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By Xianzhong Hu, Qingbo Yu, Qin Qin

"Oxy-fuel combustion is one promising option among different CO2 capture technologies. The object of this work is to show the effect of CO2 dilution on the laminar flame speed, flame structure and reaction pathway for methane oxidation at O2/CO2 atmosphere. In this paper, kinetic simulations were made using CHEMKIN with GRI-Mech 3.0 mechanism, which was validated by experimental data of laminar flame speeds. The reaction pathway of CH4/O2/CO2 mixture was derived from reaction flow analysis. Results showed that CO2 decreased the flame speeds, lowed concentration of major intermediates and increased flame thickness. The major chemical pathways of CH4 to CO2 have not changed at O2/CO2 atmosphere comparing with O2/N2 atmosphere, but contributions to major intermediates formation from each related elementary reaction have changed a lot. In addition, the secondary chemical pathways of CH3 oxidation became different at O2/CO2 atmosphere.IntroductionNowadays, as the global economy is developing fast and the pollutant levels (especially global warming gases) are increasing, a lot of researches are focusing on new technologies which can cut greenhouse gas emissions [1]. New technologies have been developed, such as high Mild combustion, flameless combustion and Integrated Gasification Combined Cycle (IGCC) technology. Oxy-fuel combustion using carbon dioxide as dilution of oxygen is considered as a promising approach for reducing CO2 emission. The properties of CO2 in flue gas are different from N2 in air. On one side, the transport, thermal and radiative properties of CO2 are different from N2 in air. On the other side, CO2 is not inert but directly participates in chemical reactions and recent researches [2-5] also present the chemical effects of CO2 on oxy-combustion. For these differences above, the characteristics of oxy-combustion are not alike with traditional combustion. It is necessary to develop the investigation of oxy-combustion.In all combustion processes, laminar flame speed is an important parameter, which links to combustion behavior. Analysis of this parameter can provide a better understanding of the effect of CO2 dilution in the process of oxy-combustion. Several investigations of laminar flame speeds of oxy-fuel flame have been improved, including experimental measurements and numerical computations. A.A.Konnov et al. measured the flame speeds of oxy-methane and oxy-ethane mixture using the heat flux method with a flat burner [6-8]. V. Ratna Kishore et al. used heat flux method to measure the adiabatic laminar flame speeds of hydrogen [9] and H2/CO mixture [10]. Adiabatic laminar flame speeds of hydrogen in O2/CO2 atmosphere are much smaller than in O2/N2 or in O2/Ar. The burning velocity of H2/CO mixture decreased with increase in CO2 content in mixture. Jeongseog Oh et al. [11] used Bunsen flame to measure the laminar flame speeds of premixed oxy-methane mixture with angle methods in atmospheric condition (300k, 1atm). The results were SL=29.1cm/s and SL=29.5cm/s respectively derived from oxy-methane from CH* images and Schlieren photos."

Jan 1, 2014

By Quinlan M. J, Ratcliffe J. S

Chemical kinetics is a dependent process which usually correlates the rate at which a reaction proceeds with the mechanism descriptive of the manner by which reactive particles interact. Given the latter, the object gen- erally is to find the reaction rate dependency in terms of an intensive property of the system - number of reactive particles present, and of the energetics of the system - usually temperature. Chemical kinetics depend on a dem- onstration that reaction considerations alone control the phenomenological process under study. For these rea- sons, chemical kinetics are usually involved in homogeneous gaseous systems. Even in liquid homogeneous sys- tems earliness or lateness of reactant mixing rather than chemical kinetics may be controlling. Considerations of transport phenomena are involved in heterogeneous systems and often control the observable rate:an additional problem in such systems is to apportion the rate due to mass transfer - usually a linear process - and that due to reaction which may be linear or non-linear. Experimentally, conditions are often chosen so that only one consideration controls but this becomes more difficult where solid phases are involved. Kinetic modelling involves considerations of chemical kinetics, transport phenomena, and factors attributable to the physical environment in which the process takes place. The latter two considerations may be quite different as between experiment and plant. The kinetic model may be a mathematical representation of a conceptual mech- anistic model of the reaction. Alternatively, it may be an empirical relationship resulting from, for example, some curve fitting procedure applied to experimental data. The latter approach may be necessary where the system is particularly complicated.

