Download or read book A Study of Mercury Oxidation and the Development of a Global Predictive Kinetic Model written by Hans Agarwal and published by . This book was released on 2006 with total page 624 pages. Available in PDF, EPUB and Kindle. Book excerpt: These reaction rate constants were further used to predict experimental data from eleven experimental mercury data sources in the literature. It was found that the predictions from the model correspond very well with the observed published data. Over 90% of the 146 data points were predicted very well.

Download or read book Dissertation Abstracts International written by and published by . This book was released on 2009 with total page 810 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Development of a Chemical Kinetic Model for the Homogeneous Oxidation of Mercury by Chlorine Species written by Rebecca North Sliger and published by . This book was released on 2001 with total page 246 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Kinetic Studies of the Oxidation Pathways of Gaseous Elemental Mercury written by Deanna L. Donohoue and published by . This book was released on 2007 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This work is the first direct measurement of a kinetic rate coefficient for these reactions, and the first work which employed one photon LIF to monitor the HgCl and HgBr products. The second aspect of this work was the development of new laser based techniques to detect atmospheric mercury and its oxidation products for both laboratory and field application. In this work a LIF technique was develop to detect HgCl and HgBr. In addition, a two photon LIF technique initially developed by Bauer et al., 2002 was verified and expanded. The two photon LIF technique was used to directly monitor Hg(0) atoms in-situ, to monitor Hg(0) evolving form a gold tube, and to monitor the Hg(0) evolving from the thermal decomposition of reactive gaseous mercury collected on a KCl coated or uncoated denuder. This work represents a significant advance in the development of a viable method the detect mercury and the mercury oxidation products in the laboratory and in the field and is the first study to observe clear differences in the characteristic desorption profiles of HgO and HgX2. This work has broad implications, it enhanced our current knowledge concerning the biogeochemical cycling of mercury, broadened our understanding of the mercury chemistry in high halogen environment, and provided new techniques which can be applied in future field and laboratory studies.

Download or read book The Forcing of Mercury Oxidation as a Means of Promoting Low Cost Capture written by John C. Kramlich and published by . This book was released on 2003 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Trace amounts of mercury are found in all coals. During combustion this mercury is vaporized and can be released to the atmosphere. This has been a cause for concern for a number of years, and has resulted in a determination by the EPA to regulate and control these emissions. Present technology does not, however, provide inexpensive ways to capture or remove mercury from flue gases. The mercury that exits the furnace in the oxidized form (HgCl{sub 2}) is known to much more easily captured in existing wet pollution control equipment (e.g., wet FGD for SO{sub 2}), principally due to its high solubility in water. Until recently, however, nobody knew what caused this oxidation, or how to promote it. Recent DOE-funded research in our group, along with work by others, has identified the gas phase mechanism responsible for this oxidation. The scenario is as follows. In the flame the mercury is quantitatively vaporized as elemental mercury. Also, the chlorine in the fuel is released as HCl. The direct reaction Hg+HCl is, however, far too slow to be of practical consequence in oxidation. The high temperature region does supports a small concentration of atomic chlorine due to disassociation of HCl. As the gases cool (either in the furnace convective passes, in the quench prior to cold gas cleanup, or within a sample probe), the decay in Cl atom is constrained by the slowness of the principal recombination reaction, Cl+Cl+M {yields} Cl{sub 2}+M. This allows chlorine atom to hold a temporary, local superequilibrium concentration. Once the gases drop below about 550 C, the mercury equilibrium shifts to favor HgCl{sub 2} over Hg, and this superequilibrium chlorine atom promotes oxidation via the fast reactions Hg+Cl+M {yields} HgCl+M, HgCl+Cl+M {yields} HgCl{sub 2}+M, and HgCl+Cl{sub 2} {yields} HgCl{sub 2}+Cl. Thus, the high temperature region provides the Cl needed for the reaction, while the quench region allows the Cl to persist and