used for several years in polymerization processes. The chemical kinetics developed in such a plasma environment are extremely complicated. Therefore it is extremely important to set up optical and electrical diagnostics in order to establish the kinetics of the film growth, In this work we studied de plasmas generated ill low-pressure atmospheres of benzene for different values of gas pressure and power coupled to the discharge. The pressure range varied from 0.2 to 1.0 mbar for electric power running from 4 to 25 W, the main chemical species observed within the discharge were CH, H and C. It was observed that the CH relative concentration increases continuously with the power in the range investigated. The electron temperature varied from 0.5 to 2.0 eV with the increase of the power, for a fixed value of gas pressure. The relative dielectric constant of the plasma polymerized benzene was kept around 4.8 from 100 Hz to 10 kHz, presenting a resonance near 25 kHz. This electric behaviour of the film was the same fur different conditions of polymeric film deposition, (C) 1997 Elsevier B.V. S.A.