Jan 1, 1975

By Jafar Safarian

A new kinetic modelling technique has been applied to study the rate of MnO reduction from slags by dissolved carbon in liquid iron. Based on a consideration of the fundamental reaction kinetics, a general differential equation for the slag reduction process has been formulated, which then is solved analytically for certain special cases. By re-writing the solutions in a dimensionless form the poorly known kinetic constants are eliminated, which makes the model both flexible and applicable to a wide range of experimental conditions. For example, changes in process parameters such as temperature, metal composition, slag composition, gas composition can readily be captured along with variations in the crucible geometry. Based on a comparison with a series of experimental reduction curves being reported in the literature, it is concluded that the predictive power of the model is surprisingly good, yielding outputs that are both reliable and physically reasonable. An attractive feature of the model is that it provides an alternative way of calculating the activation energies from experimental reductions curves. For example, it suggests that the activation energy for the reduction of MnO by dissolved carbon in liquid iron is about 90 kJ/mol, which is different from the previously reported activation energies. The model also suggests that the crucible geometry, which affects both slag the volume and the resulting slag/metal interfacial area, has a significant influence on the overall reduction kinetics. This design parameter is a key to further optimisation of the process on an industrial scale.

Jan 1, 2006

By Alexandre Bonan

The paper reports on the results of a kinetic study on the oxidation reaction of aqueous free cyanide ions with H202, in the presence of Cu(2+) catalyst. The variables and respective ranges studied were the following: (CN) ° = 10 -100 mg/l pH = 10 -11 (H202/CN) mol ratio = 1 -3 (Cu/CN) mol ratio = 0 -0.25 The results lead to the development of a semi-empirical model whish incorporates both the useful oxidation reaction and the parallel alkaline decomposition of H202.

Jan 1, 1992

By Zengjie Wang

Kinetic study of hydrochloric acid leaching of Panzhihua ilmenite from China is presented. Both temperature and concentration of hydrochloric acid have significant effects on the rate process of Fe dissolution from ilmenite ore, while the ratio of liquid to solid has little effect on the Fe dissolution. The Fe dissolution is found to follow the spherical model f (??) =1-(1- ??)1/3 and the apparent activation energy is calculated as 47.21 KJ/mol, suggesting a chemical reaction controlled mechanism. The dissolving behaviors vary at different kinetic stages. At the beginning the amount of the dissolved Fe and Ti increased monotonically with leaching time, while about 15 minutes later the dissolved Ti in the form of TiOCl2 began hydrolyzed into TiO2 fines reunited on the ilmenite ore surface, as observed by SEM and EDS technique. For the unreacted ilmenite particles covered by a layer of hydrolyzed TiO2, the leaching seemed to be as a selective leaching of iron and because Ti dissolved from and hydrolyzed rapidly again into the unreacted ilmenite particles. The leaching process can be ended 4 hour later when almost of Fe has dissolved into the solution and TiO2 remains as solid residues. The effects of acid concentration and leaching temperature were also investigated.

Jan 1, 2009

By Du Sichen, S. Seetharaman, J. A. Bustnes

"The present study deals with the kinetic studies of reduction of some selected transition metal tungstates with hydrogen. The measurements were carried out by the isothermal thermogravimetric method. Shallow powder beds were employed in order to avoid the effects due to transport phenomena affecting the reaction rate. In this way, the chemical reaction rates could be selectively studied. The experiments were carried out in the temperature range 873 - 1173 K. From the experimental data, the activation energies were evaluated and were found to be around 88 kJ / mol in the case of both iron as well as cobalt tungstates indicating the similarities in W-O bonds in both cases. The activation energies obtained are discussed in the light of the position of the transition metal in the periodic table as well as the thermodynamic stabilities of the various tungstates.IntroductionThe tungsten containing hard metals, characterized by high density, belong to a class of two-phase metal matrix composites. While these types of materials have traditionally found their applications within the defence industry as armour-piercing projectiles, counterbalance in helicopters and military aircrafts, outer casings of hand-grenades, etc., commercial applications for this class of alloys also exist, including radiation shields, penetrators for the oil industry, turbines for turbo-jet engines and a wide range of sports related parts. A possible route to the production of these alloys is to reduce the tungstates such as FeW04, Co W04 and NiW04 using a reductant like hydrogen or carbon monoxide. In order to have a better understanding of the processes involved in the production, it is important to have a knowledge of the reduction kinetics for these tungstates. According to the knowledge of the present authors, while the reduction ofNiW04 by hydrogen gas has been investigated earlier in the present laboratorypl no systematic reduction study has been carried out previously for the tungstates of iron, cobalt."