oxidize the mercury in the absence of decomposition reactions that would destroy the HgCl{sub 2}. Promoting mercury oxidation is one means of getting high-efficiency, ''free'' mercury capture when wet gas cleanup systems are already in place. The chemical kinetic model we developed to describe the oxidation process suggests that oxidation can be promoted by introducing trace amounts of H{sub 2} and/or CO within the quench region. The reaction of these fuels leads to free radicals that promote the selective conversion of HCl to Cl, which can then subsequently react with Hg. The work reported here from our Phase I Innovative Concept grant demonstrated this phenomenon, but it also showed that the process must be applied carefully to avoid promoting the recombination of Cl back to HCl. For example, addition of H{sub 2} at too high a temperature is predicted to actually decrease Cl concentrations via Cl+H{sub 2} {yields} HCl+H. At lower temperatures this reaction is slowed due to its activation energy. Thus, within the correct window, the process becomes selective for Cl promotion. Key parameters are the injection temperature of the promoter, the amount of the fuel added. A successful process based on this research will add a powerful tool to the mercury control arsenal. Presently, fractional oxidation in flue gases varies widely, but averages about 50%. The amounts of promoter needed to obtain quantitative oxidation are predicted to be small ({approx}50 ppm). The H{sub 2}/CO could be supplied by conventional natural gas reformer on site, and the low expected fuel concentration would require only a relatively trivial amount of natural gas, even for a large power plant. For example, a 600 MW{sub e} plant would require the order of only 1 MW thermal equivalent of natural gas. If the mercury in the stream approaching a FGD system is highly oxidized, then high captures could be achieved without any additional cost, even for fuels of low chlorine.

Download or read book Modeling and Experimental Studies of Mercury Oxidation and Adsorption in a Fixed Bed and Entrained Flow Reactor written by and published by . This book was released on 2009 with total page 51 pages. Available in PDF, EPUB and Kindle. Book excerpt: This report presents experimental and modeling mercury oxidation and adsorption data. Fixed-bed and single-particle models of mercury adsorption were developed. The experimental data were obtained with two reactors: a 300-W, methane-fired, tubular, quartz-lined reactor for studying homogeneous oxidation reactions and a fixed-bed reactor, also of quartz, for studying heterogeneous reactions. The latter was attached to the exit of the former to provide realistic combustion gases. The fixed-bed reactor contained one gram of coconut-shell carbon and remained at a temperature of 150°C. All methane, air, SO2, and halogen species were introduced through the burner to produce a radical pool representative of real combustion systems. A Tekran 2537A Analyzer coupled with a wet conditioning system provided speciated mercury concentrations. At 150°C and in the absence of HCl or HBr, the mercury uptake was about 20%. The addition of 50 ppm HCl caused complete capture of all elemental and oxidized mercury species. In the absence of halogens, SO2 increased the mercury adsorption efficiency to up to 30 percent. The extent of adsorption decreased with increasing SO2 concentration when halogens were present. Increasing the HCl concentration to 100 ppm lessened the effect of SO2. The fixed-bed model incorporates Langmuir adsorption kinetics and was developed to predict adsorption of elemental mercury and the effect of multiple flue gas components. This model neglects intraparticle diffusional resistances and is only applicable to pulverized carbon sorbents. It roughly describes experimental data from the literature. The current version includes the ability to account for competitive adsorption between mercury, SO2, and NO2. The single particle model simulates in-flight sorbent capture of elemental mercury. This model was developed to include Langmuir and Freundlich isotherms, rate equations, sorbent feed rate, and intraparticle diffusion. The Freundlich isotherm more accurately described in-flight mercury capture. Using these parameters, very little intraparticle diffusion was evident. Consistent with other data, smaller particles resulted in higher mercury uptake due to available surface area. Therefore, it is important to capture the particle size distribution in the model. At typical full-scale sorbent feed rates, the calculations underpredicted adsorption, suggesting that wall effects can account for as much as 50 percent of the removal, making it an important factor in entrained-mercury adsorption models.

