Fast, scalable master equation solution algorithms. IV. Lanczos iteration with diffusion approximation preconditioned iterative inversion

In this paper we propose a second linearly scalable method for solving large master equations arising in the context of gas-phase reactive systems. The new method is based on the well-known shift-invert Lanczos iteration using the GMRES iteration preconditioned using the diffusion approximation to the master equation to provide the inverse of the master equation matrix. In this way we avoid the cubic scaling of traditional master equation solution methods while maintaining the speed of a partial spectral decomposition. The method is tested using a master equation modeling the formation of propargyl from the reaction of singlet methylene with acetylene, proceeding through long-lived isomerizing intermediates. (C) 2003 American Institute of Physics.

Fast, scalable master equation solution algorithms. III. Direct time propagation accelerated by a diffusion approximation preconditioned iterative solver

In this paper we propose a novel fast and linearly scalable method for solving master equations arising in the context of gas-phase reactive systems, based on an existent stiff ordinary differential equation integrator. The required solution of a linear system involving the Jacobian matrix is achieved using the GMRES iteration preconditioned using the diffusion approximation to the master equation. In this way we avoid the cubic scaling of traditional master equation solution methods and maintain the low temperature robustness of numerical integration. The method is tested using a master equation modelling the formation of propargyl from the reaction of singlet methylene with acetylene, proceeding through long lived isomerizing intermediates. (C) 2003 American Institute of Physics.

Selecting methods to solve multi-well master equations

There are several competing methods commonly used to solve energy grained master equations describing gas-phase reactive systems. When it comes to selecting an appropriate method for any particular problem, there is little guidance in the literature. In this paper we directly compare several variants of spectral and numerical integration methods from the point of view of computer time required to calculate the solution and the range of temperature and pressure conditions under which the methods are successful. The test case used in the comparison is an important reaction in combustion chemistry and incorporates reversible and irreversible bimolecular reaction steps as well as isomerizations between multiple unimolecular species. While the numerical integration of the ODE with a stiff ODE integrator is not the fastest method overall, it is the fastest method applicable to all conditions.

Modelação numérica de uma caldeira doméstica a pellets

A biomassa é uma das fontes de energia renovável com maior potencial em Portugal, sendo a capacidade de produção de pellets de biomassa atualmente instalada superior a 1 milhão de toneladas/ano. Contudo, a maioria desta produção destina-se à exportação ou à utilização em centrais térmicas a biomassa, cujo crescimento tem sido significativo nos últimos anos, prevendo-se que a capacidade instalada em 2020 seja de aproximadamente 250 MW. O mercado português de caldeiras a pellets é bastante diversificado. O estudo que realizamos permitiu concluir que cerca de 90% das caldeiras existentes no mercado português têm potências inferiores a 60 kW, possuindo na sua maioria grelha fixa (81%), com sistema de ignição eléctrica (92%) e alimentação superior do biocombustível sólido (94%). O objetivo do presente trabalho foi o desenvolvimento de um modelo para simulação de uma caldeira a pellets de biomassa, que para além de permitir otimizar o projeto e operação deste tipo de equipamento, permitisse avaliar as inovações tecnológicas nesta área. Para tal recorreu-se o BiomassGasificationFoam, um código recentemente publicado, e escrito para utilização com o OpenFOAM, uma ferramenta computacional de acesso livre, que permite a simulação dos processos de pirólise, gasificação e combustão de biomassa. Este código, que foi inicialmente desenvolvido para descrever o processo de gasificação na análise termogravimétrica de biomassa, foi por nós adaptado para considerar as reações de combustão em fase gasosa dos gases libertados durante a pirólise da biomassa (recorrendo para tal ao solver reactingFoam), e ter a possibilidade de realizar a ignição da biomassa, o que foi conseguido através de uma adaptação do código de ignição do XiFoam. O esquema de ignição da biomassa não se revelou adequado, pois verificou-se que a combustão parava sempre que a ignição era inativada, independentemente do tempo que ela estivesse ativa. Como alternativa, usaram-se outros dois esquemas para a combustão da biomassa: uma corrente de ar quente, e uma resistência de aquecimento. Ambos os esquemas funcionaram, mas nunca foi possível fazer com que a combustão fosse autossustentável. A análise dos resultados obtidos permitiu concluir que a extensão das reações de pirólise e de gasificação, que são ambas endotérmicas, é muito pequena, pelo que a quantidade de gases libertados é igualmente muito pequena, não sendo suficiente para libertar a energia necessária à combustão completa da biomassa de uma maneira sustentável. Para tentar ultrapassar esta dificuldade foram testadas várias alternativas, , que incluíram o uso de diferentes composições de biomassa, diferentes cinéticas, calores de reação, parâmetros de transferência de calor, velocidades do ar de alimentação, esquemas de resolução numérica do sistema de equações diferenciais, e diferentes parâmetros dos esquemas de resolução utilizados. Todas estas tentativas se revelaram infrutíferas. Este estudo permitiu concluir que o solver BiomassGasificationFoam, que foi desenvolvido para descrever o processo de gasificação de biomassa em meio inerte, e em que a biomassa é aquecida através de calor fornecido pelas paredes do reator, aparentemente não é adequado à descrição do processo de combustão da biomassa, em que a combustão deve ser autossustentável, e em que as reações de combustão em fase gasosa são importantes. Assim, é necessário um estudo mais aprofundado que permita adaptar este código à simulação do processo de combustão de sólidos porosos em leito fixo.