Jan 1, 1996

By G. A. Irons, D. Guo, D. Angheiina

To produce low-carbon (<30 ppm) steel in the tank degassing process, a ladle of steel with an oxidizing slag is placed in a vacuum tank equipped with bottom bubbling. The kinetics of this process are slow compared to the more prevalent RH degassing process, providing the impetus for the present work. There are several aspects to this work: water models of the fluid flow in the ladle; simulation of the decarburization (CO evolution) with C02 desorption in water; pilot-plant (60 kg) studies of the decarburization kinetics; mathematical modelling of the fluid flow in the ladle; mathematical models for each of the kinetic sites (plume, top slag and auto-nucleation); and full-scale trials. The results show that during the refining cycle the contribution from each reaction site changes, suggesting avenues for reducing cycling time and final carbon contents.

Jan 1, 2000

By J. A. Bustnes

The present work deals with kinetic studies of the reduction of molybdenum- and tungsten oxides by hydrogen. The experimental method used was therrnogravimetry under isothermal as well as non-isothermal conditions. The non-isothermal kinetics in the case of the reduction of MOO, to Moo2 has been modeled considering surface reaction as rate- controlling. In the case of the reduction of W02 to W a model was developed on the basis of the movement of the reaction front. The activation energies calculated on the basis of the models were in good agreement with those derived from isothermal experiments.

Jan 1, 1994

By Filippos Patsiogiannis

Laboratory size (4.5 kg) low carbon steel melts were deoxidized using Al and FeAl (33% Al), with and without synthetic fluxes, in alumina and zirconia crucibles. The dissolved oxygen, total oxygen, soluble aluminum, insoluble aluminum, silicon and carbon contents in the melt were determined as a function of refining time and temperature. It was observed that the reaction between aluminum and oxygen in solution closely follows thermodynamic equilibrium. Silica present in the alumina crucibles was found to be a source of oxygen for the melt, while this was not the case for zirconia crucibles. Reoxidation of the melt occurred through oxygen pick-up from the atmosphere. The extent of this reoxidation was found to be a function of oxygen content of the bath and the slag cover on the surface of the melt. The effectiveness of calcium-aluminate based fluxes in protecting the melt from the reoxidation and in increasing the rate of removal of inclusions was evaluated.

Jan 1, 1992

By Filippos Patsiogiannis

Laboratory size (5 kg) aluminum killed low carbon steel melts were desulfurized with synthetic fluxes in zirconia crucibles. The sulfur, oxygen, aluminum, silicon, and manganese contents in the melt were determined as a function of refining time and temperature. With a good argon shield and synthetic flux cover, melt reoxidation was not observed. Sulfur removal followed first order reaction kinetics. The effectiveness of calcia saturated calcium-aluminate (12CaO.7Al2O3) based fluxes in desulfurizing the steel melts was evaluated. The effects of initial sulfur level of the melt, weight of the flux (slag), and additions of tellurium, fluorspar, and barium oxide to the melt on the kinetics of desulfurization were also studied.

Jan 1, 1993

By B. D. Paphane

Since the commissioning of the Tati Hydrometallurgical Demonstration Plant (HDP), which produces Ni and Cu cathodes as well as Co salt from sulphide concentrate employing Activox® technology for leaching, no kinetic data has been generated from the plant under normal operating conditions, from start-up to steady state. Therefore, this study seeks to determine the rate of reactions in the leaching circuit with a view to obtaining kinetic data for the system under the current operating conditions. Within the five-compartment autoclave operating at temperatures of 105°C to 110°C and 1100 kPa pressure, the extraction of Ni, Cu, and Co ions into solution is achieved through the oxidation of the sulphide concentrate using approximately 50 kg H2SO4 per ton, 10 kg NaCl per ton, and 1.21 kg O2 per kilogram of S2-. The autoclave reactions showed complex kinetics, with the reactions proceeding via some intermediate(s) before the formation of products. The results suggest that the reactions were dependent on the size of the metal ion of interest and the concentrations of the metal ions in the Tati concentrate as well as in chloride leaching. The order of the leaching rate constants was Fe2+ > Cu2+ > Ni2+ > Co2+ in all the compartments studied. The rates of leaching were also found to decrease as the concentrate moves from compartment 1 to compartment 4. For compartments 1 to 3, leaching was observed to be preceded by dilution of the repulp liquor (copper raffinate). The leaching rate for compartment 5 was slightly lower than that of compartment 1 but higher than the rates of compartments 2, 3, and 4 for all the metals studied. Keywords kinetics, hydrometallurgical plant, Activox