Download or read book The Homogeneus Forcing of Mercury Oxidation to Provide Low Cost Capture written by and published by . This book was released on 2007 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Trace amounts of mercury are found in all coals. During combustion, or during thermal treatment in advanced coal processes, this mercury is vaporized and can be released to the atmosphere with the ultimate combustion products. This has been a cause for concern for a number of years, and has resulted in a determination by the EPA to regulate and control these emissions. Present technology does not, however, provide inexpensive ways to capture or remove mercury. Mercury that exits the furnace in the oxidized form (HgCl2) is known to much more easily captured in existing pollution control equipment (e.g., wet scrubbers for SO2), principally due to its high solubility in water. Work funded by DOE has helped understand the chemical kinetic processes that lead to mercury oxidation in furnaces. The scenario is as follows. In the flame the mercury is quantitatively vaporized as elemental mercury. Also, the chlorine in the fuel is released as HCl. The direct reaction Hg+HCl is, however, far too slow to be of practical consequence in oxidation. The high temperature region does supports a small concentration of atomic chlorine. As the gases cool (either in the furnace convective passes, in the quench prior to cold gas cleanup, or within a sample probe), the decay in Cl atom is constrained by the slowness of the principal recombination reaction, Cl+Cl+M-->Cl2+M. This allows chlorine atom to hold a temporary, local superequilibrium concentration . Once the gases drop below about 550 C, the mercury equilibrium shifts to favor HgCl2 over Hg, and this superequilibrium chlorine atom promotes oxidation via the fast reactions Hg+Cl+M-->HgCl+M, HgCl+Cl+M-->HgCl2+M, and HgCl+Cl2-->HgCl2+Cl. Thus, the high temperature region provides the Cl needed for the reaction, while the quench region allows the Cl to persist and oxidize the mercury in the absence of decomposition reactions that would destroy the HgCl2. Promoting mercury oxidation is one means of getting moderate-efficiency, 'free' mercury capture when wet gas cleanup systems are already in place. The chemical kinetic model we developed to describe the oxidation process suggests that in fuel lean gases, the introduction of trace amounts of H2 within the quench region leads to higher Cl concentrations via chain branching. The amount of additive, and the temperature at the addition point are critical. We investigated this process in a high-temperature quartz flow reactor. The results do indicate a substantial amount of promotion of oxidation with the introduction of relatively small amounts of hydrogen at around 1000 K ((almost equal to)100 ppm relative to the furnace gas). In practical systems the source of this hydrogen is likely to be a small natural gas steam reformer. This would also produce CO, so co-injection of CO was also tested. The CO did not provide any additional promotion, and in some cases led to a reduction in oxidation. We also examined the influence of NO and SO2 on the promotion process. We did not see any influence under the conditions examined. The present results were for a 0.5 s, isothermal plug flow environment. The next step should be to determine the appropriate injection point for the hydrogen and the performance under realistic temperature quench conditions. This could be accomplished first by chemical kinetic modeling, and then by tunnel flow experiment.

Download or read book Mercury Oxidation Across the Selective Catalytic Reduction SCR Unit written by Ana Suarez Negreira and published by . This book was released on 2013 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Mercury emissions from coal-fired power plants represent 32% of the total anthropogenic mercury emissions in the United States (60 tons in 2012, 2000 tons worldwide). In recent years, public concern has increased due to the long-term irreversible effects of mercury on the environment and human health. As a result, the U.S. Environmental Protection Agency (EPA) proposed in December 2011 the Mercury and Air Toxics Standards (MATS); which require U.S. natural gas and coal-fired power plants to install air pollution control devices to prevent 91% of the Hg present in flue gas from being released. Currently, there are several air pollution control devices designed to reduce Hg emissions in power plants and whose working principles depend on the nature of the mercury species. Mercury is present in the flue gas in three forms: elemental (Hg0), oxidized (Hg+2) and particulate (HgP). Oxidized Hg is highly soluble in aqueous solutions, as compared to the insoluble and nonreactive Hg0, thus allowing for the removal of the former by conventional air pollution control devices. As a matter of fact, the promotion of Hg0 oxidation along the path of the flue gas from the boiler to the stack is currently the best approach to remove it by using current emission control technologies. The catalytic oxidation of mercury can be obtained through specific Hg oxidation catalysts such as noble metals or as a co-benefit of existing control technologies such as the Selective Catalyst Reduction (SCR) unit for NOx reduction. The latter option would be particularly attractive due to the associated low economic investment, since 40% of electricity from coal sources is produced in power plants that are already equipped with SCR units. However, little