Hydrogen sulfide measurement by headspace-gas chromatography-mass spectrometry (HS-GC-MS): application to gaseous samples and gas dissolved in muscle.

The aim of our study was to present a new headspace-gas chromatography-mass spectrometry (HS-GC-MS) method applicable to the routine determination of hydrogen sulfide (H(2)S) concentrations in biological and gaseous samples. The primary analytical drawback of the GC/MS methods for H(2)S measurement discussed in the literature was the absence of a specific H(2)S internal standard required to perform quantification. Although a deuterated hydrogen sulfide (D(2)S) standard is currently available, this standard is not often used because this standard is expensive and is only available in the gas phase. As an alternative approach, D(2)S can be generated in situ by reacting deuterated chloride with sodium sulfide; however, this technique can lead to low recovery yield and potential isotopic fractionation. Therefore, N(2)O was chosen for use as an internal standard. This method allows precise measurements of H(2)S concentrations in biological and gaseous samples. Therefore, a full validation using accuracy profile based on the β-expectation tolerance interval is presented. Finally, this method was applied to quantify H(2)S in an actual case of H(2)S fatal intoxication.

Measurement of biologically available naphthalene in gas and aqueous phases by use of a Pseudomonas putida biosensor.

Genetically constructed microbial biosensors for measuring organic pollutants are mostly applied in aqueous samples. Unfortunately, the detection limit of most biosensors is insufficient to detect pollutants at low but environmentally relevant concentrations. However, organic pollutants with low levels of water solubility often have significant gas-water partitioning coefficients, which in principle makes it possible to measure such compounds in the gas rather than the aqueous phase. Here we describe the first use of a microbial biosensor for measuring organic pollutants directly in the gas phase. For this purpose, we reconstructed a bioluminescent Pseudomonas putida naphthalene biosensor strain to carry the NAH7 plasmid and a chromosomally inserted gene fusion between the sal promoter and the luxAB genes. Specific calibration studies were performed with suspended and filter-immobilized biosensor cells, in aqueous solution and in the gas phase. Gas phase measurements with filter-immobilized biosensor cells in closed flasks, with a naphthalene-contaminated aqueous phase, showed that the biosensor cells can measure naphthalene effectively. The biosensor cells on the filter responded with increasing light output proportional to the naphthalene concentration added to the water phase, even though only a small proportion of the naphthalene was present in the gas phase. In fact, the biosensor cells could concentrate a larger proportion of naphthalene through the gas phase than in the aqueous suspension, probably due to faster transport of naphthalene to the cells in the gas phase. This led to a 10-fold lower detectable aqueous naphthalene concentration (50 nM instead of 0.5 micro M). Thus, the use of bacterial biosensors for measuring organic pollutants in the gas phase is a valid method for increasing the sensitivity of these valuable biological devices.