Jun 1, 2013

By José Roberto de Oliveira

Based on literature review one can see that the main objectives of MnO reduction is the comprehension of slag interactions and reactions with other elements beyond carbon. That&apos;s because it is worthwhile to study pure MnO reduction, where there will be not oxides interaction and just carbon will be the reduction agent. By a thermodynamic analysis we know that Si can react with MnO, then it&apos;s important to study this influence, so as Mn content. Our work aims to develop kinetics parameters for the MnO reduction, varying Mn and Si contents in bath. This has been given by pressure measure of CO in a Fe-C bath. The CO is generated by the oxide reduction with carbon. It has been proved that: - Mn content decreases the MnO reduction; - the MnO reduction is mainly influenced by Si content in a bath containing Iron, Carbon and Manganese so as Silicium

Jan 1, 1997

By Jorge Alberto Soares Tenório, Viviane Tavares de Moraes, Denise Crocce Romano Espinosa, Franco Alves Lavacchini Ramunno

"The traditional process for recovery of metals from waste electric and electronic equipment (WEEE) usually involves pyrometallurgical processing. However, the application of this technology to processing waste printed circuit boards (WPCBs) might lead to the formation of dioxins and furans, due to thermal degradation of flame-retardants and polymeric resins present in the board substrate. Therefore, this paper proposes a hydrometallurgical route for the recovery of copper. The acid leaching behavior of copper has been investigated at three different temperatures (25°C, 50°C and 75°C) with and without the addition of an oxidizing agent (hydrogen peroxide - H202). The dissolution kinetics for acid copper leaching was calculated based on chemical analysis by ICP-OES (Inductively Coupled Plasma - Optical Emission Spectroscopy). At 50°C with 1 mol/L H2S04 added 10 mL H202 (30%) each half hour under pulp density of 1 g I 10 mL, 100% of copper was extracted after 3 hours. The dissolution kinetics of copper with H2SO4-H2O 2 followed 1 - (1 - X)113 =Ket, i.e. chemically controlled reaction model.IntroductionThe information regarding the generation of waste electric and electronic equipment (WEEE) are still difficult to obtain because the estimates should take into consideration the historical production and sale of various products and the rate at which they reach the end of their life cycle, whose duration depends on the behavior of consumers [1]. Thus, the estimated overall WEEE generation varies between 25 and 50 million tons each year, which corresponds to more than 5% of all municipal waste generated [2], and this amount will increase at a rate of 3 to 5% per year, approximately three times faster than other individual types of waste [3].Printed circuit boards (PCBs) are essential parts of electric and electronic equipment (EEE), being found in virtually all electronic products, as well as in weapons systems [4]. A PCB is a basic component, which consists of a board where copper tracks are deposited. While the board behaves as an electrical insulator, the tracks connect electrically the various components attached to the board [ 5]. In addition to glass fibers, paper and resins, the PCBs contain significant amounts of metals, such as copper, iron, nickel, lead, stain, silver, gold and palladium [6]. In general, the weight fraction of metal is around 28% and the remainder of the boards is composed of plastic (19%), bromine (as flame retardant - 4%) and ceramic material (49%) [7]."

Jan 1, 2014

By Baozhong Zhao

Laboratory experiments have been conducted on the removal of As, Sb and Bi from molten copper by SF 6 injection. The results showed that the impurities can be removed by SF6 injection in the? sequence of Sb >As >,Bi and the rate of Bi removal is affected significantly by the concentration levels of As and Sb in the copper melt. Analysis of the experimental data indicates that the impurity removal process is under chemical reaction control rather than by mass transfer of impurity through the molten copper phase. On the basis of experimental results, a kinetic model was developed and the order of chemical reaction and the volumetric chemical reaction rate coefficients of impurity removal were determined.