is known about the fate of mercury across the SCR unit, since most of the research work has been devoted to their applicability for NOx reduction. Understanding which are the key factors controlling the oxidation of mercury and developing a detailed mechanism of Hg oxidation across the SCR unit is a primary objective of this dissertation. One of the main achievements of this work has been the integration of an atomic-scale model with bench-scale experiments to identify key factors in Hg oxidation as a co-benefit of the SCR unit. Widely employed materials in commercial SCR catalysts include titania-supported vanadium and tungsten oxides, i.e., V2O5-WO3-TiO2, which were therefore investigated in this study. Theoretical models were used to assess the role of each component, namely, the support (TiO2), the active phase (V2O5) and the promoters (WO3), on the activity of this catalyst towards Hg oxidation. These include both density functional theory and ab-initio thermodynamic calculations; the latter are applied to investigate the effects of temperature and flue gas composition (which is coal dependent) on the reactivity of the catalyst under realistic operating conditions. Active phase, support and structural promoter were incorporated progressively into the analysis, thereby modeling the SCR catalyst with an increased level of complexity. The DFT results show that the active phase, V2O5, alone is not reactive under flue gas conditions and that the presence of the support leads to an increase of its reactivity toward Hg oxidation, presumably due to the higher dispersion of the vanadia phase on the TiO2 surface. Particular focus was given to the interaction of water with the supported system, due the significant concentration of water vapor present in the flue gas (≈ 10%). It is shown that water interacts with the surface in either a molecular or dissociative fashion, depending on the water coverage, which is in turn temperature-dependent. Interestingly, a stabilization effect is observed at low water coverages, as the latter tends to dissociate on the surface, thus yielding a reconstructed surface with attached hydroxyl groups. Moreover, a dehydration process is observed that takes place with increasing temperature and that leads to a water-free surface above 390 K. The analysis of the reactivity of the supported vanadium oxide catalyst was completed by a study of the adsorption energies of gas species that likely play a role in Hg oxidation (i.e., Hg, HgCl, HCl and H2O). Hereby, it was observed that surfaces with high water coverage show higher reactivity towards HgCl (the gas specie with the highest adsorption energy) followed by HCl. The adsorption energies of Hg suggested a negligible interaction with the vanadia dimer. Ab initio thermodynamic calculations were carried out to take into account the effect of temperature and entropy loss on the adsorption energies of these species; based on these results, a mechanism to explain Hg oxidation to HgCl2 was proposed, which involves the adsorption of HCl and HgCl, following a Langmuir-Hinshelwood mechanism. As a final step in the theoretical analysis, the incorporation of WO3 into the model shows that these ternary systems (V2O5-WO3-TiO2) are even more reactive than the binary systems (V2O5-TiO2). First, the effect of the surface coverage was studied by comparing the reactivity of the low- and high-loading binary systems. This analysis indicated enhanced reactivity of the SCR catalyst toward HgCl, HCl and Hg, with increasing loadings of the active phase. The effect of the surface composition on the reactivity of the catalyst was estimated by comparing the reactivity of the binary monolayer systems (i.e., 100% V2O5-TiO2 or 100%WO3-TiO2) against ternary systems (V2O5-WO3-TiO2 with different V2O5/WO3 ratios). This study showed a higher reactivity of the ternary system, with the 75%V2O5-25%WO3-TiO2 system representing the optimal catalyst composition toward Hg oxidation. The theoretical studies were complemented by Hg oxidation experiments carried out in a lab-scale packed-bed reactor with the purpose of benchmarking some of the predictions of the computational work. The effects of flue gas composition, catalyst formulation, temperature and space velocity on the Hg oxidation efficiency of different SCR catalysts were examined under typical flue gas conditions. The effect of the catalyst composition on the activity toward Hg oxidation was analyzed by testing four different SCR catalysts: 4%V2O5-10%WO3-TiO2, 1%V2O5-10%WO3-TiO2, 1%V2O5-TiO2 and 10%WO3-TiO2). It was shown that the binary systems have a lower activity compared to the ternary systems, thus supporting the predictions from first-principles calculations described above. Through the kinetic analysis, parameters such as reaction orders and the apparent activation energy were derived. By using the power law equation, it was found that O2 is zeroth-order and Hg is first-order in terms of the Hg oxidation rate. For the case of HCl, the reaction order could not be estimated using such a simple equation, and a more complex equation is necessary to capture the complexities of the heterogeneous reaction pathway. The activation energy takes a value of about 40 kJ/mol and is in reasonable agreement with data from the literature. It is worth pointing out that the intrinsic difficulty of measuring very low Hg concentration (≈ 5 ppb) results in large uncertainties associated with relevant parameters such as oxidation efficiencies and reaction rates.