The use of heterogeneous chemistry for the characterization of functional groups at the gas/particle interface of soot and TiO(2) nanoparticles

Six gases (N((CH3)3), NH2OH, CF3COOH, HCl, NO2, O3) were selected to probe the surface of seven combustion aerosol (amorphous carbon, flame soot) and three types of TiO2 nanoparticles using heterogeneous, that is gas-surface reactions. The gas uptake to saturation of the probes was measured under molecular flow conditions in a Knudsen flow reactor and expressed as a density of surface functional groups on a particular aerosol, namely acidic (carboxylic) and basic (conjugated oxides such as pyrones, N-heterocycles) sites, carbonyl (R1-C(O)-R2) and oxidizable (olefinic, -OH) groups. The limit of detection was generally well below 1% of a formal monolayer of adsorbed probe gas. With few exceptions most investigated aerosol samples interacted with all probe gases which points to the coexistence of different functional groups on the same aerosol surface such as acidic and basic groups. Generally, the carbonaceous particles displayed significant differences in surface group density: Printex 60 amorphous carbon had the lowest density of surface functional groups throughout, whereas Diesel soot recovered from a Diesel particulate filter had the largest. The presence of basic oxides on carbonaceous aerosol particles was inferred from the ratio of uptakes of CF3COOH and HCl owing to the larger stability of the acetate compared to the chloride counterion in the resulting pyrylium salt. Both soots generated from a rich and a lean hexane diffusion flame had a large density of oxidizable groups similar to amorphous carbon FS 101. TiO2 15 had the lowest density of functional groups among the three studied TiO2 nanoparticles for all probe gases despite the smallest size of its primary particles. The used technique enabled the measurement of the uptake probability of the probe gases on the various supported aerosol samples. The initial uptake probability, g0, of the probe gas onto the supported nanoparticles differed significantly among the various investigated aerosol samples but was roughly correlated with the density of surface groups, as expected. [Authors]

Performance Analysis of Two Quantum Reaction Dynamics Codes: Time-Dependent and Time-Independent Strategies

The computer simulation of reaction dynamics has nowadays reached a remarkable degree of accuracy. Triatomic elementary reactions are rigorously studied with great detail on a straightforward basis using a considerable variety of Quantum Dynamics computational tools available to the scientific community. In our contribution we compare the performance of two quantum scattering codes in the computation of reaction cross sections of a triatomic benchmark reaction such as the gas phase reaction Ne + H2+ %12. NeH++ H. The computational codes are selected as representative of time-dependent (Real Wave Packet [ ]) and time-independent (ABC [ ]) methodologies. The main conclusion to be drawn from our study is that both strategies are, to a great extent, not competing but rather complementary. While time-dependent calculations advantages with respect to the energy range that can be covered in a single simulation, time-independent approaches offer much more detailed information from each single energy calculation. Further details such as the calculation of reactivity at very low collision energies or the computational effort related to account for the Coriolis couplings are analyzed in this paper.

A reassessment of models for hydrocarbon generation in the Khibiny nepheline syenite complex, Kola Peninsula, Russia