Jan 1, 1996

By A. Ballester, F. Gonzalez, M. L. Blázquez

Pyrometallurgical process are usually used to recover valuable metals from metal sulphide concentrates. However, their use is diminishing as the cost of energy rises and pollution controls become strictes. An alternative method of treatment sulphides could be bacterial leaching due its simplicity and negligible contamination (1-2). This process is presently used commercially to re cover metals such as Cu and U from low grade ore concentrates. In spite of numerous researchs during recent years (3-5) there exists very little kinetic data concerning the speed of bioleaching process. The kinetic analysis of bacterial activity is related with the metabolism and growth of microox ganisms . This fundamental information permits ma- king the best utilization of bacterial oxidation and to suggest techniques which might increase the production of the products desired. However, bio- kinetic models are especially complicated due to the existence of many metabolic routes and parallel reactions which are important for the life of the bacteria. Microbiological oxidation of a mineral substrate is influenced by its own inicial concentration: This influence can be determined by means of a kinetic study. In a medium with sufficient concentration of nutrients (nitrogen, phosphorous and potassium) and an adequate supply of 0, and CO2, as the only & L source of carbon for the biochemical synthesis, the substrate concentration would remain the only limitation in the rate of leaching. In this case the Michaelis-Menten model could be applied (6). The model is based on an association of the enzyme (El with the substrate (S) with consequent decomposition of the latter into enzyme and products [ ] The rate of dissolution is defined by the equation : [ ] Were V is the rate of metal extraction (mg 1-1 1 h-1 ) ; S is the pulp density Mn is the maximum rate for metal extraction (mg 1-1 h-1) and K is the constant of Michaelis (concentration of substrate that yields Vm/2). This method is applicable only when the rate of bacterial growth is similar to the rate of metal extraction. It would therefore be sufficient to control the concentration of metal in the medium over the period of time. In the present work a systematic study of the kinetics of ZnS and CuFeS bioleaching in sphalerite and complex ore concengrates was carried out. The rate of dissolution of the Zn and Cu as function of the pulp density and temperature was determined. However, most oxidations of sulphide dissolution take place with a very slow kinetic; but, this can be accelerated considerably by the addition to the solution of suitable catalytic ions, as was Suggested many years ago by Bjorling (7). Such ions can exercise an important influence on the rate of the oxidation-reduction reactions, both homogenous and heterogenous, which take place during the leaching of sulphides; they also affect the nature of the reaction products. The action of catalytic ions has been fully developed in aqueous systems, but in the absence of bacteria (8 - 11) although the actual machanisms is not totally known. The mechanisms proposed as hypotheses in the literature (8) indicate that, in the case of ZnS, the catalyst ion act through an electrochemical mechanism according to the reactions: [ ]

Jan 1, 1989

By Mamookho Elizabeth Makhatha, Mbal Henock‑Michel Mwanat, Kubangala Brest Kasongo, Ntumba Edward Malenga

This study investigated the operating parameters that affect the kinetic dissolution of copper and cobalt from sulfidic ores. The sulfuric acid concentration, temperature, sodium chloride concentration, particle size range, and leaching time were selected to deduce the kinetic mechanism of the leaching reaction. Other parameters, such as a stirring speed of 250 rpm and the percentage solid 10% w/v, remained constant. The results reveal that an increase in acid concentration enhances the leaching rate of copper and cobalt. Copper and cobalt dissolution was positively affected by the addition of sodium chloride. The highest leaching rates of copper and cobalt were 24.71% and 15.65%, respectively. The chemical control and diffusion control by shrinking core models are well fitted as the kinetic models representing the dissolution of the minerals. The respective activation energies for copper and cobalt dissolution of 10.92 and 31.023 kJ mol− 1 for the chemical control and 18.83 and 37.28 kJ mol− 1 for diffusion reaction control were established from temperature-based experiments.

Aug 26, 2022

By Inkap Choi

Asbestos is a broad term embracing a number of fibrous silicate minerals. These minerals look extremely fragile, yet their fibers have a tensile strength equal to that of piano wire. Chrysotile asbestos is the only mineral that can be woven into cloth, and its fibrous structure is, if anything, even more amazing than its remarkable ability to withstand heat. Because of its unique physical properties asbestos has achieved great industrial importance, and more than 3,000 current uses are known, ranging from use in the kitchen to use in space missiles. Because their minuscule fibers are eminently respirable, asbestos minerals have also found their way into the lungs of humans, where they apparently produce serious biological effects such as asbestosis and lung cancers. 1, 2,3 Because of both their usefulness and their hazardous properties, these minerals have attracted a good deal of attention from research workers during recent years. For example, the surface properties of asbestos minerals have been studied by many investigators. 4, 5, 6, 7, 8, 9 However, even for the important mineral chrysotile, the literature data are more or less conflicting. Pundsack4 measured a PZC (point of zero charge) of 10.1; Martinez and Zucker5 measured 11.8; Chwastiak reports 10.8-11.0; and Raddick measured three sepa-rate apparent PZCls at about pH 8.3, 10.0 and 10.9. More recently Trivedi8 reports 10.11. Naumann and Dresher9 have studied surface charge enhancement of chrysotile by metal ions, and describe how the mineral reacts with contaminantions. In the present paper, the mode of dissolution of magnesium and hydroxyl ion from asbestos minerals placed in water was studied by kinetic experiments involving rate at which these items leave the minerals. Also, some study was made of interaction between dissolved species.