Download or read book Experimental and Kinetic Modeling Investigation of Gas phase Mercury Oxidation Reactions with Chlorine written by Andrew Rodger Fry and published by . This book was released on 2008 with total page 768 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Experimental Investigation and Kinetic Modeling of Homogeneous Mercury Oxidation by Halogens written by Brydger Cauch and published by . This book was released on 2008 with total page 216 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Mercury Emission and its Control in Chinese Coal Fired Power Plants written by Jinsong Zhou and published by Springer. This book was released on 2015-01-13 with total page 159 pages. Available in PDF, EPUB and Kindle. Book excerpt: "Mercury Emission and its Control in Chinese Coal-Fired Power Plants" focuses on investigating mercury emissions samplings and measurement in Chinese coal-fired power plants, mercury emission estimations and future trends, mercury speciation transformation during coal combustion, mercury control and mercury stability in byproducts. The book not only introduces mercury emissions from actual coal-fired power plants, but also presents studies on the mechanism of mercury emission and its control. This is a valuable reference for engineering thermal physicists, thermal engineers, and chemical engineers. Jinsong Zhou, Zhongyang Luo, and Mengxiang Fang are Professors in the College of Mechanical and Energy Engineering, Zhejiang University, China. Yanqun Zhu is Associate Professor in the College of Mechanical and Energy Engineering, Zhejiang University, China.

Download or read book High Temperature Mercury Oxidation Kinetics Via Bromine Mechanisms written by Terumi Okano and published by . This book was released on 2009 with total page 158 pages. Available in PDF, EPUB and Kindle. Book excerpt: Abstract: As the foremost production of electricity in the United State comes from coal-fired plants, there is much more to learn on the topic of mercury which is a common component in coal. The speciation of mercury in the flue gas determines the best control technology for a given system. Because of the difficulty in measuring mercury at different stages of the process, it is practical to use mercury reaction kinetics to theoretically determine mercury speciation based upon coal composition, plant equipment and operating conditions. Elemental mercury cannot be captured in wet scrubbers; however, its oxidized forms can. Chlorine is a reasonable oxidizing agent and is naturally found in bituminous coal, but bromine is an even better oxidizing agent because of its larger size, it has stronger London dispersion force interactions with mercury. Bromine additive technologies have recently been implemented in several companies to enhance mercury oxidation. Because capture technologies are highly dependent upon the form of mercury that is present, investigations into their speciation are extremely important. Though there have been numerous efforts to study mercury compounds as relevant to atmospheric studies, there is little data currently available for mercury compounds found in combustion flue gases. It would be particularly beneficial to obtain kinetic rate constants at various high temperature and pressure conditions typical for a combustion system. Prevalent species of mercury containing bromine in coal combustion flue gases were studied using density functional theory (DFT) and a broad range of ab initio methods. Reaction enthalpies, equilibrium bond distances, and vibrational frequencies were all predicted using DFT as well as coupled cluster (CC) methods. All electronic calculations were carried out using the Gaussian03 or MOLPRO software programs. Kinetic predictions of three first-stage and three second-stage oxidation reactions involving the formation of oxidized mercury via bromine containing compounds are presented. Understanding the speciation of mercury in the flue gases of coal combustion is paramount in developing efficient technologies to ensure its capture.