Although hydrocarbon-bearing fluids have been known from the alkaline igneous rocks of the Khibiny intrusion for many years, their origin remains enigmatic. A recently proposed model of post-magmatic hydrocarbon (HC) generation through Fischer-Tropsch (FT) type reactions suggests the hydration of Fe-bearing phases and release of H-2 which reacts with magmatically derived CO2 to form CH4 and higher HCs. However, new petrographic, microthermometric, laser Raman, bulk gas and isotope data are presented and discussed in the context of previously published work in order to reassess models of HC generation. The gas phase is dominated by CH4 with only minor proportions of higher hydrocarbons. No remnants of the proposed primary CO2-rich fluid are found in the complex. The majority of the fluid inclusions are of secondary nature and trapped in healed microfractures. This indicates a high fluid flux after magma crystallisation. Entrapment conditions for fluid inclusions are 450-550 degrees C at 2.8-4.5 kbar. These temperatures are too high for hydrocarbon gas generation through the FT reaction. Chemical analyses of rims of Fe-rich phases suggest that they are not the result of alteration but instead represent changes in magma composition during crystallisation. Furthermore, there is no clear relationship between the presence of Fe-rich minerals and the abundance of fluid inclusion planes (FIPs) as reported elsewhere. delta C-13 values for methane range from -22.4% to -5.4%, confirming a largely abiogenic origin for the gas. The presence of primary CH4-dominated fluid inclusions and melt inclusions, which contain a methane-rich gas phase, indicates a magmatic origin of the HCs. An increase in methane content, together with a decrease in delta C-13 isotope values towards the intrusion margin suggests that magmatically derived abiogenic hydrocarbons may have mixed with biogenic hydrocarbons derived from the surrounding country rocks. (C) 2006 Elsevier BV. All rights reserved.

Performance Analysis of Two Quantum Reaction Dynamics Codes: Time-Dependent and Time-Independent Strategies

The computer simulation of reaction dynamics has nowadays reached a remarkable degree of accuracy. Triatomic elementary reactions are rigorously studied with great detail on a straightforward basis using a considerable variety of Quantum Dynamics computational tools available to the scientific community. In our contribution we compare the performance of two quantum scattering codes in the computation of reaction cross sections of a triatomic benchmark reaction such as the gas phase reaction Ne + H2+ %12. NeH++ H. The computational codes are selected as representative of time-dependent (Real Wave Packet [ ]) and time-independent (ABC [ ]) methodologies. The main conclusion to be drawn from our study is that both strategies are, to a great extent, not competing but rather complementary. While time-dependent calculations advantages with respect to the energy range that can be covered in a single simulation, time-independent approaches offer much more detailed information from each single energy calculation. Further details such as the calculation of reactivity at very low collision energies or the computational effort related to account for the Coriolis couplings are analyzed in this paper.

Modeling reaction kinetics and mass transfer in ozonation in water solutions

This dissertation is based on four articles dealing with modeling of ozonation. The literature part of this considers some models for hydrodynamics in bubble column simulation. A literature review of methods for obtaining mass transfer coefficients is presented. The methods presented to obtain mass transfer are general models and can be applied to any gas-liquid system. Ozonation reaction models and methods for obtaining stoichiometric coefficients and reaction rate coefficients for ozonation reactions are discussed in the final section of the literature part. In the first article, ozone gas-liquid mass transfer into water in a bubble column was investigated for different pH values. A more general method for estimation of mass transfer and Henry’s coefficient was developed from the Beltrán method. The ozone volumetric mass transfer coefficient and the Henry’s coefficient were determined simultaneously by parameter estimation using a nonlinear optimization method. A minor dependence of the Henry’s law constant on pH was detected at the pH range 4 - 9. In the second article, a new method using the axial dispersion model for estimation of ozone self-decomposition kinetics in a semi-batch bubble column reactor was developed. The reaction rate coefficients for literature equations of ozone decomposition and the gas phase dispersion coefficient were estimated and compared with the literature data. The reaction order in the pH range 7-10 with respect to ozone 1.12 and 0.51 the hydroxyl ion were obtained, which is in good agreement with literature. The model parameters were determined by parameter estimation using a nonlinear optimization method. Sensitivity analysis was conducted using object function method to obtain information about the reliability and identifiability of the estimated parameters. In the third article, the reaction rate coefficients and the stoichiometric coefficients in the reaction of ozone with the model component p-nitrophenol were estimated at low pH of water using nonlinear optimization. A novel method for estimation of multireaction model parameters in ozonation was developed. In this method the concentration of unknown intermediate compounds is presented as a residual COD (chemical oxygen demand) calculated from the measured COD and the theoretical COD for the known species. The decomposition rate of p-nitrophenol on the pathway producing hydroquinone was found to be about two times faster than the p-nitrophenol decomposition rate on the pathway producing 4- nitrocatechol. In the fourth article, the reaction kinetics of p-nitrophenol ozonation was studied in a bubble column at pH 2. Using the new reaction kinetic model presented in the previous article, the reaction kinetic parameters, rate coefficients, and stoichiometric coefficients as well as the mass transfer coefficient were estimated with nonlinear estimation. The decomposition rate of pnitrophenol was found to be equal both on the pathway producing hydroquinone and on the path way producing 4-nitrocathecol. Comparison of the rate coefficients with the case at initial pH 5 indicates that the p-nitrophenol degradation producing 4- nitrocathecol is more selective towards molecular ozone than the reaction producing hydroquinone. The identifiability and reliability of the estimated parameters were analyzed with the Marcov chain Monte Carlo (MCMC) method. @All rights reserved. No part of the publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior permission of the author.