Jan 1, 1972

By Dewa Putu Agus Sudarmaja, Widi Astuti, Januarti Jaya Eka Putri, Yayat Iman Supriyatna, Himawan Tri Bayu Murti Petrus, Siti Nurul Aisyiyah Jenie, Ferian Anggara, Anisa Maulidia, Vincent Sutresno Hadi Sujoto, Sutijan, Wayan Warmada

With the rapid development of renewable energy technology, such as electricity reserves to store energy for electric and battery-electric vehicles, environmentally friendly energy sources are expected to continue to be tapped to meet mobility and stationary energy needs. Lithium is the most attractive candidate for energy storage development. The presence of lithium in the Sidoarjo mud in Indonesia makes it interesting for use as an alternative source of raw material. In this research work, sulfuric acid was used as a solvent, and hydrogen peroxide as an oxidation agent. Lithium recovery was studied with a leaching process at various temperatures (30, 45 and 60 °C) and sulfuric acid concentrations (0.5, 1, 2, 3, 4 and 6 mol/L). Increases in temperature, sulfuric acid concentration and hydrogen peroxide concentration were found to directly affect the lithium recovery. An increase in sulfuric acid concentration is directly proportional to the recovery of lithium in the solution. Optimum conditions were obtained at a sulfuric acid concentration of 6 mol/L and temperature of 60 °C. The shrinking core model was used to study leaching kinetics, and ash layer diffusion acted as a rate-controlling process. The activation energy of the leaching process was found to be 38.90 kJ/mol.

Jun 1, 2024

By Dewa Putu Agus Sudarmaja, Widi Astuti, Januarti Jaya Eka Putri, Yayat Iman Supriyatna, Himawan Tri Bayu Murti Petrus, I Wayan Warmada, Siti Nurul Aisyiyah Jenie, Ferian Anggara, Anisa Maulidia, Vincent Sutresno Hadi Sujoto, Sutijan

With the rapid development of renewable energy technology, such as electricity reserves, to store energy for electric or electric vehicles, environmentally friendly energy sources are expected to continue to be fulfilled according to mobility and stationary energy needs. Lithium is the most attractive candidate for energy storage development. The presence of lithium in Indonesia in the Sidoarjo mud content is interesting to be used as an alternative source of raw materials. During the research, sulfuric acid acted as a solvent, and hydrogen peroxide acted as an oxidation agent. Lithium recovery will be studied using a leaching process at various temperatures (30, 45, and 60 °C) and sulfuric acid concentrations (0.5, 1, 2, 3, 4, and 6 mol/L). The increasing temperature, sulfuric acid concentration, and hydrogen peroxide concentration will directly affect the lithium recovery. An increase in sulfuric acid concentration will be directly proportional to the recovery of lithium in the solution. Optimum conditions were obtained at varying 6 mol/L sulfuric acid concentrations and 60 °C temperature variations. The shrinking core model (SCM) studied leaching kinetics, and ash layer diffusion acted as a rate-controlling process. The activation energy of the leaching process was obtained at 38.90 kJ/mol.

Jul 25, 2023

By R. Baker

A novel electrochemical half-cell and corresponding working electrode were designed to evaluate the electro-catalytic activities of catalysts in an environment close to that of an operating proton exchange or polymer electrolyte fuel cell (PEMFC). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques were employed using the novel cell to characterize various methanol electro-oxidation parameters that contribute to the overall reaction on a fuel cell anode. The effect of temperature on methanol oxidation kinetics was examined in the potential range of 0.31 to 0.65V (vs. NHE). The data was collected in the temperature range of 20 to 80°C. Based on the experimental analysis and literature data, an equivalent circuit model (ECM) for methanol oxidation was proposed and was used to fit the EIS experimental data. The experimental data and ECM electrochemical data was used to extract electrochemical kinetic parameters for methanol oxidation such as the exchange current density, Tafel slope, and energy of activation for the reaction. Kinetic data, especially at different temperatures, is very limited in the literature.

Jan 1, 2005