Download or read book Fundamentals of Mercury Oxidation in Flue Gas written by and published by . This book was released on 2008 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: The objective of this project was to understand the importance of and the contribution of gas-phase and solid-phase coal constituents in the mercury oxidation reactions. The project involved both experimental and modeling efforts. The team was comprised of the University of Utah, Reaction Engineering International, and the University of Connecticut. The objective was to determine the experimental parameters of importance in the homogeneous and heterogeneous oxidation reactions; validate models; and, improve existing models. Parameters studied include HCl, NO(subscript x), and SO2 concentrations, ash constituents, and temperature. The results suggested that homogeneous mercury oxidation is below 10% which is not consistent with previous data of others and work which was completed early in this research program. Previous data showed oxidation above 10% and up to 100%. However, the previous data are suspect due to apparent oxidation occurring within the sampling system where hypochlorite ion forms in the KCl impinger, which in turn oxidized mercury. Initial tests with entrained iron oxide particles injected into a flame reactor suggest that iron present on fly ash particle surfaces can promote heterogeneous oxidation of mercury in the presence of HCl under entrained flow conditions. Using the data generated above, with homogeneous reactions accounting for less than 10% of the oxidation, comparisons were made to pilot- and full-scale data. The results suggest that heterogeneous reactions, as with the case of iron oxide, and adsorption on solid carbon must be taking place in the full-scale system. Modeling of mercury oxidation using parameters from the literature was conducted to further study the contribution of homogeneous pathways to Hg oxidation in coal combustion systems. Calculations from the literature used rate parameters developed in different studies, in some cases using transition state theory with a range of approaches and basis sets, and in other cases using empirical approaches. To address this, rate constants for the entire 8-step homogeneous Hg oxidation sequence were developed using an internally consistent transition state approach. These rate constants when combined with the appropriate sub-mechanisms produced lower estimates of the overall extent of homogeneous oxidation, further suggesting that heterogeneous pathways play an important role in Hg oxidation in coal-fired systems.

Download or read book The Homogeneous Forcing of Mercury Oxidation to Provide Low Cost Capture written by John C. Kramlich and published by . This book was released on 2006 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Oxidized mercury formed in combustors (e.g., HgCl{sub 2}) is much more easily captured in existing pollution control equipment (e.g., wet scrubbers for SO{sub 2}) than elemental mercury. This is principally due to the high solubility of the oxidized form in water. Work over the last several years in our laboratory and elsewhere has identified the general outlines of the homogeneous chemistry of oxidation. The goal of the work reported here is to make use of this knowledge of the oxidation mechanism to devise simple and inexpensive ways to promote the oxidation. The hypothesis is that simple fuels such as hydrogen or CO can promote oxidation via the free radicals they generate during their decomposition. These free radicals then promote the formation of Cl from HCl via reactions such as OH+HCl {yields} H{sub 2}O+Cl. The Cl (and Cl{sub 2} derived from Cl recombination) are considered the principal oxidizing species. In our studies, mercury vapor is exposed to HCl under isothermal conditions in a gas containing N{sub 2}, O{sub 2}, and H{sub 2}O. The experiments systematically explore the influence of reaction temperature, HCl concentration, and H{sub 2}O concentration. These baseline conditions are then perturbed by the addition of varying amounts of H{sub 2}, CO, and H{sub 2}/CO added jointly. The following report presents the results of a literature review associated with the dissertation of the student supported by the program. This outlines the state-of-the-art in mercury behavior. It then describes the experimental facilities and the results of tests involving the promotion of the oxidation reaction by H{sub 2}, CO, and H{sub 2}/CO combinations. These results indicate a substantial enhancement of oxidation under isothermal conditions at 900-1000 K, while the additives inhibit oxidation at 1200 K. The next step is to determine whether the existing chemical kinetic models of mercury oxidation are capable of reproducing this behavior. These models can then be used to extrapolate the findings to nonisothermal conditions typical of boiler environments. This would provide guidance on where to inject the oxidation promoters in a practical boiler, and how much promoter is required.