Origem e implicações dos ácidos carboxílicos na atmosfera

A general overview about the ambient levels of low molecular weight carboxylic acids and their possible emission sources, as well as the implication of them in the atmosphere is presented. Carboxylic acids are considered to be one of the dominant classes of organic compounds found in the atmosphere in a variety of phases, such as in rainwater, snow and ice, on aerosol particles and gas phase. They may be originated from biogenic and anthropogenic direct emissions and by photochemical reaction in situ. Emission sources and formation mechanisms of organic acids in the atmosphere are discussed.

Nitração aromática: substituição eletrofílica ou reação com transferência de elétrons?

Aromatic nitration is one of the most relevant class of reactions in organic chemistry. It has been intensively studied by both experimental, including works in the condensed as well as in the gas phase, and theoretical procedures. However, the published results do not seem to converge to an unique mechanism. Electrophilic substitution and electron transfer, in an exclusive way, are both proposed as the main mechanism for the reaction. We review these proposals and discuss the most recent findings.

The evaluation of hazardous gas components caused by the thermal degradation of plant oils and animal fats

Neste Oil has introduced plant oils and animal fats for the production of NExBTL renewable diesel, and these raw materials differ from the conventional mineral based oils. One subject of new raw materials study is thermal degradation, or in another name pyrolysis, of these organic oils and fats. The aim of this master’s thesis is to increase knowledge on thermal degradation of these new raw materials, and to identify possible gaseous harmful thermal degradation compounds. Another aim is to de-termine the health and environmental hazards of identified compounds. One objective is also to examine the formation possibilities of hazardous compounds in the produc-tion of NExBTL-diesel. Plant oils and animal fats consist mostly of triglycerides. Pyrolysis of triglycerides is a complex phenomenon, and many degradation products can be formed. Based on the literature studies, 13 hazardous degradation products were identified, one of which was acrolein. This compound is very toxic and dangerous to the environment. Own pyrolysis experiments were carried out with rapeseed and palm oils, and with a mix-ture of palm oil and animal fat. At least 12 hazardous compounds, including acrolein, were analysed from the gas phase. According to the experiments, the factors which influence on acrolein formation are the time of the experiment, the sphere (air/hydrogen) in which the experiment is carried out, and the characteristics of the used oil. The production of NExBTL-diesel is not based on pyrolysis. This is why thermal degradation is possible only when abnormal process conditions prevail.

Biocatálise heterogênea em fase sólido/gás: princípios e aplicações

Enzymatic conversion of gaseous substrates into products in aquo-restricted media, using enzymes or whole cells (free and immobilized) as biocatalysts, constitutes a promising technology for the development of clearer processes. Solid-gas systems offer high production rates for minimal plant sizes, allow important reduction of treated volumes, and permit simplified downstream processes. In this review article, principles and applications of solid-gas biocatalysis are discussed. Comparisons of its advantages and disadvantages with those of the organic- and aqueous-phase reactions are also presented herein.