Download or read book Technical Background Report for the Global Mercury Assessment 2013 written by United Nations Publications and published by UN. This book was released on 2013 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: This report details the technical background to the Global Mercury Assessment 2013 - Sources, Emissions, Releases and Environmental Transport (summary for policy-makers) that has been developed in response to Decision 25/5 III, paragraph 36 of the Governing Council of the United Nations Environment Programme (UNEP), that: 'Request the Executive Director, in consultation with Governments, to update the 2008 report entitled Global Atmospheric Mercury Assessment: Sources, Emissions and Transport for consideration by the Governing Council / Global Ministerial Environment Forum at its twenty-seventh session.' This technical background report has been developed in collaboration with the Arctic Monitoring and Assessment Programme (AMAP). As such, this report also constitutes a contribution to the work of AMAP and the Arctic Council

Download or read book Predictive Kinetic Modeling of Low temperature Hydrocarbon Oxidation written by Amrit Jalan and published by . This book was released on 2014 with total page 235 pages. Available in PDF, EPUB and Kindle. Book excerpt: Low temperature oxidation in the gas and condensed phases has been the subject of experimental investigations for many decades owing to applications in many areas of practical significance like thermal stability, combustion, atmospheric chemistry and industrial syntheses. Owing to several practical limitations it has proven difficult to understand these processes at a mechanistic level from experiments alone. Developments in scientific computing have opened up computational chemistry and cheminformatics based tools as an attractive option for exploring and elucidating the kinetics of these complex processes through detailed kinetic modeling and requires efforts in three key areas: single reaction kinetics, reaction networks and coupling kinetics with mass/momentum/energy balance models. This thesis presents several contributions employing high-level electronic structure calculations, reaction rate theory, automated kinetic modeling and empirical correlations to further our mechanistic understanding of low-temperature oxidation in the gas and liquid phase. First, an extensible framework for automatic estimation of species thermochemistry in the solution phase is presented and validated. This framework uses the Linear Solvation Energy Relationship (LSER) formalism of Abraham/Mintz and co-workers for high-throughput estimation of [delta]G°solv(T) in over 30 solvents using solute descriptors estimated from group additivity. The performance of scaled particle theory (SPT) expressions for enthalpic-entropic decomposition of [delta]G°solv(T) is also discussed along with the associated computational issues. Second, the importance of solvent effects on free-radical kinetics is explored using tetralin oxidation as a case study. The solvent dependence for the main propagation and termination reactions are determined using the Polarizable Continuum (PCM) family of solvation models. Incorporating these kinetic solvent effects in detailed kinetic models suggest oxidation rates increase with solvent polarity, consistent with experiment. Following this, electronic structure methods and reaction rate theory are used elucidate mechanistic details of new pathways in liquid-phase and atmospheric oxidation. The first of these studies focuses on pathways that establish [gamma]-ketohydroperoxides (KHP), well-known products in low-temperature alkane oxidation, as precursors to acids through a two-step process. Ab initio calculations are used to identify pathways leading from KHP to a cyclic peroxide isomer which decomposes through novel concerted reactions into carbonyl and carboxylic acid products. High-level gas phase rate coefficients are obtained using DFT/WFT methods coupled with VTST/SCT calculations and multi-structural partition functions (QMs-T). Solvent effects are included using continuum dielectric solvation models and the predicted rate coefficients found to be in excellent agreement with experiment lending theoretical support to the 30-year old Korcek hypothesis. Next, insights from the Korcek reaction are extended to atmospheric chemistry where similar cyclic peroxides are formed by reactions of the Criegee Intermediate (*CH2OO*) with double bonds. More specifically, the role of chemical activation in reactions between *CH2OO* and C=O/C=C species is explored using master equation calculations to obtain phenomenological rate coefficients k(T,P). In the case of reactions with C=O, the yield of collisionally stabilized SOZ at atmospheric pressure was found to increase in the order HCHO

Download or read book Proceedings of ASME Power written by and published by . This book was released on 2004 with total page 786 pages. Available in PDF, EPUB and Kindle. Book excerpt: